Praktikum organske hemije [Reprint 2022 ed.] 9783112676684, 9783112676677

Citation preview

n.

T A T E P M A H

nPAKTHKYM

OPTAHCKE XEMHJE nPEPAÄMO X A J H P H X

M3ÄABAMKO

BHJIAHA

nPEfly3E"ñE HAPOÄHE BEOTPAÄ,

1952

PEÍiyBJIMKE

CPBHJE

Hac;iOB

opHrHHS.ua:

L. Oattermann Die Praxis des organischen Chemikers

c HCMiuar: BopHsoje BacTHh, MHpJaua ßHHHTpHejaHfc a A-neKcaH^ap J1«k® ripe»ej)K

PeaaKTop: 'Bop^e ^HHHTpHejBHh

TwpaJK 3000 npuMepaica UiTiMnapHaj u KH>nroBe3HHua .Haymta KH.Hr«*, Beorpan, KocwajcK* jji. 2t

nPEflroBOP nPEPAlaEHOM H3AAH>y D ílpe neuiUio Butue oj.j üipunecem roauna JlyflBur raMepMüH nao je y uiUiaMüy üpBO U3nan>e meroBor yüyüicwBa 3a opranaco-xeMUcm üpatcmuKyM. CucüieM, na ce y3 üpeüapaüiuBHe üpoüuce najy u üeopucm oójauiwewa, üo* naaao ce 6e3 cyMwe nao noóap. 3a obo roBopu Beh Bejiuica pacüpocwpaweHOcHi «mure; ona je noycuaejia ocajunaecüi U3nawa. — M3ynaBan>e Memomme mexHutte 3ai¡ejio je rjiaBna CBpxa oprancxor üpaKmmyMa; Boljen icao iticüla KyBüpota BeiuüluHa u JiaÓopaHwctca yBeotcÓaHOcüi oh 6u nao cyBume müjio. CaBJtanaüiu Memonutcy 3hühu Upe caerá u paayMemu weny üpuMeny, yüoüipe6uüiu ttene MHorocwpyite u3payca¡He oójime na UpaBOM Atecüiy. Ty u jecüle cyuimuna Bpu üpaBJbetty cyücüiaHifu. Mu 3axweBaM0, na üpaKUiuKaHW ¡üeopucm cxBaüiu üpoMene, aoje ce neuiaBajy, nana panu üpeüapaüie. KoMenMap Malü ya üojenune üpeüapaüie wpeóa na ojiaKuia üperjien oÓJiacmu aoja ce yüpaBO o6paijyje u na üomcüiaKHe hü üpoynaBawe yifóenma u opuruname mmepaíüype, na üponyójbUBawe. ílouimo ce Mooice üpemüocülaBumu no je na yHUBep3uvúewuMa cmyneHtü yü03Ha¡ü c ochobümü opranctce xeMuje nana üpucüiyüa üpeuapaüiUBHUM 3anaifUMa, lüo Huje üoclüojajia oüacHoem na KOMenmap 6yne nepa3yMJbUB. HaMepno cy 3axvúeBU üpaKüiuHHe u üieopuace empane üOBehaHU y obo¡ H0B0j üpepanu. LLlUio je y üpouieKJiux üipunecem ronuna óujio nOBOJbHO nao „wkojicku üocao" mo je can cyBuuie müjio 3a onor, ko¡u xohe na panu na pemaBawy 3anaUiaKa, Koju cy u y Haytfu u y mexHuifu üocüiajiu ouimpuju u weocu. Mucao, na üpeüapaiüuBHU üpaKmmyM üocjiyoicu ucmOBpeMeHO 3a o6yxBaffiawe u yoicuBJbaBawe y opranctcy xeMujy, saxüieBajia je na ce Maüiepujaji pacüopenu ca manee rjienuuiwa cucüieMaüiuKe. Bunehe ce na üio nuje uojie oaóujbHuje yUiuifajio na üpeüapaMuBny Jiunujy ycüOHa on Jiatcmer Ka meaceM. A Kopucui Koja ce umü otemBaüiu on obokbot 3aonpyrjbenor üporpajna 3HaüiHa je. Oüuiüiu neo, a uciüo ulano u aHamniuHKU üolüüyHO cy üpepatyenu u cupahenu y üpujior üpeüapaüla. ÑOBehawe 6poja obux 3axU¡eBüJio je tiene üpoMene y cxeMaüiCKOM wony opranaior üpaitüiuKyMa. pa¡6ypr y B. 1925.

V MeBeuiHaecmo U3aan>e opurimcuinor Aejia.

XajHpHX BHJiaux

C

A .

a

H e K o j i H K o

a

P

>K a

o n u i T H X

j

n p a B H j i a

s a

p a ^ CTpaM»

5p3HHa

peaKUHje

h

TeMnepaxypa

1

ÄOÖHjatbe opraHCKHx cyncTaHUH y e

Cymeite

.

.

KpncTajia

8

cyncTaHUH

11

XponaTorpaij)CKa aTcopnuHja

-

-

-,

-

-

-

-

ÄecTHJiauHja AecTHjiaUHja

aTMOc^epcKHM

-

-

-

iiphthckom

-

-

-

14

-

-

-

-

14

aecTH^auHja

ßecTHJiauHja

y

16

BaKyyMy

17

PeumiHjeHTH

19

Cy6flHMHcaH>e

22

AecTHJioBaH>e

napoiu

23

aecTHJiaunjou

25'

-

28

AnapaTH 3a eKCTpaKUHjy

29

yoaftaibe

ca

boachom

pacTBapa^a

EKCTpaxoBaite

27

C y m e a e pacTBopa Paß

ca

12 13

oa

n

H3Bopn TonjioTe ^paKUHOHa

7

KOMnpHHOBaHHM

3arpeBatt>e Meuiafte

noA

h

racoBHMa

iiphthckom

-

30 -

-

-

-

-

-

-

-

32

MyhKaH>e

Oape^HBaite

TaiKe

B .

33

Tonjbeita

-

M e T o ^ e

e j i e i w e H T a p H e

KBa^HTaTHBHO ÄOKa3HBan>e yrjbeHHKa,

-

a H a ^ H s e

BOÄOHHKa, a30Ta cyinnopa h xa-

•noreHa KBaHTHTaiHBHa

34

36 opraHCKa

ejieMemapHa

aHajiH3a

39

I. Oapel)HBaH.e a30Ta no D u m a s - y II. O ^ p e ^ H B a t t e

yrjbeHHKa

h

BöAOHHKa

III. Oapel}HBaHje xaaoreHa, cyMnopa h

40 no JlnöHry

flpyrnx

46

ejieMeHaîa

IV. OapeljHBafte opraHCKHx r p y n a

B .

O p r a H C K o - n p e n a p a T H B H H

-

-

58 67

fteo

3auiTHTa «poTHB HecpeTHHx c^yqajeBa

74

ripBa

75

onpeMa

VI

CaapiKàj

I. C y n c T H T y i ^ H j a x h r p o k c h j i b h b o ^ o h h k s Ajikoxojih h

xajioreHOH

ojiccJihhh CTpajta

1. ETHflôpoMUA H3 etHJiaJiKoxoaa

78

2 . ETHAJOÄHÄ H3 eTHflaflKOxo^a

-

80

3 . 5eH3HjixjiûpHA H3 Tcwiyoaa

84

4. Ep0M6eH30A

87

5. He3acHheHH yrjbOBOjioHHUH

91

6 . naHKOJi (eTHJieHrjiHKCwi) H3 e T H f l e u ö p o M H M 7 . H3oaMHJieTap

'

-

-

-

-

97

_

99

8. X j i o p c H p h e r a a KHcejiHHa h3 C H p h e m e k h c c j i h h c h x j i o p a -

II.

Kap6oHCKe

KHceJiawe h h > h x o b h

npocTH

-

100

-

106

RepaBaTH

1. XjIOpHAH KHCejIHHa

,

2. A h x h a p h a c n p h e T H e KHce-iiHHe 3 . AueTaMHÄ

-

-

•

-

•

-

102

-

108

4 . KapßaMHÄ h ccMHKapôaMHA

110

5. H h t p h j i h

-

-

-

114

6 . CanoHHijMKauHja h h t p h j i b y K H c e j i m i y . eHHJicHpheTHa KHcejiHHa

-

7 . E c t p j i KHce^HHa

116 117

8. Ä e r p a i i a i i H j a KapöoHCKHX KHcejiHHa ä o n p B o r H a y h e r

HiiiKer aMHHa -

125

I I I . H H T p o j e A H H > e H > a H H>HXOBH p e ^ y K i ^ H O H H n p o f f y K T H 1. HHTpoMeiaH

129

2 . H H T p o B a f b e apoMaTHHHor 3. P e a y K U H j a

yrjbOBOjxoHHKa

133

HHTpo-jeaHHieH>a y a u m i

135

4. 4>eHHJIXHÄpOKCHJiaMHH 5 . HHTpo3o6eH3cwi 6.

-

142 -

-

146

XHapa306eH30fl H a3o6eH3o;i

149

I V . CyJnJ»OHCKe

KHcejiHHe

1. BeH30JiMOHOcyjiEKBE

YBOA

213

A.

AjiHijiaicKa

HHAÎOJEJHIHCUA

1. ÜH330MeTaH

214

2 . ÄHa30CHpheiHH e c ï a p

218

B.

A p o M a T C K a

Ä H A 3 0 - J E A M B E H > A

3. /tHa30T0BaH>e aHHJiHHa. eHOJi, jofl6eH30Ji, 6eH30Ji h3 amuiHHa. MepHja ÄHa3o-jeÄHH>eH>a

H30-

-

223

4. P-TOJIYHHTPHJI H3 P-TO^YHÄHHA ( S a n d m e y e r - o B a p e a n u n j a )

-

-

231

5 . ApcaHHjjHa KucejiHHa H3 p-HmpaiiHJiHHa

-

-

-

233

-

-

-

235

-

-

'

-

6 . EHH^XHFLPA3HH

235

7. Zlo6HjaH>e a 3 0 - 6 0 j a VIII. 1.

XHHOH

XHHO^HS

je^HiteFba

H3 AHHAHHA

245

2. riapa-HHTp030-ÄHMeTHfl-aHHflHH

-

249

G. riapa-a>ÄHHO-iiHMCTHJiaiiH/iHH

251

4. Ba3He TpH(j)6HHJiMeTaHCKe 6oje 5. 4"^oypecueHH H eo3HH 6.

-

A^H3APIIH

OpraacKH RPNH>APOBA 1. Äo6HjaH>e CHHTE3A

H pHRe;I-Kpafl)Tcy.

pa^HKaJiH peaKuHja

a^Koxoaa

KETOHA

-

H3 H H T P H A A . AUE-ROIFEHOH

pHjieji-Kpa(j)TCOBa 3 . CHHTe3a KeTOHa

-

.

.

.

.

268

272

5 . 2,4-ÄHOKCH-aueTOeH.HMa boaohhkom 3. OKCHÄauHja ecTpa MajioHCKe khccjihhc y ecTap Me30KcajiHe KHcennHe ceJieHÄHOKCHÄOM 4. AAHnHH-ÄHaMexHÄ H3 UHK^IOXCKCCHH o30HH30BaH>eM -

300 ^04 305 305

XII. n p H p o R H e HaTepHje 1. $yp$ypo^ • 2-, d-rayK03a H3 TpiimaHor rnehepa 3. Pa3JiaraH>e TpiuiaHor rnehepa noa yrmiajeM caxapa3e (HHBepiHHa) 4. ß-neHTaueTHJi-r^yK03a H a-aueT0-6p0MrayK03a 5. MfleHHH rnehep h Ka3enH H3 MJieita 6. d-raJiaKT03a h3 MJienHor rnehepa. Cny3Ha KHcejiHHa. riHpoji 7. OKTaueTHJi-ue;i06H03a H ueji0ÖH03a 8. CaxapH({)HKauHja cupoôa h aaKoxo^Ho Bpeae 9. 1 ( + ) — AprHHHH-XJIOpXH/ipaT H3 »ce;iaTHHa 10. KoiJieHH H3 qaja 11. HHKOTHH H3 AyBaHCKor eKcipaKTa 12. XeMHH H3 rosele KpBH 13. FjiaBHH cacTojuH roBetje ncyiH

306 308 308 310 311 312 313 318 320 321 322 323 327

T. O p r a H C K a aHajiHsa rpyna I. OnuiTH Äeo II. KapaKTepHCTHKe nojeaHHHx rpyna

332 332

I I I . M3Bol)eH.e a H a ^ H 3 e

KpaiKO ynyTCTBO 3a Kopmuheibe opraHCKO-xeMHCKe Jimepaiype •JlmepaTypHH npenapam Ta6jiHua 3a H3pa e : M H o r e peananje Koje TeKy y3 jaKO TonaoTe Mopajy Aa ce yMepe. H npH A o ö n j a i b y pacnaAajy,

H 3a Koje je noBHiueHa

öpnHyTH o xjia^eity peaKijHOHe

cyncTaHRH Koje ce jiaKO

TeMnepaTypa

cMeme.

pa3BHjara>e

onacHa, M o p a ce q e c r o

Crene«

x^A^es.a je P33JIHHHT H

nocTHHce ce c oö3HpoM na KOJiHiHHy TonaoTe Kojy Tpeöa ocTpaHHTH H y 33BHCHOCTH O A N O T P E 6 H E TeMnepaType peaKunje TeKyhoM (8—12°), CHTHO

BOAOM

M6III3BHHOM Q Bp cTo r TeiHH

Jieaa

CRYUAHHM

KyXHÜCKe

H

YRJBEHAHOKCHAA

Ba3Ayx

JIEJIOM

COJIH

ca e T p O M

^CCMCHCKOM

HAKBAIUEHHM ca M A ^ O ( 0 A O -20°) H

H;IH a i j e T O H O M

ce npn opraHCKonpenapaTHBHHM

BOAE,

MeuiaBHHOM ( A O -80°).

paAOBHMa yiviaBHOM

He ynoTpeöjbaßa. 3 a npHnpeMaite MemaBHHe 3a xjiaJjeite oHaKBe KaKBa je Hajqeinhe

noTpeÖHa

MeTajiHOM

aBany H A o ö p o

A o ö p o ce H C H T H H JieA H3Meiua

n ö M o h y MJIHH3 3a JieA HJIH y

ca AenaTypHcaHOM

KYXNIBCKOM

CO;IH

n o M o h y jeAne Maae ApßeHe Jionaie, Hajöojbe y H H C K O M CTaKjieHOM qaHKy ca paBHHM

HJIH y

AHOM

HHCKOM

eMajjinpaHOM

jiOHijy.

TOKHHCKH

OAHOC

aeAa H COJIH y CMeuiH 3a X^aJ]ett>e Tpeöa AA 6yAe 3 : 1 . J\& 6 H ce

MemaBHHa

3a xjiatjeibe

npeno Hohn, CT3BH ce OHA y „ T e p M o c ce y H>y cTaBe nepaTypn.

MOHce TaAa Ayace

oApncajia 6ouy";

H30JI3UHJ0M

no Piccard-y,

eßeHTyajiHo H

BpeMe Aa ce OAP®aBa Ha HHCKoj T E M -

Y HCTy c ß p x y 3a Behe Ko^iHHHHe

KAeHa UH^HHApuHHa

caTHMa,

caApwcHHa enpyBeTa Koje

cjiyacn

cyA

ca

AoöpOM

Kojn MO>Ke JiaKO Aa ce HanHHH H3 Aßa CTa-

cyn,a 3a ueljetbe

A e ö e a H x 3haob3 CTaBjbeHa jeAaH y

A p y r n . / I H O cnojbH>er c y A a HcnyHH ce HH(})y30pHCK0M 3eMJbOM TOJIHKO, Aa ce

HBHUA

Maaer

cnoflaH>er cyAa,

ueHTpnqHO

nocTaBJbeHor

33THM ce M e ^ y n p o c T o p

cyAa

3eMJbOM, a r o p e H 3 M E ^ y H B H U A 3AJIHJE A o ö p o OAHOCH

KOHueHTpaunja

H3jeAHaqn

o6a cyAa Haönje

ca

HBHUOM

HHa) paAH ce o peaKunjaMa BHiuer peÄä K O A Kojnx y q e c T B y j y Bwuie — n o u i T O je 6p3HHa ÖHMOJieKy^cKHx

BCIIHHOM Aße —

MOJieKy^CKHX BpcTa.

peaK^Hja Ha 0CH0By KHHe'THMKe MOJie-

3

floöHjaite opraHCKHx cyncTaHUH y IHCTÖM CTaKby

KyjicKe TeopHje NPONOPIIHOHAJIHA 6pojy MC!JVCO6HHX cyAapa MOAeKyjia y pacTBOpy H npeMa TOME H3pa«ceHa npoAyKTOM KOHueHTpaunja: v = CA • C ß • K

(K = KOHCTaHTa 6p3HHe),

ce y C B H M cjiyqajeBHMa, i\n;e HapoHHTH npenopyqyje, A3 ce K O H u e H T p a a n j a H 3 Ö e p e m t o je M o r y h e B e h a . TO

pa3Ji03H He roßope npoTHB, peaxuHOHor pacTBOpa

T p e ö a Y ß E K H M S T H H A Y M Y , A A C M 3 H > H B 3 H > E KOHixeHTpauHje Ha nojioBHHy,

AECETHHY

qeiBpTHHy,

3HAUH

HCTO

IIITO H y c n o p 3 B 3 H > e

peaKunje

3a

neTHpH, uiecnaecT H CTO nyTa. opraHCKHx c y n c T a m m y H H C T O M CTafi>y

floöHjaifce

O H C MaTepnje Koje cy UHjb npenapaTHBHor pa^a BSIIHHOM cy QßPCTA KPHCTAJIK30B3HA

TEJI3

HJIH

TEHHOCTH,

KSTIOA

H

racoBH.

YCJIEA

BEJIHKE

MHoroeTpaHoeTH peaKi^Hja opraHCKHx MaTepnja jeAßa hksr Heica peaKanja Teqe y j e A » O M npaßuy na jeAHOM KpajiteM npoAyKTy, Beh TOTOBO yßeK AO^a3H AO c n o p e j , H H X p e a i c u H j a , IIITO je y H3pa3HToj cynpoTHocTH ca BehnaoM peanunja HeopraHCKe xeMHje. THMe je 3HaTHo 0TE>K3H0

H3OJI0B3H>E

IIITO N P E T C T A ß J B A

HHCTHX

XOMOREHHX

HsjrjiSBHHjH 3 3 A A T A K

CYNCT3HUH

H3

npenapsTHBHHx

peaKUHOHe Bem6H.

CMeme

HENAA

no-

GT3jy jeAHe nopeA Apyrax B H III e Aey. Y c ^ o b 3a y c n e x nocTynKa j e MaTepnje Koje npaTe raaBUH npoAyKT HMajy Behy paeTBopjbHBoeT n e r o JIH caMa c y n e r a H a a , H a a ocTajy p a c T s o p e H e H y 0XJiaijeH0M p a c T B o p y ( m a T H i H o j JiyHCHHH). H y oöpHyTOM cjiynajy Hajia3H npHMeHy npHHunn pa3JiHMHTe pacTBopjbHBOCTH, Harnue OHAa, n a a cnope^HH npoAyKT y a i e A CBoje Maite pacTBopjbHBOCTH y rroaecHOM p a c T B a p a q y Möwe Aa ce h 3 a b o j h h3 TaMaH 3acnheHor pacTBopa cyncTaHae. IIOIIITO öBAe pacTBop ocTaje CTajiHO 3acHheH 3a cnope^HH n p o a y K T TO OBa MeTOAa He MO>Ke, 3a pa3^HKy OA npBe, HHKBA y jeaHoj oneparuijH Aa AOBeAe AO h h c t c cyncTaHue. 3 a npenpHCTajiKcaBaHie H3 Ha Bpejio 3acniieHor pacTBopa j e Aajbe BajKHO A a K p H B a K o j a n p e i c i a B j b a 3 3 B H C H O C T p a c T B o p j b H B O C T H OA T e M n e p a T y p e Teqe IHTO j e Moryhe cTpMHje Tj. Aa ce Moh p a c T B a p a f t a pacTßapana ca nopaeroM TeMnepaType j a n o noßehaBa. CaMO ce TaA Mome nocTHhn Aa ce yHeTa KOJinunHa cyncTaHue H3ABOJ°H H3 paCTBopa ca m T o j e M o r y h e B e h H M n p i i H o c o M . H 3 6 o p npaBor p a c r ß a p a i a j e CTora ' OA ßejiHKor 3Haiaja 3a n p o u e A y p y npeKpHeTa^HeaBafta. PacTBapanw KOJ'h ce HajBHiue y n o T p e ö j b a ß a j y cy cjieAehn: B o A a , e T H i a j i K O x o J i , MeTH.na.flK0X0.Ji, e r a p , a u e T O H , r j i a u . c n p h . KHCCJiHHa, c n p h e T H H e c T a p , 6 e H 3 0 J i , neTpojieTap, x^opo$opM, yrjbeHAncy^(J)HÄ. 3 a HapoMHTO T e u i K O p a c T B o p H e c y n c T a H i x e y n o T p e ö j b a B a j y ce ceM Tora M p a B j b a k h c 6 j i i i h a , n h p H a h H, 6 p o M 6 e H 3 o . f i , HHT p o 6 e H 3 0 J i , KaTKaAa H Ke XHApoKCHJiHe r p y n e (Ha np. m e h e p , Kap6oHCKe KHcejiHHe) pacTBopHe y BOAH, a yrjbOBOAOHHUH c y JiaKiue pacTBopHH y 6eH30^y H n e T p o ^ e T p y Hero JIH Ha np. y ajiKoxojiHMa. AJIH r o p i t e npaBHJio B A ® H yrjiaBHOM ca H3BecH0M c u r y p H o m h y caMO 3a npocTa opraHcna jeAHiteifca; KOA KOMnjiHKOBaHHX cy 3aMpiueHHjH OAHOCH H, ano ce HeMa BCJIHKO HCKyCTBO, M o p a j y ce pacnojio)KHBH pacTBap a n a peAOM Aa ncnHTajy. HajBHiue ce y n o T p e ö j b a ß a a j i K o x o j i ca KOJHM ce no npaBHAy n o i H i t e ; OHAa 6H AOIIIJIH Ha peA OTnpnjiHKe B o A a, 6 e H M o » e ce pehn Aa yraaBHOM OA yoÖHiajeHHx p a * 30JI, n e i p o a e T a p . CTBapaia 6 e H 3 o Ji, x j i o p o j ) o p M h e T a p HMajy B p a o BeAHKy, a n eT p ^ o ^ e T a p H B o A a yMepeHy Moh p a c T B a p ä i t a 3a o p r a H c n e MaTepnje.

AoÔHjaite opraHCKHx cyncTaHUH y IHCTOM cTaay

5

Mano 3a MHore cyncraHue OBaj pea HE Basen, HiiaK OH Äaje H3B6CT3H ocjiOHau 3a HcriHTHBaite. TaKO heMO y3eTH npBy rpyny pacTBapaqa, aKO je npoóa cyBHiiie TeniKo pacTBopua y ajiKOxojiy, a Apyry ano je y H>eMy cyBHiiie JiaKo pacTBopHa. K O Ä T C U I K O pacTBopHHX MaTepnja O Ò H I H O ce 6npa xoMOjior H3 HCTe KJiace ca BHIIIOM TaiKOM KJbyiaiba; Ha MecTO HHHcer ajiKOxoJia y3HMa ce np0nHJia.ziK0X0.fl HJIH A M H J I A J I K O X O J I , HaMecTO 6eH3o^a T o y a o j i HJIH K C H J I O Í , jep ce npn noBHiiieHoj TeMnepaTypH KJbyqaHja noßehaßa H pacTBopjbHBOCT. HecTO ce A E M A ß A && ce IIPHJIHKOM Ä O Ö H J A I I A Hene cyncTaHue Ä0Jia3H Ä O a.Mopy pacTBopjbHBocr, Beh je HJIH cyBHiiie JiaKO H;IH cyBHiue TeuiKO pacTBopHa. PacTBapaqn, Kojn ce Mory 3ajeAHO Aa ynoTpeóe, Mopajy MeljycoÓHO Ä3 6y^y MeuiJbHBH. BehHHOM ce npHMeft>yjy: A^koxo^, iviau. CHph. KHcejiHHa, aiteTOH ca B O A O U — eTap, aueTOH, 6eH30Ji, xjiopocJiopM ca n e i p o j i e T p o M — N H P H F L H H ca B O Ä O M , e T P O M HJIH aJIKOXOJIOM, ce pa^H T A K O , A A ce K O H U E H T P O B A H O M pacTBopy Ha xjiasHO H;IH H A Bpejio AO^aje Kan no Kan cpeACTBo 3a pa3ÓJia>KHBaH>e ÄOK ynpaBO He HacTynH 3 a M y h e H O C T ; crajaiteM u m Tp;baH>eM CTaKJieHHM iuTanwheM ca O H Í T P H M HBHuaMa H333HB3 ce KpHCTa^H3auHja. KaÄ je 3ano*ie./ia KpncTa^H3aiiHja najKJbHBo ce pa3Ó;ia>Kyje ,n,ajbe. norpeuiHO je pacTBopeHy cyncTaHLiy t3jio)khth OÄjeflHOM ^OÄaTKOM BejiHKe KOJiimuHe cpe^cTBa y KOMe ce Majio pacTBapa. H

TO

K O Ä C B H X j p n e p a u H j a K o j H M a ce join H e B JI a Ä a T p e ó a H 3 B e c T H n p e T x o ^ H e o r JI e ä e y e n p y B e T » . H a TO Tpeóa npaKTHK3HT Aa ce Ha-yHH OA caMor noMeTKa. Kao C Y A 3a N P N X B A T A Í T E ({JUJITPATA CJIYXCH K O Ä B O Ä C H H X pacTBopa n e x a p , K O Ä opraHCKHx pacTBapaqa Me^yTHM e p j i e H M a j e p KOJ'H He ÄonyuiTa HcnapaBaft>e H cnpeqaBa T3KO 06pa30BaH>e Kope. ^ a 6H ce xo-

6

HeKOJiHKO onuiTHX npaBHJia 3a

paa

M0reH0CT KpncTajiH33Ta MorJia Aa KOHTpoAHiiie Beh H no CSMOM H3IVIEÄY> HE T p e ö a

PEMETHTH

Moryhe

6ojbe

TOK

KPHCTAJIH3AIJHJE,

ce

CTBOPHJIH

UITO

JE

( j i o p M H p a H H K p n c T a j i H . 3 a 6 ; i y A a j e npeTnocTaBHTH,

Aa y

BehHX

HHAH-

BHÄya. YS TO AOJia3H, Aa ce KÖÄ Jieno 0Öpa30BaHHx KpHCTajia MOMte MHoro •naKiiie yAOBOJbHTH 3axTeßy KOJ'H opraHHiap He cMe Aa nponycTH, a TO je Äa HCNHTA

CYNCTAHUY

6HJIO

JiynoM,

noA

x0M0reH0CT.

HA 6HJIO

noA

noBehaH>e je A0B0JbH0 — He eine Aa c e AKO- je y pacTBOpy

nocTHrHyTO

TO c e KOJIHQAHA KpHCTajiH33Ta

OBO

— 5 0

AO

100-CTpyKO

npeHeöperHe.

3acHheifee Ha coÖHoj

MO®E

npenapaTa

HCNHTHBAFT>e

MHKPOCKOIIOM

jorn

TeainepaTypH

AaJbe Aa noßeha

CTaBJbaiteM

cyAa y JieAeHy BOAy, HJIH y MemaBHHy 3a x;iai)eH>e. CyricTaHiie

Koje

ce

HHCKO

To n e

H3Aßajajy c e npw xjiatjeity

HjHXOBKX Ha Bpejio 3acnheHHx pacTBopa KaTKaA Kao y jb a. TaAa c e pacTBop Mopa joui

HemTO BHine

Aa

pa3ÖJia)KH.

Tpeöa noöpHHyTH, Aa c e xjia^eibe BpuiH

XUjbe c e y TSKBHM cnopo

cjiyqajeBHivia

H Ha Taj HanHH UITO he

öajiOH ca BpejiHM pacTBopoM Aa c e yBHje y Kpny HJIH Aa c e nycTH Aa c e oxjiaAH y BejiHKOM n e x a p y HanyiteHOM BOAOM HCTE TeMnepaType. O A MaTepnja, Koje TCUIKO KpHera;iHmy, Tpeöa 3aAP»aTH yBen jeAHy Ma;iy n p o ö y Koja 6H c e ynoTpe6;baBajia Kao

„KJiHixa

3a

KpHCT3JiH3aiinjy".

FIo-

Mohy oße h e c e noMeHyTa TeuiKoha Jiano Aa caBJiaAa Ha Taj HaqHH, UITO h e KjiHua Aa c e yHece y pacTBop Kojn c e jorn HHje CSCBHM oxjiaAno Tpjbajyhn npn TOMe CTaKjieHHM uiTannheM o 3HAOBe cyAa. H3BO^eite:

6H c e

Ha

npnnpeiviHO

Bpyh

3acnheH

pacTBop,

npe-

jinje c e cyncTaHita Kojy Tpeöa npeiHCTHTH, Hajöojbe y öajiOHy c a KpaTKHM BpaTOM, c a Ma.no pacTBapaqa, 3 a r p e j e a o Kjbyqaita H AOAajy wiajio no Majio HOBe KOJlHHHHe paCTB3p3»J3 AOK Ce CBe He P3CTB0PH. riOUITO CHpOBe cynCT3Hue q e e r o caApace HepacTBopHe npHMece. T p e ö a npn'pacTBapaity TaqHO nocM3Tp3ra, noTnyHo

KaAa H Aa jih c e

pacTBopnjia.

MHore cyncTaHue

cyncraHua

CyBHuie A y r o

jiaKo pa3Jia>Ky.

Kojy

KyB3H>e

Tpeöa

Tpe6a

n p n ynoTpeÖH

pacTBapana

KJbyq3H>a ncnoA 8 0 ° 3arpeBa c e H3 BOACHOM K y n a r a ^ y T p e ö j b y j y h a ycnpaßjbeHH K0HAeH33T0p;

BehHX onepsitfija, Aa c e Ha ÖSJIOH CTSBH jeAaH c^yqajeBHM3 Be»ce c e

H yHoineibe

KOJ'H AonyuiTa HBPCTHX

c a KOCO nocTaBjbeHHM

jep c e

C3 TS^KOM

Koje Kjbyqa y n o -

HOBe KOJIHMHH6 pacTBapana Mory

Aa c e AOAajy Kpo3 KOHAeH3aTOp noMohy JieBKa. (no Anschütz-y) (CA. 2 9 )

npeKpncTa^HcaTH

H36eraB3TH,

Bojbe je, HapoiHTO KOA AßOKpaKH

JISKO AOCHnaite,

cyncT3Hua.

U E B ' Koja je

K0HAeH33T0p0M,

a Kpsj

HacT3BaK

a y H3BecHHM noA

yr^OM

ycnpaBHe ueBH

Kpo3 Kojy c e Aocnna 33TBopH c e njiyTeHHM 3anymaqeM. BoAa

H Apyrn

pscrBapaqH

Haj6ojbe Ha a3ÖecTHoj noÄ.no3H y

KOJ'H Kjbyqajy Ba60B0M

H3HaA 8 0 °

^eBKy

3arpeBajy

ce

HJIH Ha a 3 Ö e c T H o j

üoöHjafte opraHCKHX cynctaHUH y ihctom CTatty A k o j e Tamca Kjbyqaifca

7

3H3tho ( > 2 0 ° ) H3HaA Tanne

Kjby-

naiba BOAe, t o ce Mopa Kpo3 K0H,a,eH3aT0p nponyuiT3TH 3 a r p e j a H a

Bo^a,

MpeacHUH.

noiuTo nocTojH 3 a me h h

onacHOCT

iiinpoKOM

Aa

K0H¿eH3aT0p

h iiyroM

K0HaeH3aT0p)

TpeöH OÓJIOMH

b j i s j k h o m (JjHOTapxapTHjoM. K o a o r ; i e A a

Kaaa

ce

K0HAeH3aT0p

li e b h

(Ba3ÄyuiHH y enpyßeTH

Koja

h j i h ce

npcHe,

cthkjiëhom

npeMa

no-

KOHAeH3aT Tpeöa Bpahara, Hapo^HTo

je noroAaH cneunjajiaH m3jih K0HAeH33T0p npeTCT3BjbeH Ha cn. 2. 15 cm,

Oßaj ce cacTojn h3 eraKJieHe ueBH A y r e

yHyTpaimter

npeqHHKa

6—8

mm,

oko

Koja je

Ha

je^HOM Kpajy 3aTonjbeHa. Ha yAajbeHOCTH o a o k o 3 cm OA A p y r o r Kpaja npanojeHa j e noA npaBHM yrjiOM jeAHa Taita

ueB AyatHHe

3 cm

Koja je caBHjeHa Ha CTpaHy

Ay>Ker Kpana neBH — Aa 6 h ce K0HAeH33T0p Morao o6eCHTH o jeAaH rB03A6HH npcTeH — a Koja o a b o a h BOAy 3a xjial^eibe

npeKO

TaHKor

ryMeHor

upeBa.

BoAa

3a

Ca. 2

xjia^efte a o b o a h ce noMohy jeAHe caBHjeHe TaHKe cra-

h Koja ce Ha OBaj

K^eHe ueBH Koja Aonnpe a o AHa Maaor K0HAeH33T0pa

npHMBpcTH KOMaAHheM ryMeHor upeßa. Oßaj npaKTHiHH K0HAeH3aT0p npHHBpcTH ce Ha enpyBery noMohy 3anymaqa Ha KOMe ce h3ji33h ype3. JXa

6 h ce H 3 ô e r j i o BpJio a o c 3 a h o

Aaje ce npe KOMaAnha KojH

ce

noveno

neqeHe KaA

nperpejaHH

3arpeBaH>a

r^HHe

H30CTajaH>e

hcko^hko

Be./inqHHe noaoBHHe

Koa

jaKHx

yAapa

3a

ao-

KJbyqaifee

—

3pHa rpamKa — y ôa^OH,

npecTaHy A a AejcTByjy 3aMeH>yjy

pacTBop!).

KJbyqaita,

KaMeH«inha

hobhm (He y ô a i i H B a T H y

n p e n o p y q y j y ce n p H

p a A y ca

BehHM KOJiHHHHaMa ApBeHH uiTannhH. R a 6b ce oACTpaHHJie o ô o j e n e npHjaaajy 3a 6e36ojHy

cyncTaHijy,

koj'h je 3acnheH Ha Bpejio ca

HeqncTohe,

Koje qecTO qBpcTO

KyBa ce jom npaTKO BpeMe pacTBop

jkhbothhjCkhm

y r Jb e m hjih ca cneiiH-

ja^HO npenapHcaHHM a p ß e h h m y r Jb e m KojH ce A O A a j y h c k o j i h k o

nyTa

Ha Bpx HO^ca. n o i u T o Ba3Ayx KojH 0An^a3H H3 yrjba n p o y 3 p o K y j e acecTOKO Hanno neHymaH>e H3

BOAeHor

ce

Mopa ce y H o m e a e pacTBopa

HajjiaKiue

bpuihth

naxcJbHBO

aTCopôyjy

ôojeHH

y3 Myhicaite.

npaTHOUH

3Óor

H>HX0B0r KOflOHAa^Hor KapaKrepa. Il,e^eH>e: HH OHAa KaA

PacTBopH h3 koj'hx Tpeóa Aa ce H3AB0je km ce AOAaje

yrajb 3a o6e36ojaßan>e

KpHCTa^H HHcy

noTnyHO

ôhctph h

Mopajy ce 3Ôor Tora u c a h t h . PaAHje Hero jih h a 6 p a h h ^ H J i T a p y3eTH oÓHHaH O K p y r j i H

h ji t a p koj'h ce noTnyHO noACCH y3 CTaKjieHH

aeBaK, Koja BehHHOM HeMa oAroBapajyhw y r a o , nocjieAtteM

caBHjaifcy

Tpeôa

KBaApaHTH

cjioace

noA

Ha Taj HaqaH,

Aa ce npn

m3h>hm yrJiOM h OHAa äa

u e ^ e f t e ynoTpeÓH BehH KynnH OMOTaq. 3a ne^efee Tpeôa Aa ce ynoTpeÓH y oprsHCKO-npenaparaBHOM paAy C3MO J i a K o

nponycTJbHB3

„pan3B3"

xapTHja

3a

ue^eae.

8

HeKOJiHKO onuiTHX npaBH^a 3a paA HecTO

HCKpHCTajiHuie

pacTBopeHa

pacTBopa,

ue^eifae. O ß a

He3r0.ua Moace

jieBaK

KOMe j e

MHoro BOAOM

ce Koja

BOÄOM

CN.

KojHM ce rpeje. r p e j e

TeqHocTH NJIAMEHY

3ana™

T. 3B.

ÄP)KN

TaKoije

(ca.

HaKBacH

CT3BH y

ce

ynoTpeÓH KOHyca.

HCIIOA

jieBKa

ca

jieBKa

4

Cn.

aoöpo

A a ce y n o T p e ö n

yMeTHyra

ropa

ña

Äa ce u e ^ e

Tano ce

H

BPE.no M

3arpeBa

KOA

Ha

njiaMeH

5

H

jieBaK

caMO Majie 3arpeje

HeiiiTO

yr^eHHcaita

Ha

Ko j H

KOJIH^HHC AHPCKTHOM

ajiKOxojia

xapraje,

pacTBopa

BOACHMX

n o p u e j i a H C K O M

ynoTpeöe

eMaj^HpaHH

^A

KJby-

Ka& c e

KOÌH

ce

NPH q e i u y

ce

oKpehe.

nocTaBJbeH

npe

(jiHJiTap c a

ÄO n o i e T K a

Hapo^HTO ce ije^eite

BanyyM Mopa

cnpeiaßa

H

JiHitíeHOM O M O T a q y .

cnojbaimteM

AKO T p e ö a

5).

X0PH30HTAJIH0

je npeTxo^HO

aKo

1-cm)

ÄO

3a u e l j e i b e

noBpuiHHa

CN.

Moace

ce

HJIH

KaTKa^a,

AO

(1/2

c e MO«ce n p a 3 a H JieBaK n p e T x o Ä H o

TO

npenopynyje

OBA

ce

Hajia3H y

jieBKy

ce H3ÖerHe

KpaTKo

ynoTpeöa

3

n a p o M

H nycTH

JIEBAK

Kora

ce

fla

H a p o i H T O H3 Bpjio KOH-

caMOM

3anajbHBH p a c j B a p a n n M o p a ce ripe u e l j e i t a y r a c H T n

ynoTpeôjbaBajy

ce

yHCKOJiHKo oacetieHa

npenopyuyje

(CJI. 4 ) K O A

qajioM

ueB

OÄBOÄH3

BHiiie

cyncTaHua,

ycjie,a; x j i a ^ e i b a B e h y

ueHTpoBaHHX

^a

,n,o6po

Kojn

H y n y

3anTHBa;

ca

ToruiOM

BOAOM

Hajöojbe H

OBa

ue^e,

e

Ha

Aa

ce

T3KO

Ta.ua

3arpeBa

KÄ>YQAFT>A.

A K O ce npH ueJjeH>y Henor pacTBopa ycnen HCKpHCTaJincaBaH>a cyncTamxe fyumap 3anyuiH, TO r a HH y KOM CJiywajy He Tpeöa npoöyuiHTH Beh ce (jJHJiTap nocraBjbeH ycnpaBHO HCKyBa y MaJioM nexapy ca CBOKHM pacTBapaneM H Tajia Kpo3 HCTH (JJH^Tap npoue^H pa3ÖJianteHHjn pacTBop. UeJionynHH ce pacTBop Mopa y T 3 K B H M cjiyiajeBHMa na KOHuempHixie HcnapaBatbeM.

ce

AKO

>Ke^IN,

KpHCTajiH, A0Jia3H CTBop,

AO

TO

3a ueljeHje, HJIH

po3Hor

KOA

a3ÓecT,

CTaK^a.

noHOBo

caMO

ce

KOMe

Aa 3arpeje

nolano

y

HH

J'HKHX

6a3a

BehHx

je

H

QECTO AOK

noTriyHO

i i e l j e a e M

a Hajóojbe

KOÄ

npnjiHKOM npeKpHcrajiHcaBaita

(JjHjrrpaT, y

KpHCTana

H S A B A J A I T E

BYHA

ce Aoówjy

n y c T H Aa ce

ue^eH>eM B e h y B e K THjy

Aa

Mopa

H3FLBAJAIBA,

Ta^a

H

ce

cjiynajy

B a K y y M

KudejitiHa y3HMa

UCAHTH

KOJIH^HHS

Kpo3

3a BpeMe

He A o ö n j e

Ha M « p y

KOM

Ha

ce

Beh

öacTap

pa-

OXJIAßH.

He

BpuiH

OÔHHHHM

ynoTpeôJbyjyhH ce Tanoije

Schott-OBE

cyneraHiie

ji e n H aeijeita

Tpeöa

H

xap-

cTaKJieHa

(JjHJiTpe

OA

no-

ynoTpeójbaBaTH

ZtoßHjaite opraHCKHX cyncTaHUH y MHCTQM c T a a y

Büchner-y

JIEBaK

NO

npaBOM

OAHOcy

T.3B. Hyn (CJI. 6) MHj'e AHMeH3Hje T p e ö a

npeMa

MacH

Koja

ce

cm

npeiHHKa.

Y

aa 6 y a y

y

ueAH.

n o T n y H O je norpeiiiHO neAHTH OA 6 HJiH B u i n e

9

HCKO^HKO rpaMa c y n c r a i m e Ha H y q y

MHOTHM c J i y q a j e B H M a

H a p o ^ H T O OH^a a n o

HM3 Aa c e u e ^ e MaH>e KO^HHHHC T p e ö a yMecTO nopuejiaHCKor Hyqa y s e r a n j i o ^ H u y

3a

u e ^ e i t e

no

Witt-y

{CJI.

7). IlpeHMyhcTBo c e cacTojH y

CJI. 6

TOMe,

NITO

ueijeffce, TOMe

ce

Hero

MOtfce JIH

CJI. 7

MHOTO ö o j b e Aa KOHTpOJiHuie q n e r o h a n p n ö o p a 3a

KOA

HenpoBHAHor

nopnejiaHCKor Hyqa, a npe cßera

y

UITO Hcnnpaffae T a l o r a , y c j i e A Mnoro Matte noBpuiHHe ocHOBe, H3H-

cicyje AaJieKO MaH>e Ko-anqKHe

pacTBapaqa.

3a npHtipeMatte (jHiJupa npeBHje ce MajiH KOMaAHh ({iHJiTap-xapTHje npeKO ropH>e HBiiue njioMHue 3a UE^EITE H TaAa ce MaKa3aMa Hceie KOTyp 2 — 3 mm Beher noJiynpeiHHKa. HjiTap KojH je HaKBaujeH pacTBapa'ieM npmbyöH ce 3aoÔJbeHHM CTaoeHHM uiTarwheM HAH KOÄ BehHX njioia HOKTOM TaKO na ce H3rjiajie uam Haöopii. AKO T p e ö a

fla

ce u e A e

cacBHM

MAJIE

KOJIHIHHC

cyncTaHue

OA HeKOJiHKO cg HJIH MAH>e, OHAA c e nao NOA-^ORA sa. n e r e t t e ynoTpeöJbaBajy Majie C T A K J I E H E OA CTaKJieHHx

NJIONNNE

uiTannha

OA 0 , 5 — 1 cm npeiHHKa K o j e ce npaße

Ha Taj HaqHH, Aa HM c e jeAaH

Kpaj pa3MeKiua y naaMeHy AyßajbKe H TaAa

Ha rB03Ae-

HOM JIHMy HJIH nOpne^aHCKOM T3H>Hpy npHTHCKOM enjbOUITH

(Diepolder).

AyraiaK,

Aa

CTAKJIEHH uirannh Mopa A A Ö Y A E TOJIHKO

Moace AA npotje Kpo3 UEß jeAHOr

CÜCBHM

Ma^or jieBKa H Aa Ma.no H3BHpyje H3 neBH. K a o (J)H.aTap cjiyjKH jeAaH

HeuiTO

Behn

OKpyrao

KOMaAHh (Jmjrrap-

xapTHje KojH A o ö p o Hajie)Ke (CJI. 8). Jla 6h ce riocjie ueljeita cyncTaHua CKHHyjia ca iuioinue, noCT3BH ce fleBaK oKpeHyT

Haaojie

H3iiaa jeAHe mojbe HJIH caxaTHor

CTaKJia H JEAHHM TSHKHM CTaKJieHHM iiiTanHheM HJIH öaKapHOM JKHUOM

CJI. 8

njioinua noTHCHe taKo aa cBe naaHe Ha noAMerayTy noAJiory. flJioiHua 3a uetjefte ce yKjioHH noMohy nHHue/re, a (jjHJuep-xapTHja Ten nocjie cymeita. AKO je ueî)eH>e BprneHO

noMohy

„craKJieiior ayrMeia"

noTHCHe ce ctaKJieHH liiTaimh ca ÄOH>er Kpaja KojH

H3BHpyja H3 jieBKa, THMe OAJiemi (jiHJiTap xapmja OÄ 3HÄOBa jieBKa H CKHHe noMohy ITHH-

10

HeKcuiHKO onuiTHs npaBHJia 3a paa

uexe. CyncTaHua Koja je 3aociajia Ha neBKy cKHaa ce 6e3 ryöHTKa jeaHHM koco 3aceieHHM KOMaAHheM KapTOHa. OHOTpaT c e npmiHKOM iietjeita Ha BaKyyMy XBaTa y HapoMHToj 6 o u h 3a i t e ^ e i b e

Ha

BaKyyM,

qwja c e BejiHiHHa n o A e c « npeMa 3anpeMHHH

pacTBopa. 3a ueljeibe Majinx KOJiHHHHa n p H M e i t y j e ce e n p y ß e T ä aa u e ^ e i b e (cji. 8 )

Ha B a n y y M y

pa3JiHqHTHX BejiHqmia.

o j i o b h o m nocTOJby hjih a p b c h o m

öaoKy

Oßa c e Ha;ia3H yHBpmheHa

ca 0TB0pHMa 3a e n p y ß e i e

y

pa3;iH-

HHTHX npeHHHKa. Kano

ÄOÖHjaH>e

c k h '3HaMaj, t o

n 0 M 0 H H Hajßehy Be3

aHajiHTHHKH

Tpeöa

noneTHHK

Aa

ce

OAÖaun h a h h h , Aa c e KpHcrajiH

y o n u i T e T p e ö a Aa t o k h

npenapaTa paAH

no

CBa'Ka nojeAHHa peaKunja pa3Jiora

A a ßeh k o a

H3paAe

k b 3 h t h t 3 t h b h o .

MoryhcTBy

HHje Mepo^aßaH 6 p o j npenapaTa, H3 obhx

mctoa-

Ha n o p o 3 H y nopuejiaHCKy maoMy h Ha i t o j

3ajeAHO ca pacTBopoM H3Jinjy ckhx

cyricTaHijH HMa b c ^ h k h

namay.

npeAOMHiujhaiba

Hcnwpajy.

hhcthx

npaKTHKaHT y opraHCKoj xeMHjH Mopa TexHHUH ueijeiba Aa

opraH-

3a

ycnex

ßeh öpnaubHBOCT h caßecHOCT K o j o M ce

H3boah.

He cmc ce

„oueÄHHa"

CMaTpaTH

Kao OTnaAaK,

hhth ce CMe 3aHeiiapHTH. hbeHa BpeAHocT he öhth jacHa Ten opraHHqapy KojH p a ^ H HayiHO, aan h noneTHHK y npenapaTHBHOM p a A y T p e ö a H3 H>e Aa H 3 ß y i e CBe u i t o c e c 0Ö3Hp0M Ha UHJb i b e r o ß o r pa.ua, h3 ibe Aa H3Byhn. 3 ö o r T o r a c e HMa 3a-

H c n H p a a y T p e ö a y ß e K y n o T p e ö j b a ß a T H h c t h pacTBapaq h

Moryhe

m a h> o j k o j i h h h h h ,

to

nouiTO ce cyncTaHija y H>eMy

h Ha xjibaho pacTBapa, uito Moace Aa n p o y 3 p o K y j e

Maft>e

h^h Bebe

ryÖHTKe. 3a ßpeiue Hcnupaifea He CMe c e npHKJbyiHßaTH Ha BaKyyM; T a a o r c e cKpo3 HaTonn pacTBapaneM h Ten TaAa ce n y c ™ y p a A BOAeHa nyMna. KopncHo je aa ce Ha By;ie. hboMe ce M ö w e He caMO Jiaso aa HCKJbyqw aejcTBO BoaeHe nyMne, Beh ce MOiKe h aa p e r y j i H u i e npoineHa npnTHCKa uito je y mhoi-hm CJiyiajeBHMa noTpeÖHO. na npHKJbywH y3 CBaKy BoaeHy nyMny,

Koa

MaTepnja, K o j e c y ßeh Ha x ^ a h o

Jiano pacTßopHe, Mopa c e pa-

CTßapan KojH c e y n o T p e ö j b a ß a 3a H c n n p a i t e npeTxoAHO Aa oxjiaAH y CMerna 3a x^aijeft>e. JJoK^e r o A c y KpHCTaJiH j o u i HaKBauieHH pacTBopoM, He CMe c e Kpo3 oueijeHH T a a o r Aa n p o n y u i T a jiano

HcnapjbHB

pacTBapaq.

CTpyja H3

Ba3Ayxa,

ano c e

pacTBopa 6 h c e HHaqe

ynoTpeÖÄ>aBa

H3ÄßojH^e h He"

11

ÄoöHjafte opraHCKHX c y n c t a H u a y mhctom c r a f t y Hapoqtrro KOR

HHCTohe H HHje CHrypHo,

jiaKO pacTBopHHx c y n c r a m j H , Aa

he ce HeHHCTohe HcnnpaiteM Mohn noHOBO noTnyHO

yKflOHe.

Ma^e KOJiHiHHe cyneraHue ncnnpajy ce ÄOÄajyhH pacTBapaq Kan n o Kan. ToMe cjiyacH h t. 3b. u e B q n u a CTaKJieHa

3 a k a n 3 h> e (cji. 9).

ueB, H3ByneHa y He OABeh ycKy Kann;i3py;

T o je je^Ha

OHa MOHce

BeoMa KopHCHO ^a nocJiyîKH 3a H3Boi)eit>e MHornx p e a K u n j a H K>eHOM ynoTpeôoM pa3BHja ce CMncao 3a qncT pa£. O Ô H i a j KojH ce Meció HaiHH n a c e p a c x ß o p

3ana>Ka,

Hcnapn

.na ce cyncTaHue

„npeimiihaBajy"

ä o c y ß a y uiojbH 3a KpHciaaH3auHjy>

Ha Taj

HapaBHO

ne

boah uHjby, jep ce Ha OBaj HaiHH HeiHCTohe He yK.iatt.ajy. M a ; i e KOJiH^HHe T a l o r a Koje ce TeniKo u e ^ e Mory c e 3r0AH0 h 6p30 h3aboj'hth noMohy Ma^e ocjioöoäh h nocjie^ifcHx

p y qh e

aeHTpntjiyre.

H h c t n p e n a p a T Mopa n o m y H o a a c e

CyiiieH>e c y n c T a H u ; « :

TparoBa

3aocT3.nor

jaHe cyncTaHiie c y m e ce Haj3ro,a,HHje

p'acTBapaqa.

flocTO-

H3Meîjy JiHCTOBa x a p m j e 3a

u e ^ e i t e Ha qncToj noAJio3H Ha coÔHoj TeMnepaTypn, t 3 k o iuto c e ocTaBe

Aa

bhcokom

CToje je^aH ä o ä b a aaHa Ha B 3 3 A y x y .

T3HK0M

cyuiHHun

Tonjbeibs

HJiH

oaioöaijajy

Ha B o ä e h o m

ôpjKe

ce

Ky naTHJiy;

C y n c T a H u e capacTBapaqa

y

MeijyTHM o b o c e

Mopa BpniHTH yBeK ca H3BecHOM o n p e 3 H o m h y . HajcHrypHHja

3a n p e n a p a T e

g

3a 3HajiH3}' je^HHO

MeTOÄa j e c y m e i t e y B â K y y M - C K C H K â T O p y noKJionua j e BeoMa

npHMe&HBa

y KojeM c e Ha.na3H kohiî.

M O ^ e ^ CMaipaMo Kao HsjnoroflHHjH.

cyMnopHa KucejiHHa. C T a p a Scheibler-ob 3 a 3ariTHBaH>e

(

BawHa

KOH3HCTeHUHj£

m a c t h; aajnoroÄHHjH j e

hjih MemaBHHa jeaHaKHX nejioBa r o b e f) e r J i o j a il B a 3 e ji h h a. UeB ca cjiaBHHOM 3ao6jbeHHX HBHua objibhch c e ca Majio r j i H u e p u H a h adeps

lanae

anhydricus

y a y q e y ryMeHH 3 a n y i u a i KojH j e upeTXOÄHO CTaBJbeH y T y ö y c ; p y n a 3 a i i y u i a i a Mopa TaiHO na ouroBapa BejiHHHHH ueB h. K a o jKHue fla

ca BHiiie

6h ce

y ji o >k a k

c j i y w H jeÄHa nopuejiaHCKa njioqa Ha Tpn ho-

KpyjKHHx OTBopa y KojH ce cTaBjbajy

cnpeiHJio

noMepafte

Majie

yjiouiKa TaMo h OBaMO

rnojbe,

c a x a r a a cTaKJia h t. ä. y j i o i u n a h 3H«a

y r j i a B e c e H3Metjy

encHKaTopa TpH noroÄHa H3pe3aHa KOMaaHha nJiyTe. Jla He 6 h npnjiHKOM

OTBapatta eBaicy-

koj'h CTpyjH y n y T p a pacnpuiHO c y n c T a H u y , CTaBii ce ripe« T y ô y c h yHBpcTH yjiouiKOM KOM3A KspTOHa h t. cji. C T p y j a i t e B a 3 a y x a KojH yjia3H y H y i p a yôna» y j e ce joui u TUMe uito ce npe oTBapaiba c^aBUHe cthbh n p e a cnojbHH oTBop ueB h KaMaaHh «aßajy Boay H apyre pacTBapaie Tano ynopHp, na ce HH y BanyyMy Ha CO6HOJ" TeMnepaiypH He Mory OÄ O B H X na ocflo6oae. Taaa ce cyiiiH y BanyyMy npH n o B H i u e H o j TeMnepaiypH Ha Taj Ha e

(BHAH

cji.

npenopyqyje

c e HapoHHTH

33).

AKO j e n p e K p H C T a j i H c a B a f t e B p i u e H o n o M o h y TeniKO HcnpajbHBHx p a CTBapana, K a o ca

BHCOKOM

LUTO

T p e ö a KpHCTajie HHTH, Kao

c y iviauHjajiHa

T3HK0M

HITO

HCKYBA™

j e eTap,

ca

HCKHM

6eH30Ji,

TeiuKO p a c T B o p H a y rJiaiiHjajiHoj TeiiiKO p a c T B a p a H y Bpjio

(J)HHO

CHPIIETHA

KHCEJIHHA,

HHTpo6eH3o;I

K^YQAFTA,

H

T.

TO

npe

cyiuefta

p a c T B a p a q e M KojH c e Äa c a n i n e

ra3o;iHH. cnpheTHoj

yoo-

ce cyncTaHua Koja

06HeH y noneTKy h thmc noMepe HJW chcbhm ncnepy caCTojuH

KojH

qßpcTO

He

npHjaifeajy.

Obhm

„ p a 3 b h j a h> e M "

ÄOÖHja

ce

„ x p o M a T o r p a M " (b. c.i. 58). IlojeAHHe 30He ce nocjie cymen>a c r y ö a MexaHH^KH OAßoje jea,Ha o a Ä p y r e h ca noroÄHHM pacTßapaneM „ e j i y m u y " . H 6 e 3 6 0 j h e cyncTaHije Mory no obom b3>khom nocTynKy necTO Äa ce OÄBOje h ÄOÖnjy y hhctom cTaiby, ano je Moryhe Äa ce xp0MaT0rpaM y iieBHHUH 3a ue^ette m y b h 0 . i c t a k .ji a hjih K B a p u a paciaBH Ha Ae^OBe noÄ >khbhhom jiaMnoM Ha 0CH0By nojaBa (j^yopecijeHue. T a n o je Ha np. 6uno Moryhe £ a ce KapoTHH paciaBH Ha 3 KOMüOHeHTö (R. Kuhn,

P.

Karrer).

MH heMO ÄOtiHHje, KOA xjiöpotJwjia, A a ™ je^aH npHMep 3a OBy Bp^o MOAepHy MeTOAy (XII, 12). 2.

KapaKTepncTHHaH

flecTHJiaijHja

K o ä npeqmuhaBaiba A e c T H J i a u H j o M cyncTaHua ce y napHOM c r a i t y o a b o ä h h x ^ a ^ e a e M Ha ApyroM MecTy npeBOAH oneT y Te^HO hjih QßpcTO a r p e r a n i o c T a ^ e . npeAycflOB 3a npnMeHy OBe Merode npeHHiuhaBafta jecTe n0CT0jaH0CT MaTepHje Ha cßojoj TeMnepaTypH Kjbyqaiba. Oßa ce Mome chh3hth H c n a p a B a n e M y B a K y y M y . Tanna KJbyHan>a CHHjKaßa ce y BaKyyMy Kojn ce nocTHJKe Ha yoönnajeH HaqHH noMohy ßo^eHe nyMne ( 1 2 mm) npocenHO 3a 1 0 0 — 1 2 0 ° y oAHoey Ha raHKy K ^ y n a i t a noA aTMOc4)epcKHM npHTHCKOM. K o ä MarepHja Koje noA oöhhhhm üphthckom Kjbyqajy H3HaA 250° oßa ce pa3^HKa noßehaßa. 3 6 o r Tora ce Mory A e c r a jiOBafteM y BaKyyMy Aa npeiHCTe Bpjio necTO cyncTaHue Koje ce pacna^ajy Beh hciioa cßoje HopMajme TaHKe Kjhyqaita, nouiTO ce OHe OBaKO H3Jia>Ky MHoro hhhchm TeMnepaTypaMa. CyncTaHue n p o e r o r cacTaßa, a npe cßera h jiaKo HcnapjbHBe, Kao iiito c y yrjbOBOÄOHHUH, aJiKoxoaH, ecTpn, HH)Ke KHce^HHe, aMHHH h t . cji. ÄecTHflyjy noA aTMOccJjepcKHM npHTHCKOM. K o ä cbhx MaTepwja Koje ce p a c a a a a j y , Kao h k o ä ohhx Koje KJbynajy HapoHHTo bhcoko, Tpeöa Aa ce BpiiiH AecTH^auHja no^ cMatt>eHHM npHTHCKOM. K o ä ^ b p c t h x kphct3jih30B3HHX Tejia n p e Ä y 3 e h e ce ÄecTH^aiiHja caMO OHÄa aKo npeHHiuhaBaH>e KpncTajin3auHjoM 3Öor cyBHiue BejiHKe paeTBopAHBoera hjih h3 Ä p y m x pa3Jiora He boäh itHjby. MoryhHOCT ÄecTHJiaunje (6ea pacnaÄaiba) Mopa ce HapaBHO y cbskom cflynajy npeTxoÄHO Aa yTBpÄH.

HeicoJiHKo oniuTHx npaBHJia 3a paÄ

14 XlecTH^auHja, CAYJKH HE CAMO 3A

6HJIO ÜOÄ ATMOCa ( ( J J P A K U H O H A a e C T H J i a u H j a).

^ecTHJiai^Hja no,n aTMOctjiepcKHM n p i i THCKOM: Kao cyÄ 3a ÄecTHJioBaibe o i y a i H npocT ö a j i O H 3 a < j ) p a K U H O H H c a t t > e ca KOCO

HA

FLO^E

NOCTAßJBEHOM

3a TenHOCTH Koje KJbyqajy ÖAJIOH

ca

BHCOKO

UEBH HHCKO

NOCTABJBEHOM

(CJI.

11);

y3HMa ce

UGBH,

a

3a

Koje KJbyqajy BHCOKO y3ehe ce 6 a ^ 0 H KOÄ Kora je U E B NOCTABJBEHA HHCKO TJ. Ö^WACE jionTacTOM Ä E J I Y . TCMHOCTH

T e p M O M e T a p ce cTaBJba Ha öajioH noMohy HHCTor, npoöymeHor 3anymaHa; nape cyncTaHue Mopajy noTnyHo m oö^HBajy KyiviHiiy ca Ä H B O M , OHa AaKJie Mopa Ä a ce HAJIA3H H C I I O Ä y m h a 6 o H H e O ^ B O ^ H E U G B H. Cn. 11

NOUITO cy OÖHIHH jiaöopaTopnjcKii TepMOMCTpn qecTo HeTaiHH, Mopajy ce npe ynoTpeöe ynopeflHTH ca HopMajiHHM TepMOMeTpoM. Baxe je HajTaiHHje Kaaa ce o6a TepMOMeipa nociaße jeaaH nopeji apyror y KOHuempoBaHy cyMnopHy KHcejiHHy HJIH napatfiHH, 3arpejy Ha 250° h Tana npn xJiai)eH>y nocMatpajy h 6ejiexce TeMnepaType y pa3MaunMa OÄ no 10°. TepMOMeipn 3a ÄecTHJiauHjy Tpeöa na HMajy M a JI y « y r j i y , Äa 6H HHÄHKaunje TeMnepaType ycJiejiHJie UITO 6p«ie. BeflHqHHa ßajiOHa 3a ÄecTHJioBaibe Tpeöa Äa ce H3Öepe TaKo, Äa öajioH öyAe HanyaeH TeHHomhy ÄO nojioBHHe H;IH HajBHuie ÄO ÄßE TpehHHe. H a 6H ce H3Öerjio 3aÄp)KaBart>e Kjbyqaita H THMC H riperpeBaifee, CTaBe ce y öajiOH 3a ÄecTH;ioBaH>e npe cBaKe ÄecTHJiaunje KOMaAHhn Heivia3HpaHor nopne^aHa ( K a M e H q n h H 3 a K j b y i a a e ) Be^HHHHe n0Ji0BHHe 3pHa rpauiKa. AKO H nopeÄ Tora Äoije ÄO 3aÄP>KaBaH>a Kjbyqaiba Mopajy ce KaMEHHHHN N 0 H 0 B 0 Ä O A S T H , a;IH He y nperpejaHy TCHHOCT, Beh TCK NOUITO ce OBa Majio oxjiaAHJia. BAJIOH CE NPHMBPCTH H 3 H 3 Ä OÄBOÄHE ITEBH UITHnajbKOM OÖJIOJKCHOM N^YTOM. M S B O P H T O N J I O T E : T e i H o c r a Koje KJbynajy ncnoÄ 8 0 ° 3arpeBajy ce Ha B O i e H Ö M K y n a T H J i y (eMajjinpaH JiOHaq; H;IH nexap); T e i i n e p a T y p a K y n a T H J i a T p e ö a ÄA Ö Y ^ E O T n p n j i H K e OKO 20° H3H a Ä T a h K e K J B Y I A I T A c y n c T a H u e . OAp®aBafte TaiHe TeMnepaType 3arpeBaH>a je OÄ BejiHKor 3Haiaja, nouiTO ce KOÄ cyBHiue BCJIKKOT noBHrneHja TeMnepaType Äoönjajy y o i e Ä nperpeBaita cyBHUie BHCOK6 TaqKe Kjbyqafca ÄCCTH;iaTa. KOÄ

MaTepnja Koje Kjbyqajy

RÄE c e Ä 0 3 B O J B 3 B A

HHTEPBAJI

BHCOKO

OÄ HCKO^HKO

Mome ce y npenapaTHBHe cßpxe, CTENEHH 3A TAHKY KJBYHAH>A, ÄA

Äo6HjaH>e opraHCKiix c y n c T a m w y «IHCTOM C T a a y

ynoTpeÖH

cjioöoAaH,

noieTKy ,0npe3H0 B a 6 O-JI e b k y KaÄ

ce

hjih

3axTeßa

öerHe

Ha

MaxaiteM;

yc/ieA

aerype,

hjih pacTon

ji h t p e ,

oöoje

y

Koje

CyncTaHue

K 0 H f l e H 3 a T 0 p y ueB

öa^iOHa

3a

oTnapaBafta,

öouom

3a

ce

ue^eite

xjiaAH JieaoM Koa 6h

TeiHOCTH

ce

koj'h

Koa

jia3H

npeTCTaBJbeH

boaom,

nouiTo

OMOTany

ce

noKpHBeHa

jioBHMa

qecTO

Kao

ce

no

3aBpmeHoj

no

MyKe

ce

y

uia-

J I m ö h t o b o m

3anymaqa H3ÖerHe

Ha

OABOAHy

cbskh

ryÖHTaK

je^Hor

xBaTaite

HacTaBKa

ca

AecTHJiaTa, h

Koja

100°

AOBO;baH

je

koh-

k p a t a k

KOJinqHHa H a p o n n T O c e jeAHor

OABOAHy H3aaA

O M O T a i a

neB

öajioHa

npenopyqyje

3a 3a

xjiaijeite

AecTHJiOBaibe.

22.

120° o ö h h h o

3 a x.aai)eH>e y

nocreneHO

ce

AOAnpy

tchhoct

3arpeBa.

x .nabelte

nocjie H3

3ä

KaA

He xJiaAH

ca

BHuie

BpejioM

napoM

x J i a t j e i b e BOAa

Koja

Tanna lobynaiba

npe-

B a s A y x o i u

KOHAeH3aiinje

ÖajIOHa

h

(umpoKa

H ryÖHTKa y3HMa

hjih

ueB

3ä

ApyrHM

Aa

Ae;iy

cTatt>e,

a^H

He C M e j y

c a yCKOM aeBH

ce

ce

OABOAHOM 3arpeBaiteM

3anymeHa

MecTa

Ae-

orayme

h

BpeMeHa. öajiOH

caBajeHOM ueBH ÄecTH^aaHjn

OHBpcny

cjioöoahom

TeqHo

Mory

He

6p3o

(J)paKIJHOHHCaH)e y

y

3anyuiaHHMa

OAMax

3a

AOAyme

Aa n p e B e A e

totobo

MHOTO j a ^ a

c a ö j b a

ce

M(me

oneT

Koja cy

.3aTO

ueB

Aa

3a

Ha c.a. 1 9 h

npocTO

Koje

ÄeCTHJIOBaTH

iieBH; ^ecTHJiaT

3aÄajy

3a

Po3eoBe

hjih

OMOTaqa).

CyncTaHue

n^aMeHOM

Ha

je

6h

Koja

bhcokhm

KynaTHJio,

H a T p n j e B e

Be5Ke n p e n o

O B A e c;iy>KH K a o

1 5 0 ° ÄOBOJbHO j e

xjiatjeibe 6e3

ca

h

xohe

oko

Kjbyqaita

npcHe;

npeiua

h

H3-

xjiatjeibe.

Ma;iHx

HenocpeAHO

jiaKo Aa

HHK3A

3a

Kjfayuajy

TeMnepaTypa

TeKyhoM y

ce

noMohy

Koja a y » H

AecTHjioBaiby

HaByqe

Taie opraHCKHX npenapaia, He Möwe iaK HH Ha KJbyqa.noM BOÄCHOM KynaTHJiy noinyno na 0ÄB0jH OÄ Hene MHoro Matte licnapjbHBe cyncTaHue, nano je H>eroßa TaiKe KJbyiaH>a 35°. üpyrH no3HaT npimep npeTCTaßjba H3ÄBaJaH>e 6eH30Jia y KOKcapaMa, no y TO ce MeljyTHM OB^e He M o » e Ay6.te y^a3HiH. Tmvie c e o6jaiuH>aBa a a

H y

T e a n o NPETXOAHH H h3KH3AHH ce « c i m a ™

HaKHaAHOM T o n y UMS iviaBHor n p o A y K T a ,

TOK

npecT3BJbajy

3H3THnje

KOJIKIHHC TO

Aa c e o 6 a OBS AEAA OASOJEHO, npeina A3THM NPABHAHMA NOHOBO

AeCTHAHUjy. 4>paKi^HOHa A e c T H J i a u , H j a : JI>HBHX n p o A y K a T 3 H e K e OAHOCH TaiKe

HHCy

BHUie

T3KO

KJBYQAK>3 A e a c e

A K O j e n o T p e Ö H o Aa c e B H in e

p e a K i ^ n j e A e c T H A a n n j o M OABOje j e A a H npOCTH K30 IHTO j e T O p e

ÖAHJKC j e A H 3 A p y r o j ,

OA

H3HeceHO.

ncnapApyror,

yKOAHKO

yT0JiHK0 j e 3 3 A 3 t 3 K TeiKH, H

Beh HHje A3KO A a c e ca OÖHIIHHM j i a ö o p a T o p n j y M C K H M cpeACTBHMa KOJIHKO TOAHKO n o T n y H O j e A H a OA A p y r e Haaa

p a a A H K y j y 3a riyT,

noHaBAjSHe

HH)Koj T e M n e p s T y p n npHMeHOM T. 3B. K0HAeH3auHjy ycAeA OBHX

q n j e c e T3HKe

oABoje Kjby-

10°.

K o j n A03BOA>3B3,

BHiiiecTpyKO

cyncTaHue

AA c e

Hsjnpnö^HJKHHje AO^E AO

AecTHAauwje.

Moace

KOAOHa

KOA cyncT3Hun

Koje

c e TO H3BPUIHTH y j e A H o j j e A H H o j 3a

4>paKUHOHHCaH,e;

uHA>3,.jecTe K J b y n s j y Ha onepaunjH

TO Cy CHCTßMH 3a

KOJ'H c e y K A > y q y j y y n a p H y (J)a3y n p e KOHanHe KOHAeH3auHje.

xAa^eita

B33AyxoM

napa c e KOHAeH3yje y

KOAOHa 3a A e c T H A a i j H j y ,

Koje

Mory

nojeAHHHM

6HTH p a a ^ H i H T e

OAejbUHMa

KOHCTpyKUHje

Ä o 6 n j a f t e opraHCKHX c y n c t a H U H

(H. np. CJI.

13),

h HOBa

napa

Kója

y

HHCTOM

HaHJia3H

17

ctafty

Mopa Aa npojia3H

Kpo3 OBe

KdH^eH3aTe KOJ'H j o j Jiexce Ha n y T y . n p H TOMe c e K.eHH Teace HcnapjbHBH cacTojitfi

AOK

KOHAeH3yjy,

ce

ca

MKiue

HcnapjbHBHM

a r p a noHaßjba y H^yheM qjiaHKy KOJioHe. T a n o AOJia3H ÄO

JE^HOR

HH3A

o^roBapa

H

JiaraHOM

OÄBajaH>e. K0Ji0He

NOJEAHHAQHHX

H3BoJ)eH>y

3a

Köje

OBy cy

HapoiHTO

onepai^Hje

CBpxy

cy

HanyiteHe

KJieHHM P a i X I H r O B H M pajia",1)

AECTH;IAIIHJA,

JIOUTH KOJIOHC UITO n p «

6pojy

ce

6poj

MHJN

n a hí jb H b O M

0M0ryhaBa

Aoöpo

n o r o A H e H UHJiHHApHqH.e

6e3

HapoMHTor

paAa

cTa-

npCTCHOBHMa,

Aoöpo

noKa3a./ia „BnAMepoBa

npHKa3aHa Ha CJI. 14, « o j a

cnn-

H3pal¡eHa y MaifeHM

ÄHMeH3HjaMa H ycal^eHa y rpjinh ßajiOHa 3a AecTHJiOBaibe MOHCe H3BpCHO Aa nOCJiy)KH H npH (JjpaKUHOHOM AeCTHJiOBaity MaibHx K O J I H M H H 3 cyncTaHije. TexHHHKO H3Bo{jeH>e npHHunna $paKunoHe ÄecTH^amije HaJia3HMo y cfjaöpHKaMa umypmyca, nao H KOÄ H3ÄBajaH>a apcwaTHHHiix yrjbOBOÄOHHKa H3 ;iai{or yjba KaTpaHa KaMeHor yrjba, Koje ce BpiUH Ha HCTH HaiHH. MeuiaBHHe

TCMHOCTH

C N. 13

BHiue Tanne KjbyqaHba ( ^ > 1 2 0 ° )

pa3ABajajy ce Ha CBoje cacTojKe Tano, Aa c e Hajnpe pa3Jio>Ke AecTHJiaiiHjOM y BHiue ^paKHHja K o j e KJbywajy y n p n 6 ; I H ) K H O

HCTHM

TeMnepaTypHHM HHTep-

BajiHMa. nojeAHHH AecTHJiaTH ce ( y MattHM óa.iOHHMa 3a 4>PAKIIHOHHCAHJE)

n0H0B0 pa3ABajajy AecTH^iHixHjoM. paK-

ilHje, K o j e c y no

CBOJ'HM

TaqKaiua

KJBY

naita öjiHCKe, Ae-

CTHJiHuiy ce 4>paKUHOHO j o n i BHtue nyTa y 3 CBe.oiiiTpHje CY)KABAH>E

rpaHHua T a ^ K E

KJBYQAFOA.

ce xohe,

AKO

LUTO

ce BeoMa n p e n o p y q y j e , H OBAe Aa ynoTpeÖH r o p e noMeHyTa BaAMepoBa cnnpa^a, ce

ce Mopa KO^iOHa y

TO

KOJ'OJ

cnnpa.na Ha^a3H, A o ö p o Aa H30Jiyje a3ÖecT0M. Cße ce MeuiaBHHé He M o r y oaboJHTH AecTHJiauHjoM;

K3AK3A MaTepnj'e K o j e KJbyuajy p a i y p a w a A a j y AecTHJiaTe

Ha pa3JiHHHTHM Teianenpe;ia3e Ha KOHCTaHTHOj

KOJ'H

TeMnepaTypn. O

Teopnjn

IJ. Erepül,

(JJPAKUHOHE

flecTHJiaijHja CJI.

Mopa yBeK

14

ca c

T

a 6

H A

He.

flejcTBo

KojHMa

—

cyncTaHiie He Widmer,

y

NOBHINEHE

BaKyyMy:

Ha y M y ,

HM3TH

paAH

ca

BHAH

ÓJIHJKC

AA

cy

-XeMHHap-opraHHqap TOTOBO

CBE

MaTepnje

iyieAnuiTá 1 TepMOAHHaMHKe

TeMnepaxype je

jeBHMa n0B0.ft.H0 3a y c n o c T a B j b a i t e pacnaAaK.e

AECRAJIAUNJE

yjjöeHHK 4)H3HiKe xeMHje.

HCTHHCKC

MEIJYTHM

paBHorexce

—

y

Meia-

CBHM

cayna-

OBAE TO

3H3HH

H 3 0 o r T o r a heMO ceÓH nocTaBHTH Kao npaBH.no Aa CBoje AOBOAHMO

HENOTPEÖHO

y

ONACHOCT.

H e l v , c h i m . act. V I I , 59 (1924).

IlpaKTHKyM opraHCKe xeMHje

2

18

HeKOJiHKO onuiTHX npaBHJia 3a paA

Tor pa3Jiora ce

H 3 3HAQAJ

ce paay

T y p a KjbyHaH>A

AA

npenapaTHBHOM

ce

NPH

paay y opraHCKoj X C M H J H N P H N A J E B C ^ H K H npn q e i u y M O A C E T € M n e p a 1 0 0 H BHLUC creneHH. OpraHHqap M o p a y .

n o Ä CMaH>€HHM npHTHCKOM

ÄECTHJIAUHJH

3a

CHH3H

y6p30

HAYHHTH

casnam

^A

K>EHY

METOÄHKY,

paHHje H A B H K H E H A T O , FLA Ä ß C T H J I A U H J Y Y B A N Y Y M Y onepaunja", B e h nao j e ^ H Y O Ä HajejieMeHTapHHjHX

IIITO

„KpyHy

ßopaTopHjcKe

onepaunja

Jia-

npaKce.

HajnoÄecHHjn PberoBC)

Aa

H

cxBara Kao

HE

BeoMa

CYA

3A

je

ÄECTHJIOBAIBE

uejmcxoAHO

paiBaite

Koja KJbyqa, JX&

Ciaisen-OB

Ö A A O H

IUTO

je

KOÄ AecTHJiaiiHje

y

CTyna, y c H c a B a j y c e K p o 3

onacHO.

KJBYQAITA

BaKyyMy

MEXYPHHA

Koja K j b y q a ,

TC^HOCT

BA3AYXA

—

oceTJbHBHx n p e M a B a 3 Ä y x y KANHJIAPA

Koje

B p j i o Jiaico Ha-

n o M o h y j e Ä H e BeoMa e

6H

(CJI.

ueBH c n p e q a B a n p c K a i t e

KOÄ

BOÄOHHK

erajiHO

CYNCTAHUH HJIH

C 0

2

.

CE H3BJIAMH H 3 JEÄHE AOBOJI>HO AYRE

CTaoeHe ueBH mwpKe 4—8 mm, Haj6ojbe KanHJiapHe ueBH, Ha nnaMeHy AyßaJbKe H HaKHaAHO JOJ CE ITOHOBHHM H 3 BflaaefteM Ha MSJIOM nJiaMeHy Aaje AOBOJbHa cJiHHoha. flpe YNOTPEÖE CE HCNHTA N>EHA nponydJbHBOCT, TAKO AA JOJ ce Bpx 3apoHH y eTap y jeAHOj Maaoj enpyßeTH H Aysa Cji. 15 y H>y YCTHMA. MexypoBH Tpeöa AA H3Jia3e N O J E A H H A m i 0 H n 0 J i a K 0 , KANN-rcape 3a a e c T H J i a m i j y y B A K y y M y TPEÖA TeK npw cHaJKHOM ayßaiby Aa nponycTe nojeAHHe Mexypwhe Ba3nyxa H TO TeuiKO. KaTKa.ua nocTojn noTpeöa, HaponHTO KOÄ TCMHOCTH Koje ce neHyiuajy, Aa ce peryJinme npncTyn Ba3Ayxa Kpo3 Kannjiapy. To ce nocTHMte Ha Taj na e M. Tpe6a MefjyTHM HM3TH Ha yiiy, Aa he npHJiHKOM npeKHAafta aecTHJiaimje cnojbHH npHTHcaK Ba3Ayxa noTHCHyTH TewHOCT H3 öajioHa y jorn eßaicyHcaHy KamwapHy ueB — eBernya^HO CBe AO ryMeHor upeBa — IUTO ce H36eraßa Ha Taj HaiHH Aa ce npe npeKHAa uiTHnajbKa 0npe3H0 OTBopa. KOÄ ynopHor n e i i y m a n a CTaBH ce, H30CTaBA.ajyhH TepMOMeTap, H y npeAfty ixeB K^e3eH0B0r öajioHa (b Ha CJI. 15) jeAHa Kannjiapa. 4>nHa cipyja Ba3Ayxa Kojy oHa ycncaßa 1 ÄOBOÄH MexypoBe ÄO npcKaaa npe Hero IUTO Mory Aa npeljy. ) KANH^apHa H

HeoiiiTeheH

CTaje

y

u e B c e cßojHM

ryMeHH

BPXOM

3 a n y m a q (ca

ueB a K^e3eH0B0r

öajioHa.

yßyqe HCUITO

ü,a

nocTaBfl>eHa, T p e ö a j , a c e Kpaj K a n n a a p e 3HHH HajHHJKe TaqKe

öajioHa. y

ryMeHOM

AKO

ÄOÄHP

3anymaqy.

c a KayqyKOM

TO

ce ce

K p o 3 j e ^ a H TaqHo

rjiHuepHHa) KojH TaqHo

KariHJiapHa Ha,«a3H y

ueB ö y ^ e

Äa

YNOTPEÖ^aßa

H3ÖerHe, fOie3eHOB

öa^OH

ca

MajiHx KOMa^Hha nyniaqa

KOÄ

upeBa

KOJH

c e HaByKy 0 Ä 0 3 r 0 .

ÄecTHJiaunja y B a n y y M y

E. Dorrer,

Dissert. München 1926.

Tpa)KH

ynoTpeöa

BCJIHKO

ÄO^e

y y

cyKeHHM noMohy

nJiyTeHHx

HCKyCTBO«

6na-

Taicoije

cyncTaHua

n p a j e B H M a ueBH y K o j e c e CTaBÄ>ajy KannjiapHa u e B H TepMOMeTap

npH-

npaBH^iHO

HajHenocpeÄHHjoj

ueBH b Ha^a3H c e TepMOMeTap

JKCJIH

H3öymeH

3a-

floónjaibe opraHCKHX cyncTaHua y IHCTOM cTaH>y

19

X^ai]eH>e c e Bpmn npeiua Ä S T H M y n y T C T B H M 3 ; O B ^ e c e H A P O I H T O npen o p y q y j e M B J I H K0HAeH33T0p ca B O A O M KOJ'H c e H A B J I A I H n p e n o O Ü B O A H E BieBH öajioHa 3'a AecTHJiOBaite. Peii,HnHjeHTH: A K O ce oqenyjy caMO jeAHa HJIH A B C $paKUHje, y n o TpeôjbaBajy ce Kao penHnnjeHTH e n p y ß e i e 3 a u e i j e i b e Ha B a n y y M Kao iiiTO je npeTCTaBjbeHO Ha ca. 8, oAroBapajyhe BejiniHHe (3a npeTXOAHH T O K y3HMajy ce HajMaite) HJIH K O A Behnx KOJIH^HHa cyucTaHije Maae D O U E 3 a ueljeibe Ha B a K y y M y. OHe Tpeôa npeTxoAHO Aa ce n o A e c e npeMa R Y M E H H M 3 A N Y M A H H M A npeno KOJ'HX ce B E 3 Y J Y 3a U E B K 0 H A E H 3 A T 0 P A . KOÄ npoMeHe peuHnnjeHTa Mopa ce, HapaBHO, AecTHJiauHja ^a npeKHHe. A K O c e T O JKCJIH A A H3öerHe, HJIH ano c e o i e K y j e BHiiie cJjpaKUHja, cjiyjKHMO c e jeAHHM ypeijajeM KOJ'H A 0 3 B O J B A B A A A c e p 3 3 J I H H H T H peuMnaJ E H T H P E A O M cTaBjbajy N O A y u i h e O A B O A H C UeBH, H KOjH HMa OÔJIHK KaO U1TO je Ä3T X ij ip. Ha np. Ha en. 16, H KOJ'H c e JiaôopaTopnj-

CKHM

je3HK0M,

HABA

Kao

Beh

„nayK",

npeMa

oßjiHKy, 03Ha-

„Mcaöa",

„c

B H H> 4

e"

HJIH „ B H M e ". Ha Kpajy Tpeóa noMeHyra H a c TaB a K CJ] J 6 c a c j i a B H H O M no Anschütz Thiele-y (en. 17) Koj« c e H3BpcHO noKa3ao Hapo^HTo K O Ä AecTHJianHje Behnx KOJIHHHHa cyncTaHite: K O A i t e r a ce no 3aTBapaiby cjiaBHHa H b MOKe noMohy uiTHnajbKe c Aa ycnocTaBH y peijnnHjeHTy aTMOc4>epcKH npn-

Cn. 17

Cji. 18

THcaK H Ha Taj HaiHH M O M I E peuHrmjeHT Aa c e H3MeHH. F I O N I T O c e 3aT H M o n e ? 33TBOpH KOA c H OTBapajyhH b oneT cByAa ycnocTaBH BaKyyM, M O H I E c e npn OTBopeHoj C J I 3 B H H H a A A J B E Aa Aecrajiyje. T p e h a cJiaBHHa MOHce Aa H30CT3He. Joui npocTHj'H je H a c T a B a K ca T p o K p a K O M CJIABHHOM (CJI. 1 8 ) K O A Kora c e peijHnHjeHT npeKO jeAHor OTBopa Ha 2*

20

HeKcuiHKo onuiTHx npaBH^a 3a paa

cJiäBHHH MO»e AOBeAe y s e 3 y ca ciKUbHOM aTM0c e : CaMO ce ca bcjihkom yBOKÖaHouihy MO>Ke 3arpeBaite koä AecTH^auHje y BanyyMy Aa Bpiun ahpckthhm n;iaMeHOM. M H o r o je noy3AaHHje HHAnpeKTHO 3arpeBaH>e npeno K y n a T H J i a . H oBAe ce Mopa TeivinepaTypa KynaTH^a Aa noAecH ca HajßehoM 6pn)KJbHB0iiihy npeMa TeMnepaTypn KJbyqaiba cyncTaHue ( o k o 20° BHine; koa bhcoko noCTaBJbeHe oaboahc ueBH Mopa ce pa3^nica j o i u Aa noßeha); icaA ce aoCTHrHe Ta^Ka Kjbyqaiba jeAHe 4)paKUHje, TeiunepaTypa K y n a r a j i a Tpeöa Aa ce A P » « K0HCT3HTH0M. BaaoH ce y p o H H y KynaTHJio to^hko, Aa hhbo tchhocth Koja ce AecTHJiHine jiokh h c n o a hhboh tcíhocth y KynaTHJiy. BajioH Tpeöa Aa je Hanyit>eH cyncTaHiiOM HajBHine ao noJioßHHe. K a A ce AecTH^yjy cyncraHue ieß>e

THCKa

äo oBe rpaHHue

cmmaBa

oä

npHTaiKy

K j b y q a a a 3a n p o c e r a o 1 5 0 ° y n o p e l j e f t y ca

K j b y q a i h a noÄ aTMo-

TeMnepaTypoM

c^epcKHM OÄHOcy je

Ha KOÄ

TaMKacTHM

y To

BaKyyM BOÄeHe n y M n e .

H3pa»ceHo

KpHBe I

a 3a o k o 4 0 °

npHTHCKOM,

npoÄy>KeH>eM

HHTp06eH30Jia

(Koja

HHje

KOHGTpyHcaua Ha 0CH0By MepeH>a). Oä BHHe

KaKO c y yBeÄeHe t . 3b. jk h -

ÄH(J)y3H0He

b h c o k h

BaKyyM,

nyMne

3a

6e3 Kojnx ÄaHac

CBaKaKO HHje h h jeÄHa yHHBep3HTeTCKa jiaöopaTopnja,

ÄecTHJiaunja

bhcokom

y

BaKyyMy He npeTeraßjba n p o u e Ä y p y K o j y je

TeuiKO

h k o j e Hayqno Äa

H3BecTH,

H3BeÄe oÖHHHy ÄecTHJiaunjy y BaKyyMy BeuiTO h c n r y p H o , Mohn he Äa ÄecTHJiyje h

y

bhcokom

BaKyyMy,

aKo

ce

Halje

5 4 3 2 10 Kjiyvo/ta SSXS^, npeÄ OBHM 33ÄaTKOM npH HeKOM JIHTe-

mmHg

paTypHOM npenapaTy. 3 6 o r oeeTJbHBoeTH

Cn. 20

anapaType — HHKe —

n p e n a p a T e KojH c e p a Ä e Kao BeJK6aH>a, HiiiBHHa ÄHijjy3H0Ha nyMna n o CKOM 1I1KOJ1CKOM

y

HHje o n m ö p H H j e h h onncaH.

T p e ö a j i o 6 h ÄaHac Äa ce Ha;ia3H y

H3BpcHa

cb3kom

opraH-

jiaöopaTopHjyMy.

C M e

H e

h 3 6 o r Tora

Volmer-y

6ap y nor.ne.ay Ha noqeT-

HHje OBaj nocTynaK yHeT Metjy

B a K y y M y

c e

h h k s ä

a a

n p o n y c T H T H

3 a iii t h t e

c e

Ä e c T H J i a u H j n

n p n

o i h !

CyßjiHMHcaH»e K o a ^a3H HeKaÄ hhto

y

Hf.napjkHBHX

qßpcTo je

noroAHHje

OHAa

jbHBOCTH opraHCKoj

CTaae

KaA

je

oTeacaHo. xeMHjH

Aa

MaTepnja, y

oöjiHKy ce

qaja

KpncTajia

npeiHiuhaBaae

npeKpHCTajiHcaBaibe I~Io3HaT

napa

npHMep

npHMeayje

ce

npn

3ao6HJia3ehn BpuiH

ycjieA

noctynaK

AnpeKTHO

TaKo TaiHy

cyöjiHMHcaiteM,

«apoHHTHX

npeTCTaBJba

oHaj

xjialjeiby

0AH0ca

npeqmiihaBaibe HapoHHto

koa

a

npe4>a3y> Hapo-

pacTBopj o A a .

y

x h h o h a.

CYÓJIHMHCAIBE Be^e

H3Me^y

cyncTaHua Koja

THJ'OM HQjiy ca

ABa

Kojy

Tpeóa

Majio

npejia3H

H36ymeHa

HcnynqeiteM

CTaKJio

r o p a e M

CTaioiy

CTa^Hhn

onex

CTaK^o

Ha

rope,

IIITO j e

HJIU

A K O

./IH

cyó^HMHine

TeK

A J I H S A P H H , K O A

—

noüiTQ

ce

TO

Moate

H

noTnyHO

y

ce

OB,a,e

TOMe,

.na

Hero

napa,

cpa3MepHO

AKO

AIYJKHMO yBeK

ce

npHKJbyqeHOM

HJIH

cjiyqaj

ce

caojeM

y

H

BejiHKoj

KJbyqaita

6h

rip3KTHqH0

Ha

He

BofteHOM

np.

H ce

3arpeBa

y

KOHAeH3yje).

cyBHme 3aTHM

K0HfleH3aT0py,

nexa-

HJIH

p a c h o n a

TeK

3a

Ha

x-íialjeite. K3a

je

necTO O H

HHflycTpHjH. Mory

K a a ce y

TeinnepaTypH n0H0B0

HajnoroAHHjH MaTepnja

y

aa

He

ce

ocHHBa

JieüKe

3HaTHo

H > H X yBO,n,H

BO^eHa

Bo^eHe

nape,

KOHAeH3yjy

y

TeuiKo

BOAH

H

,na

je^HOM

TeopHjcKH

H

caMO

Hajnpo-

pacTBopHa,

p3CTB3p3.

cyncTamje H enpyBeiy,

BehHM

Kojn

OAOSAO

H36erjio

je

n a p o M

KJbyqaita

Koja HX n p a r a ,

HM3MO,

ca B O A C H O M

BpaTOM

KOJ'H

peTopia).

HJIH

anapaT

ca

B o A e H o M

atina O T n p n í i H K e 2 mi

pa3MepaMa

napoM,

He

cMe

ca M a ^ o aa

njiaMeHHKOM BejiHKO nycTH

nocTaBH

aa

cya

6yae

ao

CT3BH Boae

CTpyj«

ce y

6^H3y

BO^A

XBaTaite

oA

TeMnepaType

y

Kojy

Tpe6a

jeflHe

H

Sa^OH TpehHHe

KA.yqaHja

yc^eA

NPHKJBYQEHOM flecTH^aTa

3 a M y-

n p o c T p a H

BHiue

3anpeMHHe

Boae.

napoM.

cyncTaHua,

je^aH

HanyH>eH

noBehaBaae

3a

napoM,

Boae H sarpeBa

n a p y K o j a ce p a 3 B H j a y H e c e c e ,HOH>H K p a j j i p y r e

n o K a 3 y j e a a j e c y n c T a H u a n c n a p j b H B a c a BOiieHOM

H3BoljeHje

AyrHM

y

npeinuihaBa

e n p y B e i e H a n y i i e H e ;ie,noM, H JIPHCH A O K c e H a H>OJ He KOHfleH3yje K a n a n u a

ca

ce

TO

H H A R T O

ynoTpeójbaBa

HcnapaBajy

nape

« o K J b y q a i b a (KaMeHMHhii 3a KJbyiaH>e!). Y

3a

(JmjiTap-

fía^OHHMA, ce

(6ajioHMHh ce

fla 6 H ce H c n m a j i o na JIH j e H e x a c y n c T a H u a i i c n a p j b H B a

AecTHJioBaTH

Kpnropite

JIGBKOM

Koja

Kao

BAKYYMOM

TanKe

Bo^e,

napoM

cHereMy (B. a o j i e )

K a n A H u e

&& ce

cyncTaHue,

jiOHqHhmvia,

cyncTaHija

xeMHCKoj

nnje

aanoHy

CBOMC

c r a B H c e jeflHa Majia n p o ó a

faeibe

xjia^HOM

BJiaacHe

je^HHM

C I A ^ O

npe«MiuhaBaii>a

MaTepnje,

3ajeAHO ca B o a e n o M

CTHJ'H

Ha

Z[a

^ o a e

neumaHOM

cnpeqaBa

CTaKJio=

na3HTH

ca

H3MHH

Beh

TaqKa

Ha

oxjia^H.

MHore

BHrne

craKJio

c e ca^,a

3ryuiH>aBa

KOJIHIHHE

THMnepaTypn,

Tpeóa

BajKaH

JiaóopaTopnjH,

Ha

Behe

BPIIIHTH H y

flecTH^oBaibe ÜBaj

cpeAH>eM

caxaTHo

N;iaMeHOM

BHiiiecTpyKHM

caxarao

flp.

H

BHCOKOJ'

cy6jiHMHcaii>a ce

Bpejio

4)HJ?Tap-xapCBOM

A K O

(JmjiTap-xapTHja

m -

eraBH

Kpne.

r o p a e

ueBHiua Ha

MaJima

ce

ce

CTaKao.

ce

peTopTaMa,

a p y r o

UITHNAJBKOM.

,na

AOH>e

n o j a je y

Hcnapwjia

nofee

ÜOKPHTH

BJia>KHe

3aMeHH

Hero

Cy6jiHMHcaK>e pHMa,

ce

Ha

cyójMMHiiieMO

FLA

anapaTy

MaftH

je

3RO#Ho H a

OKpyiviOM H

0A03r0

jiaraHHje

KpncTa/ie:

Harpar

KOMaAHhHM

noKpnje CTaK;ia,

npHTerHy

Koja

MOMte

BejiniHHe.

nocTaBH

06a

H

o6pa3yjyhn na^ny

je^HaKe

HBHIÍS

MecTa,

cyncTaHua

xoheMO

OÜHC3HOM

npeKo

inoryhe

xJia,n;njio, M o a c e

xapTnje,

Hernro

BHiiie

ce

TO

cyncraHiie

KOJIHHHH3 CTaK^a

cy6;iHMHcaTH,

Ha

3arpeBa

KynaTHJiy,

MAIBHX

caxaTHa

23

cyncTaHiw y IHCTOM CTaay

,Ho6HjaH>e o p r a H C K H X

TCK

BO,ne

(^a

6H

Koja

ce

J Y R A Í K O M ca^a

yBO^;«

24

HeKOJiHKO oHuiTHx npaBHjia 3a paa

AocTa jana CTpyja nape. UInpoKa ueB 3a yBoljeite nape Tpe6a Aa Aonnpe AO

AHa

6^H3Y

óajiOHa H Tpeóa AA je cnpefla

HeuiTo

y JiaóopaTopHjH

AKO

Jiaunja

3a

npOH3BOAH

AOBOA y

(CJI. 2 1 ) .

caBHjeHa He

noerojn nape,

BOACHC

HHCT3napa

ce

jeflHOM JIHM6HOM Ka3aHHeTy

HA KOME ce HA^A3H n e a 3A OABOA

nape H

BOAOMEPHA UEB H KOA Kora j e KPO3 OTBOP HA Bpxy n o M o h y NJIYTEHOR 3anyinaHa np,OAyraqica

ByqeHa Koja

Aonnpe

ycnpaBHa AHA

craKjieHa

KA3AHHETA,

nao BCHTHJI CHrypHOCTH.

CJIY)KH BHJIY

AO

ce

IIECTH^YJE

CTHJIAT HE OTHNE

CBE

AOTJIE,

f l p npaAOK

AC-

A K O GYNCTAHUA

óncrpo.

KPHCTAJINUIE H H3£BOJH ce y ^E^E,

ueB

H. Koja

UEBH 3A x a a -

TO ce 3A KPATKO BPEME AEJIHMHHHO

HcnyCTH BOAa H3 K0HAeH3aT0pa; napa Ta^a HCTona Cj¡. 21

UEBH.

KpHCTajje H cyncTaHua

c e MEJJYTHM NA3HTH, ÓHTaKa

ycjieA

eraHuy.

T o r a UITO

HeK0HAeH30BaHa

napa

nyuiTan^e BOAE 3a XJIALJEFBE y

RIOHOBHO

n o T e i e H3

KAFL c e NPEAY3HMA OBA MEPA, Aa

HE AO^E

noB^aqn

Bpeo

Mopa

AO

CO6OM

ry-

« cyn-

K0HAEH3AT0P

Mopa

Ce BpUIHTH o6a3pnBo. r i o 3ABPMETKY AecTHJiauHje, npe Hero UJTO ce HCKJbyiH AOBOA nape, Mopa ce npeKHHyTH Be3a H3Mel)y ueBH 3a napy H óa^ioHa, j e p 6a TeqHOCT

«3

fíaioHa

y Ka3aHqe., H a

cenHane

Mordía Aa nonne Kpo3 ueB 3a yBoljeite nape a y a n j e

OBO

ce

HapoqnTO

Mopa AS na3H, aKo ce napa y3HMa H3

HHCTajiaunje 3a BOAeHy napy. M a i t e KO^HMHHe cyncraHue Mory c e AecTHAOBa™ ca BOACHOM napoM H H3 JEAHOR A0B0JbH0 BejiHKor S a c o n a 3a (JjpaKUHOHacafte ca BHCOKO noCTaBJbeHOM OABOAHOM ueBH, a napo^HTO junco HcnapjbHBe MaTepnje H 6e3 AOBO^eft-a nape, npocTO 3arpeBan>eM Bpjio

TeuiKO

H o M BOAeHOM

Hcnap/bHBe

napoM.

napHoj ueBH caBnjeHoj 3a AOBOA nape

ca BOAOM.

cyncTaHue

nperpejaBaae

AecTHJiyjy ce ca

nperpeja-

ce BpniH Haj3roAHnje y jeAHoj 6a-

cnnpajiHO y KOHyc, Koja ce yKjbyqn H3Mel]y ueBH

H SajiOHa, H 3arpeBa njiaMeHHKOM.

Hajia3H ce y yjbaHOM Kynarajiy

BajioH ca cyncTaHUOM

Koje je 3arpejaHO Ha BHuiy TeMnepaTypy

(OKO 150°). EpeHTyajiHO ce H 6e3 , n p e r p e j a « a Ao;ia3H AO unjba, ano c e y 3a AecTH./i0BaH>e y KOMe c e Hajia3H cyBa cyncxaHUH KynaTH^y

yBOAH

UITO

j e M o r y h e cyBjba napa.

6anoa

H Koja c e 3arpeBa

y

C y n c x a H u e , n o j e ce ¿iaKO

p a c n a A a j y a HcnapjbHBe c y , A e c T H A y j y c e KaTK3A ca BOACHOM napoM

noA

CMatbeHHM npHTHCKOM, AaKJie npn CHHaceHoj TeMnapaTypa. O TeopHja

flecTHJiaijHje

c a BOfleHOM n a p o M : HAeajiaH cjiynaj npo-

ueca HM3MO oHAa. KaAa je MaTepnja, Koja Tpeóa Aa ce. a e c i w i y j e , -y B O A «

flofiHjatbe opraHCKHX cynciaHUH y

ctaity

HHCTOM

?5

Ma.no pacTBOpHa (npHMepn: ronyon, 6poM6eHH A N O H H n a p e B O A E H cyncT3Hije J E A A H H A ApyrH He yTHHy H J I H Ma;io y T n q y . CacBHM ApyKqwjH O A H O C H HacTynajy K O A MaTepnja Koje c e Meuiajy ca B O A O M (a^iKoxoji, cnpheTHa KHcejiHHa); OB^e c e jaBA>a T e o p n j c K n KOMnjiHKOBaHa C J I H K 3 eH HanoH n a p e Aa p a c T e npeMa K P H B O J ' Koja j o j j e eBojeTBeHa, H T O He3aBHCH0 O A HanoHa n a p e B O A E . f l o j a B a K J b y q a f t a h e A A HacTynn Ka A 3 6 n p napHHx npaTHcana o 6 e MSTepwje 6 y A £ paBaH 3TM0C(J)epcK0M npHTHCKy Kojn y T O M MOMeHTy BJia^a. O B O j e c j i y q a j , Kao C I T O c e Moace n p o I H T S T H H3 KpHBHX npHTHcaKa n a p e , noA HopMajiHHM ycjiOBHMa ( 7 6 0 m m ) KOA 9 5 , 2 5 ° . HepacTeopHa

TaqHHje

HJIH

3OJI,

HHTPO6EH30JI),

KAA3

AAK.RCE

BO^E

H a OBOj T e M n e p a T y p a 639 mm, H>HXOB 36np

H3HOCH A3K;IE

TeH3Hja 6poM6eH3o;ia 121 m m , TeH3nja 760 mm.

y n a p H o j 4>a3H c e npeMa TOMe no ABoraApoBOM npaBHJiy n a d a s e o ó e K0Mfi0HeHTe y 0AH0cy 1 2 1 : 6 3 9 , T O 3H3MM Aa h e y n a p H o j $ a 3 H 6 H T H 5 , 2 8 nyTa BHiue MO^eKy^a BOAe Hero jiu MOfleKyjia 6poM6eH3o;ia. A n c o JiyTHH O A H O C y KOMe n p e j i a 3 e 6p0M6eH30./i H B O A C H S n a p a A o 6 n j a c e np'oC T O aKO c e y3My y p a q y H MO^eKyjiCKe TeacnHe. H a 1 M O J Í 6 p o M 6 e H 3 o ; i a Mo^eKyjiCKe TejKHHe 157 AOJia3H 5,28 MOJIOB3 BOAe MO^eny^cKe TejKHHe 18, hjih c a 157 TejKHHCKHx A e ^ o B a n p B o r npeji33H S , ' 2 8 - 1 8 = = 9 5 A e a o B a B O A E , L U T O O A R O B A P A npHfíjinjKHo O A H O C Y 6 p 0 M 6 e H 3 0 ^ : B O A A K a o 5 : 3 . n p e M a TOMe c e MO>Ke, n o 3 H 3 B a j y h a KpnBy TeH3Hje HeKe MaTepHje Koja c e He Mema ca B O A O M , J I S K O Aa H3paqyHa npHÓJiHJKHO CTeneH Haene H c n a p j b H B o c r a ca B O A C H O M napoM caMO n p a ó ^ H J K H O CTora H I T O npeTnoCT3BK3 MeijyCOSHe HepaCTBOpjbHBOCTH npBKTHHHO HHje HHK3A HCnytt>eH3. O AecTH^suHjH peAH VII. A. 2 b.

ca BOAeHOM napoM

noA

yKJiaH>aH>e p a c T B a p a i a IlomTO

KOA

CM3H>eHHM npHTHCKOM y n o -

AecTHJiau,HjoM

npenapaTHBHHx opraHCKHX

Tpefía

P3AOBA

BPAO

qecTO

AA

c e H30/iyjy c y n c r s H u e H3 pa36Aa?KeHor pacTBopa, TO OB3 o n e p a a n j a cnaAa y noc^oBe

KOJ'H

ce

CBSKOAHCBHO

Bajyhw Ha n a p H O M

H;IH

o6aBjb3jy.

E T S P

ce A e c m n y j e

K y n a T H J i y , Hajóojbe y 3

B O A C H O M

33rpeBaynoTpeóy

3MHjacTor K0HAeH33T0pa, H n o c j i e eBeHTyajiHor npeqHujh3B3it>3 n0H0B0 c e YNOTPEFÍJBABA.

AKO

33APJKH

HCNAPJBHBE

KHCEJIHHE,

H3MyhKa c e c a

P A C T B O -

P O M c o f l e , a n o HanpoTHB caApwH HcnapjbHBe 6 a 3 e , H3MyhKa c e 3a p a 3 SJIAJKEHOM

C Y M N O P H O M

NOUITO

H cnpeqH^o

je eTap

K H C C J I H H O M .

BeoMa

H C N

Aa c e He 3 a n a j w ,

a p

JB H B,

TO

ynoTpeó^aBa

Aa 6 H c e H 3 6 e r ; r a r y ó n i i n

ce Kao peiuinHjeHT ó o u a 3a

u e l j e a e Ha BaKyyM, K o j a c e njiyTeHHM 3 a n y m a q e M Beace H

Ha HHjy c e OABOAny neB, paAH CHrypHOCTH,

c a paAHor C T O ^ a . í l p n

paAy

ca e

T

p o

M

H

CT3BH

C B H M

3a K0HACH3a.T0p

upeBO ^3KO

TSKO

A3

BHCH

3 A N A J B H B H M

26

HeKojiHKo onuiTHX npaBHJia 3a paa

p a c T B a p a q H M a He CMe na p a ^ H O M O T B o p f i H n jia m e h.

ciony

Harje

Aa

ropn

A k o Tpeöa Aa ce Hcnape b e ji h k e k o j i h h h h c p a c T B a p a q a h ano ce nocne aeroBor yKJiaH>aH>a xohe Aa AecTHjiyje H cyncTamia noja je 6H.ua pacTBopeHa, to, aa 6h ce H3Öerao cyBHiiie bc^hkh cyA, nyiina ce pacTBop H3 a e B K a 3a K a n a i t e Äa ce yjiHBa y noroA'aH öajioH 3a 4>paKUHOHHcaibe h to y 0H0j MepH y koj'oj' pacTBapaq omapaBa (KaMeHHHhn 3a KJbyqaite). A k o He CTOja Ha pacnojiojKefby napHO KynaTHJio, Beh ce MOpa AecTHflOBaTH H a boachom Kynamny, Mopa ce npn cbskom AOflHBaii>y (aeBaKl) Äa yracH miaMeH. ripn TOMe ce oöhhho 6pace AOJia3H ao uHJba, a«o ce iHTaB pacTBop omapaBa H3 je^Hor Beher öa^oHa hjih epjieHMajepa, H Ta^a ocTaTan ca Majio pacTBapana (a;iH nomyHo) cnepe y MaH>H cyA. M a j i e K O J i H H H H e JiaKO HcnapjbHBHX TeqHOCTH Mory Aa ce otCTpaHe HcnapaBaiteM m enpyBeTe hjih H3 Majior öa-noHHHha ahpcktho Ha BO^eHOM KynaTHJiy. EnpyBeTa ce cb3kh nyr nanyHH caiwo Ao bhchhc oa 2 — 3 cm h yBen iiohobo Aony&yje. 3a BpeMe KJbyqaifaa Ha boachom KynaTHJiy Mopa ce cTaJiHO M y h n a T H hjih m e i i i a t h TaHKHM craK;ieHHM uiTanoM. Flo oßoj npocToj mctoah H3BOAe ce CBe n p e i x o ^ H e n p o ß e ca p a c T B o p H M a H HcnnTyjy ocoÖHHe ociaTKa. PacTBopn cyncraHiiH, Koje ce JiaKO pacnaAajy, HcnapaBajy ce y tom ijHJby Ha caxaTHOM CTaKJiy hjih y Majioj LuoJbH 3a KpncTajiH3auHjy 0TB0peH0 Ha Ba3Ayxy. A k o ce paah o TOMe, Aa ce n o m y H o OACTpaHe pacTBapa^H, kao iiiTO cy a J i K 0 X 0 J i hjih 6 e H 3 0 J i , OH^a to He Moace aa ce yqnHH Ha napHOM hjih boachom KynaTHJiy, nouiTO TaiKa Kjbyiaita ca nopacTOM KOHueHTpauHje CBe BHiue h BHiue pacTe; a h koa e T p a to ihhh TeuiKohe. Oha3 ce y3HMa yjbaHO Kynamflo, hjih ce jorn uernhe paAH y BaKyyMy KojH ce ycnocTaBH KaA KÖHAeH33T npecTaHe Aa Kanjbe. /JoBOJbHO je Aa ce ct3bh Kanwjiapa h Aa ce öaJiOH Ap®n y nopuejiaHCKoj uiojbh hjih einaJbHpaHOM JiOHuy Ha cpeAHjOj TeiunepaTypH y3 AHpeKTaH npHKjbynaK Ha nyMny, Aa 6h ce BehHHa pacTBapaqa, a TaKo^e h boa3, 6p30 h norayHO yKjioHHjia. C T a K J i e H H c y a o b h t a h k h x 3 h a o b a, Kao e p a e H M a j e p n , ö a j i O H H ca p a b h h m a h o m h e n p y B e T e , He CM'ejy ce h h k a a e ß a K y n c a T H , aok ce to Moace yBeK y i h h h t h ca OKpyrjiHM öajioHHMa eßeHTya^Ho ca öouaMa 3a ueijeite na BaKyyM Koje ce MeijyTHM Mopajy naÄJbHBO Aa 3arpeBajy. Ako Tpeöa Behe KOJiHHHHe pacTBapaqa Aa ce oAcrpaHe HcnapaBa&eM y BaKyyMy, Kao uito ce to BehHHOM Tpa>KH koa oceTjbHBHx MaTepnja, BpiiiH ce KOHAeH3aunja paAH y6p3aH>a y He oAseh MajiOM K0HAeH33T0py H pei^HnnjeHT xjiaAH npeMa norpeÖH joui jieAOM. KoHAeH3aTop HHje noTpeöaH, aKO ce 3a peuHtinjeHT y3Me ofinnaH öa^OH 3a 4>paKiiH0HHcaii>e koj'h ce nojio»cH Ha bcjihkh jieBaK CHaöAeßeH oaboahhm apeBOM h 0A03r0 no^HBa boaom h3 boaoboa3. Kpaj oäboahc ueBH 6a;iOHa 3a AecTH^aunjy Mopa Aa Aonnpe ao cpeAnuiTa 6ajiOHa koj'h

floóHjaibe

opraHCKHX cyncTaHUH y

cnyacn nao peuHiiHjeHT. OBaj je ype^aj HapoHHTo TpHcaite BOAeHHx pacTBopa. ypeljaj, KOJH je npHKa3aH BAKYYMY

6E3

NPEKHAA

27

HHCTOM CTatby

noroAaH 3a KOHijeH-

Ha CJI. 22, A03BOJBABA AA ce ucnape y

BEJIHKE

KOJIAQHHE TC^HOCTH,

HAPO^HTO BOAC.

Kp03 cjiaBHHy ce c BpeMeHa Ha Bpeine HaAOKHa^yje ycncaBaiteM H3 pe3epBoapa KOJiHiHHa TeqHOCTH Koja je npeiujia. yHyTpauift>H npeqHHK ueBH 3a AOBOA TenHOCTH T p e ó a A A je HITO je Moryhe BehH. CTA^HO n e H y n i a i b e BOACHHX paCTBOpa npH ACCTHJiaiíHjH y3poK je necTo ' jbyTffcH H ryÓHTKy BpeMeHa. OBO ce M ( m e cnpeiHTH T3KO Aa ce pacTBopy AOAa OTNPHJIHKE 3 % OA FTEROBE 3ANPEMHHE H 3 O-

a M H í a j i K o x o a a , Joui cnrypHHje ce n o c T n » < e UHJB, ano ce y npa3aH 6a^0H cnpeMaH paBa

3a

BOAA.

TeMao

Aecm/ioBaite Zl0B0AHa

ycHcaBaita

ijeB

cn. 22

p a c r B o p y 0 H 0 j MepH y nojoj Hcnay OBOM c a y u a j y Ha CBOM yuihy cyaceHa, a

ycncaBa je

ce Moate

TaiHO

Aa

noASCH uiTHnajbKOM ca 3aBpTH>eM

(en. 22). EKCTpaxoBaH>e Jla 6H c e HeKH peaKUHOHH n p O A y K T , KOjH HHje qBpCT KpHCTajIHHHiaH

Kojn He MOHÍE AA ce ueAH, n3AB0jH0 H3 BOAeHe c y c n e H 3 H j e HJIH TaKoije H3 pacTBopa, HJIH AA 6H c e OABOJ'HO OA HepacTBopHHx M a T e p n j a noje ra H

n p a T e , e K C T p a x y j e c e noroAHHM pacTBapaqein; n a o T3K3B c n y m H eTap.

C

J

. J \.

Tano

ce

Ha np. e K C T p a x y j e

KOHAeH33T

BehHHOM AO6HBCH

AecTH^auajoM ca BOACHOM napOM, yKOJiHKO ycJieA Hapo^HTO üOBOJbHHX

OAHOca

Ha

rpaHHqHoj

n o B p u i H H H HHje

Moryhe

AHpeKTHO OABajaft>e. 3a O A s a j a f t e ABS crioja y n o T p e 6 j b a B a ce ^ e s a n 3a O A B a j a i t e , a KOA MaitHX 3anpeMHHCKHX Ko^iHqHHa .neB S K 3 a K a n a t b e (CJI. 23) (cBe' AO 25 mi 3anpeMHHe) KOjH je KOHCTpyHCaH Ha HCTH HÜHHH, H 'Hija OABOAHa IíeB Tpeóa Aa 6yae HajBHiue 5 cm A y r a H ( 3 6 o r " oraiía^s) KOCO n p e c e i e H a . 3a e n r i a r e TeqHOCTH y jieBaK 3a oABajaite c^yiKHMO ce yBeK oóh^hhm JICBKOM. n o c j i e pa3ABajaita AOftH cnoj ce HcnycTH Kpo3 cJiaBHHy, a r o p i t H cjioj ce H3JiHje Kpo3 T o p a n Tyóyc (jieBatc). Tpe6a yBeK npnqeCa. 23 k3th Aa ce Teaca TCMHOCT npaKynH Ha AHy, a KOA e K c j p a xoBatba eTpoM Tpeóa Hapc>HHTO H36eraBaTH, Aa c e , ca eTpoM H3JiHjy H AeJIOBH BOAeHor pacTBopa. Majie n p e T x o A n e n p o ó e H3AB3jajy ce y ueBH 3a K a n a a e y Kojy ce npeTXOAHO ycncajy (CJI. 9).

28

HeKOJiHKo onuiTHx npaBiwa 3a paA

ripa

MyhKaity

3Hje, ca

Henor BOAeHor pacTBopa, a join BHiue Hene cycneH-

HeKHM opraHCKHM

eMyji3Hje

pacTBapaqeM,

Hacrajy necTO Bpjio He3roAHe

Koje OHeMoryhyjy TaqHO OABajaibe.

HajcnrypHHje cpeACTBO

npoTHB OBora je, Aa ce yonuiTe H36erHe itaxoBo cTBapaibe, Ha Taj HamiH, iiiTO he ce Meiuaite

BpiunTH

nam^HBO.

Rajba

cpeacTBa Koja A e j i y j y Ha-

cynpoT CTBapaity eMy;i3Hje j e c y : CTBapan>e BaKyyiua y jieBKy 3a 0ABajaH>e, AOÄaBaifce

hckïwihko Kan« ajiKoxojia, 3acHhaBaite BOAene eHa y te^HocT. P a f l c a KOMnpHMOBHHHM racoBHMa CßaKa je yHHBep3HTexcKa jiaóopaTopHja AaHac CBaKano CHaÒACBeHa qemqHHM ôouaMa Koje caApace HajBajKHHje racoBe koj'h ce ynoTpeöjbaBajy y KOMnpHMOBaHOM c r a n k y . TO

Cy

1. K H C e O H H K ,

boaohhk,

a30T.

2. yrvbeHAHOKCHA, xjiop, aMOHHjaK, cyMiiopAHOKCHA. E^eMeHTH Hajia3e

CTaiby.

ce

y

noA

1.» ^nja

6oM6aMa

KnceoHHK,

y

kphth^h3

racHOM

T e M n e p a T y p a jieacH B p j i o

CTaity,

b o a o h h k h a30T

MaTepuje

noA

2. y

hhcko,

t e h h o m

Hajia3e ce BehHHOM KOMnpnMOBaHH

Ha 150 aTM, y qejinqHHM óoijaivia o a 10 JiHTapa 3anpeMHHe;

OHe caAP^e

Pa« ca KOMnpHMOBaHHM racoBHMa

31

Beh npeMa n y i t e i t y 1,5 cbm raca I I O A aTMOccjjepcKHM I I P H T H C K O M . 3aBpTH>H KOA 6oua ca B O A O H H K O M HMajy oöpHyT X O A 3aBojHHixe, Aa ce 6 o u e ne 6 H rpeniKOM nyHHJie K K C C O H H H K O M . C ß e 6 o u e 3a r a c o B e y J i a ö o p a T o p H j n T p e ö a Aa c y CHaöÄ e ß e H e p e a y K U H O H H M B E N T H I H M A , o qnjeM ce HcnpaBHOM OApacaBaiby Tpeöa Aa öpnHe acHCTeHT. YnoTpeöa caMO naaBHor BeHTHJia o r e KaBa pery^acan>e CTpyje raca, H B O A H y C B 3 K O M c^ywajy a o cyBHiue B C J I H K C noTpoiiiH>e. C 3 a cße racoBe (H 3a xjiop) Mory ce ynoTpeÖHTH K O H y C H H B e H T H J I H OA A J I Y M H H H J Y M O B E 6pOH3e Koje Mome jeBTHHO Aa HanpaBH C B 3 K H BeoiT MexaHHn a p (CJI. 27). ripH C B H M p a a o B H M a ca r a c o B H M a — 6 H J I O T O H 3 q e ^ H M H E 6oije 6 H J I O H 3 KnnoBor anapaTa — MOpa C e B p i U H T H KOHTpOJia 6 p 3 H H e CTpyj a ii> a. 3a T O je AOBOJbaH M 3 J I H ö p o j a q M e x y p oBa, HanyiteH K O H U . C Y M N O P H O M K H C C J I H H O M — C E M KOA AMOHHJAKA — Kojw M O M T E A A ce N P H Q A P C T H H A caaiy 6 o a y . BehHHOM he ce, paAH HCT0BpeMeH0r cyrneita, Y K J B Y Q H T H J E A H A H C N W P A ^ H U A Koja H E 6 H T p e 6 a . n o Aa öyAe H3 Aßa Ae.aa ca öpymeHHM caCT3BK0M, jep ce npn HajMaH>eM HaTnpHTHCKy orßapa 1 . AKO racoBH Tpeöa HapoHHTO Aoöpo Aa ce cyuie, TO CJI. 2 7 H«je AOBOJbHa J E A H A H C N N P A ^ W A A ca K O H U . C Y M N O P H O M KHce^HHOM. TaAa ce yKJbyqe joiu 1—2 U - ueBH, Koje ce HanyHe ( } ) 0 p n e H T 0 K C H A 0 M K O J H ce pa3acTpe no CTaK^EHBJ B Y H H . A M O H H J A K ce npOBOAH K P 0 3 paCTBOp K a ^ H j y M X HAp 0 K C H Aa 1 : 1 , H 3 3 T H M paAH cytueiba joiu Kpo3 Topaib K O J ' H je HanyiteH ca I B P C T H M K O H H C a O . Tpeöa HMaTH Ha yMy äa ce ca yoÖHiajeHHM jiaöopaTopHCKHM npnöopoM He Monte aa pa.nn ca racoM H 3 öoue y 3aTBopeHoj anapaTypw noa I I P H T H C K O M . A K O ce Ha np. >KejiH na ce H C K H pacTBop, y KOMe ce OÄHrpaBa peaKUnja, OCT3BH aa CTOJ'H noÄ I I P H T H C K O M H2 HJIH C0 2 , TO ce He cMe cya 6e3 flauer aa npiiKJbyin Ha öouy ca racoM. 3a OTnyinTaite npnTHCKa H3 anapaType yKJbyqH ce y BOÄ 3a rac je^Ha T-ueB I N J « ce O Ä B O Ä H H KpaK BeHce ca je^HOM CTaK^eHOM ueBH Koja je ypoaeHa y UHJiHHßap ca K H B O M HJIH B O Ä O M . 3rojiHHje je na ce y TaKBHM cayqajeBHMa nocjiyÄHMO K H n o B H M anapaTOM, HJIH K O Ä A 3 0 T A , r a c o M e i p o M , KOJ'H je HanyibeH H 3 öoMöe. HcKycTBO Kaace Aa ce r a c cyBHiue pacnna, j e p noqeTHHK BekHHOM yonuiTe iinje pa3MHCJmo Koje cy My K O J I K ^ h h c raca noTpeÖHe 3a H>eroBy peaKUHjy; TO MeijyTHM Tpeöa AA ce yqHHH. C B H racoBH K O J H cy y peAOBHoj ynoTpeön, ceM a30Ta, Mory ce y o i y q a j y noTpe6e Aa AOÖnjy no jeAHOCTaBHHM no3H3THM MeTOAaMa.

Be3a H3Meljy qejiHqHe öoue H HcnnpajiHue Tpeöa yßeic nocjie ynoTpeöe KHHe, aa 6H ce cnpeqH.no na ce cyMnopHa KHcejiHHa nonHe y ueB H «onpe ÄO 1

aa ce npeöoue.

HeKcuiHKo onuiTHX npaBH^'a 3a paß

32

3 a r p e B a H > e n o A npHTHCKOM AKO CTBopn

ce

pa,n;H

noBehaita

H>HxoBe Tanne K j b y q a i t a , ceM

y cTaKjieHy

r p e ß a j y , 6HJIO y 3aTB0peH0M MeTajiHOM c y A y

aTMO-

ueB y Kojoj

c e 3aTHM 3 a .

(ayTOKJiaß).

OBO je, Kao

IIITO c e jiaie

Koje c

OBHM

OÖHHHO

He

npHTHCKa

peaKitHje,

nouiTO

HAe y n o p e A O , npoy3pOKyje

no-

6 e 3 3HaMaja j e 3a 6p3HHy

HHKaKBy

3H3THHjy

npoMeHy

KOHUEHTPAUHJE.

nouiTO

ce

pacTBopH

BehnHOM

Kojoj npHTHcaK n a p e pacTBapana Ha TeMnepaTypaMa H Ca 3H3THHM

npHTHCUHM3.

eBeHTy3JXH0 H a e r a j y A3 o q e K y j y MHHHMO

ynoTpeöJbeHor

O npHTHCUHMa,

npeACT3By

nape

pacTBapana.

snco^YTHE y

ueB.

ueBH

3acHheHe n a p e ,

T3C0B3 KOJH

KojH c e HMajy

T p e ö a ceÖH Aa Ha-

Ha OCHOBy

MH y 33TBopeHoj

yBeK npHTHcaK

TO c e

H3HaA 100° HMa Aa paqyHa

p e a K u n j e y 3aTonjbeHoj ueBH,

pacTBapaqa,

peaKunja

BHiue

Y 3 O B e Ce 3AHp3]y H npHTHCUH

H3BCCHy

ueBH y

OÄpetjyje y H y T p a m i t H npHTHcaii,

3HaTHo

npiwiHKOM p e a n u H j e .

npnjiHKOM

npHÖJIHJKHO

P3THBHHX

Koje Jie^Ke

3 a r p e B a j y y 3aTonjbeHoj

Kp HBe HMSMO

Te H3Hj e KOA

npena-

T. j. pacTBop

nopeA

flpHTHCSK CTora He 3ABHCH OA

KOJIHHHHC

pacTBopa

AJIH KSKO n p e

KOJH

je

CT3BÄ.CH

CBera T e n H a BOAA, a

CTora

H pSCTBapa^H KOJH CaAP^fe BOAe, H3 BHCOKOj TeMnepaTypw NPSBHJIY

pacTBapajy CTSKJIO, He nyHH c e ueB n o BHiue

npn;IHKOM

OA no.noBHHe 33npeMHHe.

peaKUHje

AKO c e

CTBapa r a c , H3HOC CJIOÖOAHOR

r a c H o r n p o c T o p a n r p a HapaBHo y j i o r y y OAHOCHM3 NPHTHCKA. YOÖHHAJEHE

UEB H

JeHCKor

3a

p a a

CKOM

OA

CT3KJIA

y3Me y

o Ö 3 H p XCMHCKO A^JCTBO

c a npHJiHHHOM CHrypHomhy THCKS O A 2 0 A O 2 5

Oße

ueBH

noA Mory,

n p H T HAKO c e

He

HA CT3K./IO, Aa

ce

H3Ji0JKe AejcTBy

npn-

aTMOC^epa.

Tpeöa

yBeK

Aa

c e nyHe

noMohy

jieBKa, yHyTpauiKbH 3HA y 6JIH3HHH MecTa Ha KOMe h e c e BpuiHTH 3aTanaH>e Mopa Aa ocTaHe HHCT.

O

p a A y ca OBHM neBHMa y n o p e A H B. III. 1. AKO c e ca TeMnepaTypoM HcejiH Aa HAe caMO A o 100°, ueB c e yMOTa y Kpny H oKaneHa n o M o h y KaHana HJIH )KHue 3arpeBa y HapOHHTOM B O A C H O M CJI. 28

KynaTHJiy.

33

3arpeBaH>e ncm npHTHCKOM

A K O c e HE c T B a p a YMECTO

ca

NPHTHCAK,

NATEHTHHM SATBAPA^EM, K o j a c e

PaA

y

3aTonjbeHHM

pe^IATHBHO Jbanajy

MaJie

a n o j e HACTAJIH

OJIOBHHM N P C T E H O M

nocTeneHO

a TO c y

Y

6aHe. A y r o K J i a B e T p e ó a K o A

CBHX

cy

3arpeBa™

PF UNGSt-y

yBeK y

o

CJIHKS

ycjieA

H>nxOBe ynoTpeó-

KOJ'H HCTO-

cyAOBH (CJI. 2 8 )

ce

3anTHB3

q n j e c e MATHUE peAOM

Kao

yjbaHOM Tpefia

ayTOKJiaB3 OA

NAPOMHTO

Hcnpo-

KynaTHJiy. A a

3 a IU T H T e

ce

(J)H3H^KHX 3aKOHa CTBOPH

ce Ha 0CH0By

Aa

Kynarajiyi

KOHCTpyKijHje

ÍIPHTHCKOM

noTpeÓHO

npeTXOAHO NPNÓJIHJKHA

pa3He

U e B H no

p a A o B a ca

o I H. H C T O TSKO j e

3aTBopeHH

MBJIH,

c o A a B o a y

KOJIHIHHC

floKJionaií

6 — 8 33BPTATT>a,

ca

3a

3aMeTaH

T o r a c e 3a B e h e

MeTajiHH

ynoipeÓH

HCTahn T. 3B.

npHJinqHo

npHTHCKe.

H NPNQBPCTH

3aTerHy.

KOJ'HX r p e 6 a

36or

H Behe

H3Ap»aBajy

je

NPHTHCAK

6 o u a

HA BOACHOM

3arpeBa

ijeBHMa

3anpeMHHe.

ayroKJiaBH,

BpeMeHO

Aa

HJIH

3ATONJÍ>EHE U E B H Y N O T P E Ó J B A B A c e OÓHHHA

ecj)eKTy K o j n 6 H c e M o r a o

THM

anapaTOM

nocTHrHe. Meuiaibe /I,OK

ce

y

pa^n

h

XOMOTCHOM

MyfcKaH>e

HHje noTpeÓHO

pacTBopy

MexaHHiKo

MemaHDe, caM AKO c e JKCJIH j a ce HeKa M 3 T e p n j a K o j a c e nocTenfcHO A O A a j e (J)paKunoHoj

HJIH c y c n e H 3 H j e , ce

y

HITO n p e AOBEAE

CMeuiH

AO (J511116

O B O B3>KH H a p o i H T O TaAa

AHcnep3Hje —

a n o peaKUHOHa T o m i o T a

Koja

.FLOKAJIHO jeBJba, Ha n p . n p n A O A A T K Y KOHU. c y M n o p H e K H c e j i H H e , A O B O A H

onacHOCT h c k h oceTJbHB

ripw

TOME

MEXAHH^KHM

MEUIAIBEM

3ATONJBEHA

Apyror

c e p a c T B o p M Y H K A I B E M pyKOM HJIH

AA

CTAJIHO

noKpehe.

c y HA A O I T E M

CTAKJIEHA

nejiepa. K a o B O T I J A Y3HMA CTAKJIEHE

npenapaT.

je HEONXOAHO

KJIEHH i u r a n HA K O M E

Kpajy

IUAN H N P M I B P C T H y

y

KPWJMA

Kao HJIH

MeiuajiHija

y

BHiue P E A O B A

BHAY

npo-

c e K O M B A HeuiTO

rnnpe

HJIH 0 A r 0 B a p a j y h a

UEBH

qaypa

yiueTHe y

3 a 3 a n y u i a H e . BOJJHUA c e

c e ca

IHTO

je

NOAMA3AH,

JEAHO

SYUIANA

NJIYTEHH 3any-

B E P T H K A J I H O M n0Ji0HA

NPCTEH)

(RJMUEPHHOM

MBJJH

K3]HIIIHHK

HJIH H)KJbe6jbeHH n j i y T e H H OAHOCHO rynieHH 3 a n y i u a H K o j e M j e N P H H B P M H E H A M e m a j i H i j a . ILOKPETAIFEE

PaóeoBe

noMohy

BpuiH

Bo A e He

ce

T y p 6 H H e, , a

KOA n o r o A H o r n p e H o c a H n o M o h y Majior e JI e K T p o M O T O P A BOAE

(AOBOJBHA

OAJIHHHO

UIHHe MaJIH KOJ'H c e

C Y A Y

1/16

je

Y3

AA

HP).

NOKA3AJIH

Ca

YNOTPEÓHTH

Tpe6a

HJIH

ce

MOTOpH

Mory

AKO

cy

ce

TAMO nao

TOnJIHM H 3A A p y r e

Mema

HCJOBPEMEHO

ripaKTHKyM opraHcne xeMHje

y

RAE

noroHCKe

HEMA Ma-

B33AyX0M CBpxe.

3 3 T B 0 P E H 0 M

3arpeBaH>e

ca

6ojte

cjiy>KH CTa-

HOM uiTunajbKOM. H a r o p i t o j HBHIJH BOLJHAE O K p e h e

y

pacTnopa

CJI. 29

H3HAA

HeKojiHKo onuitHx npaBHJia 3a pa«

34 ycnpaBJbeHHM bhhhm ^yTHM

K0H^eH3aT0p0M,

3aTBapaqeM He

Kao

uito

Moate Aa y n o T p e ö n ,

ce

to

jkh-

Memaaima 3anTHBa

n o K a 3 y j e cji 29.

O ß a j ce

y p e i j a j Me-

aKO y anapaTypw hm3mo noBHiiieHH npn-

THC3K. A k o Tpeöa je^Ha HaA Aa

A a c e H3Meuiajy

tc^hocth

K o j e c e Hajia3e y Aßa c a o j a

A p y r o M , a K o j e ce HHaie caMe He M e m a j y , Mopa ce MemajiHua

Tano,

nocTaBH

Aa j o j KpHJiua A o l j y

H3Metjy o 6 a

cjioja.

CneuHtjwqHO

Teace MaTepHje K o j e n a A a j y Ha a h o , Kao Ha np. juhhk y n p a x y hjih HaTpHjyMaMa^raM, He M o r y A o ö p o Aa c e 3axßaTe msjihm ctskjichhm MeuiajiauaMa. y

T3KBHM j e c^yqajeBHMa MexaHHqKo M e m s i t e necTO HJiy30pH0, h j a q e

ÄejcTBO

nocTHJKe

MemaibeM ca CTaKJieHHM

uiTanoM,

apbchhm

ce

uiTanHheM

hjih qemhHM MyhKas>eM pyKOM. OßAe

Tpeöa

aa

fce

ynoTpeön

MexaHHiKa

MyhKajiHija

Koja

HMa 3a UHjb Aa y xeTeporeHOM cHCTeMy n o c r a r H e Hapo^HTO (J)HHy AHenep3Hjy. n p «

TOMe c e 3a cyAOBe y3HM3jy t o t o b o

HCKjbynHBO 6 o u e ca ycKHM

BpaTOM h öpyuieHHM CTaKJieHHM sanyiua^eM Kojw A o ö p o 33iithb3.

Sanymaq

ce npHHBpcTH KOMaAOM r y M e H o r utpeßa K o j e c e c t s b h n p e n o 3 a n y m a q a , h MßpCTO Berne T3HKOM JKHIJOM 3a Bp3T

ÖOIje. PeSKHHje KOA KOjHX ce pa3-

bhJ3

He CMejy

r üc

hjih

mhgto

t o n JI o t e,

ce 6e3 A3Jber

h3boähth

Ha Myhna^HUH. OßpeijHBaifce T a n n e MncToha ce T a i K O M 3a

He«e

KpHerajiH30BaHe

Tonjbeaa.

koj'h ce

cTaßH

opraHCKe

MaTepnje

KOHTpoJiHiue

O b s k o h c t 3 h t 3 K o j a c e JiaKO y T B p ^ y j e cjiy)KH

HaeHTH$HKOBatt>e

paKTepncTHKy.

TOiUbeflba

MaTepHja,

Kao

anapar

a

koa

cJiyÄH

jeAHft>eit>a

öajiOH

n o M o h y n j i y T e H o r 3anym3Ha

es

3a

itHxoBy

AyrHM

Ö3>KAapeH

ka-

bpstom

TepMOMeTsp;

y Aa

6h c e hmso n p e r j i e A i j e j i e cKajie, Hce^e c e o i u t p h m hojkcm y3aH KOMa^wh 3anymaqa o

( c a . 30).

Kao

tchhoct

TpoßaHa cyMnopHa

öajioHa a o 3/4 Cßoje CTaßH y r|a, !

Majie

3a

3arpeß3ft.e

cjiyacH

qHCTa

KOHueH-

kHcejiHHa koj'om ce HcnyHH JionracTH A e o 3anpeMHHe.

cTaiuieHe

npsße o a enpyßeTa

ueB^Hije

(Hsjöojbe

oa

CyncTaHua tshkhx

ce

cnpauiH

3haob3

ouiTeheHHX,

h ce

ajiH cyßwx h

h h c t h x ) Ha cJieAehn h3hhh. E n p y ß e T a ce 3arpeßa y A y ß a j b K e y 3 ORpeTaite a o k He noMHe Aa ce

Koje

Tonn

njiaMeHy

h 6p30 x e

H3Byqe; Beh n o c j i e KpaTKe Beacöe noroAHfae c e npaßa AeöjbHHa; yHyTpauiH>H npeiHHK T p e ö a Aa h3hoch. 1 — 1 , 5 mm. Ü 3 MaTep n j a j i a koj'h ce a o ö h o H3BjiaqeH>eM nceKy c e MaKa3aMa n o r o Ahh AeJiOBH H a j ö o j b e , rAe j e M o r y h e , y A ß o c T p y K o j

J

ueBqnue ( o k o cpeAHHy

Ay«HHH

12 c m ) TaKo, Aa ce, KaA ce ueBHHua CTonn H3

(cacBHM m3jih naaMeH) h pa3AßojH, A o ö n j y Aße

ro-

TOße ueBMHiie 3a 0Ape^HB3H>e TaqKe T o n j b e f t a .

Ca. 30

JeAna Maaa

npoöa

TyiKOM, HJIU mnaTy^OM

cacBHM c y ß e

cyncTaHue 3ApoÖH c e

Ha caxaTHOM, cTaKiiy, hjih Ha MaaoM

35

Oapet^HBaiie taiKe Ton^eita

KOMa^y

Her^a3HpaHor

KanHJiape y

Kpaj

bhchhh

nopuejiaHa,

oioja

npax,

Kana^ape y

oa

h

caxaTHO

nyTa

H

Hajöojbe

je

ripn

Aa

ce

npaxa

nycTH

Typnnje

Ha

ce ypoHH

oTßopeH

ce Aa

npeno

aho

cyncTaHija

CTaKJieHy ueB Ha c r a K a e H y

Kannaapa naoiy

hjih

KanHjiape

no-

npHjaaajy cn;iH3Hy Ha a h o .

qßpcTO

Kann,napa

npHJienn

BpxoM

KHcejiHHe K o j a c e

Kpaj Kannaape. r i p a

Aeo

tomc

Be^iHKe a A x e 3 H j e

Ayry

Koje

jeAaH

JiynKaíteM. n o c T H m e A a

;iaraHHM npeBJianeibeM

cTHHce c e Aa c y n c T a H n e kohu. cyMnopHe

2 mm.

Koa

naAHe K p o 3

cTaKjio.

oko

yöauH

naiKJbHBHM

ca 0TB0pa CKJIH3H6 y H y T p a . HeK0JiHK0

h

3a

TepinoineTap

KanjbnuoM

HaHece Ha

TepMOMeTpa

ropn>H

TOMe c y n e r a H i j a T p e ö a Ä a c e Hajia3H y b h c h h h

cpe-

A h h e jKHBHHe K y r j i H H e . CaMa K y i v i n u a M o p a A a j e npHJiHKo,M O A p e t j H B a i t a nomyHO

ypoaeHa

y

KynaTHJio. K y r a a

MeHOM K o j n c e ä P ® h öajioHa.

AnapaT

koco,

Mopa aa

Koja ce Tone b h c o k o

ce 3arpeBa

h K o j n c e jiaraHO h paBHOMepHO

ce

ocBexjbaBa

MOJKe c e y

Tpeßa aa

CTaßHjyMy

cyncraHqe

o M e K i u a j y ae^iHhH

ua r o p e .

AOAupa

Ka^a

ÖHCTpo

HCTon^eHa.

CJiyjKH j e A H O MHora nojbaBa

je

y

Koja

npoöa, Koa

TaqKy

noqeTKy

ce cyncraHUH

6p3HHe

OApe^HBafty

pa3JiaraH>a,

noce

He T o n e

Obo

6e3 pa3Jiaraita.

a BehHHOM h y T a i K y

3arpeBaita,

ce

pa3BHjaiby TaKBe

hc-

raca

cyncTaHije

pa3Jiarait>a

TaKo Aa c e k o a

He-

Koja

6p)Ker

je no:

ce npoöa

Beh

oö^HKa

hoioä

Koja ce

H33HBa

Ta^Ke T o n j b e i t a MaTepnja,

6p30

Aoera

ao

npoMeHH n o A y T H u a j e M

TaMKe

Tonjbeita

K o j e ce jiaKo

pasjiaxcy

ncnoA

TeMnepa-

Ha 1 0 — 2 0 CTeneHH

a 3aTHM c e T e M n e p a T y p a

CKynn h

„ c h h t e p o b a h> e " .

noÄHHce

caMO

no 5

CTeneHH

MHHyTy. riojaBa

pa3Jiaraft«a

npepaHor 3HaK

je

cHHTepoBait>a

3a H e n o T n y H y

koa

cyncraHUH

MHCTohy,

Koje

h H3HCKyje c

c T p a H e n0H0BH0 n p e K p H C T a j i H c a B a i i e h j i h ACCTH^HcaH>e. MaTepnja Koje ce CHHTepoB3H>a, je

Tonjbeifca j e

T o n j b e i b a He n 0 3 H a j e M 0

n o 3 H a j e A a OHe n o A ^ e a c y

npoMeHa

ce Kynarajio

ae^iy

aajia3n Biima TanKa pa3JiaraH>a, H e r o k o a c n o p n j e r .

n o c T a H e jienjbHBa, npn

obom

ropiteM

OMeKiua^a h CKynHJia

MaTepnja q a j y T a i K y

T o n j b e i b a , Beh H M a j y

y B e K 33bhch3 o a

obhx

6jih3hhh

OönqHO y

ocTajiH y

KanHJiapH m o j k c Bp.no o u i T p o Aa 3ana3n.

iiito

y

y

jeAHibeita

T o n j i O T e n o TOMe,

Type

je

n p o me h h 6oje,

BHiuaBaH>a T e M n e p a T y p e

3arpeBa

KojH c y

a y

Tejía

OApeJ)HBaK>e 3a o p H j e H T a i j H j y .

c e opraHCKa

Majy o u i T p y

Koa

noaaKO.

oko

Koa

ca Ton/iHjoM c y M n o p H O M k h c c a h h o m , K o j a C T p y j n

npeTxoAHO

qecTo

i i i t o ce y TOTOBO

3arpeBaTH 6 p 3 0 ,

pacTe

C a ^ a ce naaubHBo 3arpeßa A a - t e ; T e M n e p a T y p a

CTHrHyTa

Kpehe

yna^HOM CBeTJiomhy.

no^eTKy

Taa T e M n e p a T y p a KanHJiape y c ^ e a

yMepeHO bcjihkhm njia-

qaK hh y

AaKJie,

Koje

HajqHCTHjeM oÖJiHKy He T o n e ce

He

Tone

ouiTpo.

y

ce

Tone

6e3

npenaparaBHe

HMa, Me^yraM, H 6e3 npeTXOAHor

Be3H

c

obhm

HeKa

, t c i h h x

KpHCTajia"

(Lehmann,

BaiKH K a o n p a B H ^ o , A a c e HeKa c y n c r a H i i a

CMe C M a T p a r a

Kao qncTa,

OBAe

yKa3aHO

Ha

nojaßy

t.

3b.

Vorländer). aKO c e i t e H a T a q K a T o ' n j b e i t a npHJiHKOM noHaBJbaifca h a B a i t a Bnuie He

npoueAype

npe^Hiii-

Meita. 3*

HeKOJiHKO onuiTHX npaBiuia 3a paa

36 P a 3 ^ o r 3a t o , koa

Hero

Aejiyjy

y

Henor

Heny

A a TaqKa TonjbeH>a

pyKy

Kao

jiokh,

pacTBOpa

hc^hcthx

MaTepnjajia j i o k h y t o m c ,

qHCTor

pacTBOpeHe

MaTepHja

Aa

MaTepnje;

Kao i u t o je no3H3To

Jie>kh

HHHte

MaTepnje — npaTHOijH

yßeK

Tanna

oqßpmhaBaifca

Hirne Hero ; i h TaiKa

o^BpuihaBafta pacTßapaqa (KpHOCKonnja). Ha o b o m oAHoey 6a3npa ce jeAaH Ba^caH

AOKS3

HÄeHTHTeTa.

Ako

mh h o b h m

nyTeM

AOÖnjeMO

hcko

jeÄHaeHje 3a Koje CMaTpaino, npeMa re>eroBoj Ta^mn Tonjbeita, Aa je hji,sht h h h o ca h c k h m

Beh

no3H3THM

HeceMO CHrypHy OA-flyKy T a K O , HHTHMHe CMeuie

oöa

t o MOJKeMO o T O M e A a

jeÄHH>eK>eM,

i i i t o heMO A a y T ß p A H M O

jeAHH>eiba.

Ako

je A

pasjiHHHTO

TaiKy

ao-

Tonjbeifea

o a B t o he o6e

MaTepHje Aa AejcTByjy Me^ycoÖHO Kao HenHCTohe, h TaiKa Tonjbeiba CMeuie he Aa ce c h h 3 h , a aKo cy h a c h t h h h h , Ta^Ka TonjbeH>a ocTaje HenpoMeiteHa. K o a „ n p o ö e T o n a e i b a M e m a B H H e " Tpeöa Aa ce CBe Tpn npoöe (A, B, A-\-B) HcnHTajy ca h c t h m TepM0MeTp0M Ha k o j ' h ce, y3 Maao Beacöe ca o 6 e CTpaHe h cnpeAa Moace Aa c t s b h no jeAHa Kannaapa, h j i h aKO j e ueB TepMOMeTpa a o b o j i > h o Aeöejia CBe Tpn Kannjiape cnpeAa jeAHa ä o A p y r e ( y HCToj b h c h h h ! ) . y koa

j ea h o m

cjiynajy

HäOMOpijiHHX 3a

CTaHiie

OApeijHBafte y anapaTy

He Moace

ce npHMeHHTH

oBa MeToAa, HaHMe

MaTepwja. TaJiKe

K A y q a a a

sa OApel)HBaii>e

TanKe

ca

Ma^HM

Tonjbeiba

BHiue ynoTpeßjbHBHX nocTynaKa, Ha np. nocTynaK no KynaTHJio

ca

cyMnopHOM

KOJiHiHHaMa

cyn-

hcto

TaKO

nocToje

KHcejiHHOM

CuBOJioöoay 1. He MO>Ke ce

yno-

TpeÖHTH 6e3 onacHoeTH 3a OApe^HBaae TanKe TonjbeH>a H3HaA 250°; mhm ce noKaaiy nojaße Kjbyqatt>a Tpeöa npeKHHyra Aajbe 3arpeßaii>e, a Tpeöa paqyHaTH Beh h paHHje ca MoryhHomhy Aa 6 h 6a;iOH Morao Aa npcHe. Bnoie TeMnepaType

( a o 350°)

nocTHHcy ce ca KynaTHJioM ca cyMnopHOM

j i h h o m , y KOMe je Ha Tonjio pacTBopeH K a ; i H j y M c y . f l 4 ) a T .

Knce-

O b o KynaTHJio

oußpcHe Ha x^aAHO, noiiJTO HCKpHCTajiHine npHMapHH KaflHjyMcyjie y r j b e H H K a , BOßOHHKa, a s o T a , cyMnopa h

xajioreHa

IicnHTHBaH>e Ha y r j b e H H K h b o r o h h k :

A k o HeKa cyncTaHtja npn

3arpeBaH>y naaiweHOM Ha njiaTHHCKOM jiHMy caropH

(H3y3eTiiH: Ha np. S),

h j i h aKO ce pa3^oacH y3 H3ABajan>e iipHor yrjbeHa, t o ce OHa Moace cMaTpaTH Kao opraHCKa cyncTaHua. HcnKTHBaae Ha y r j b e H H K h 1

B 19, 175 (1885).

boaohhk

KBajiHTaTHBHa opraiicKa anann3a

37

HCTOBPCMCHO M05KC ce H3BpuiHTH TaKO, Aa ce jeAHa npoôa cyBe cyncTaHue H3Meuia y jeAHoj MSJioj enpyBe™ ca BHiueerpyKOM 3anpCMHHOM HHcapeHor, 4>HHor óanapoiccum, npeKO MeiiiaBHHe eraBH join HeiuTO ôaKapoKCHAa, enpyBeTa BEACE noMohy iuiyTeHor 3anyni3H3 ca J E ^ H O M CT3KJICHOM ijeBH caBHjeHOM NOA npaBHM yniOM, H CA^A j a K O 3arpeBa. A K O racoBH KOJ'H ce pa3BHjajy 3 A M Y T E ÔHCTpy ôapuiïiHy Bony ( C 0 2 ) , TO cyncTaima ca^pÄH y r j b e H H K a , AOK ce npHcycTBO B O A O H H K S AA no TOMe pacno3HaTH iiiTo ce Ha ropiteM X;I3AHOM A E A Y enpyBeTe HaxBaTajy KaüJbuife BOae. HcnHTHBaibe Ha a a o T : y jeAHoj enpyBeTHun qnjH je yHyTpamitH npeiHHK OKO 5 mm, a Ay>KHH3 6 cm, 3arpeBa ce y iuiaMeHy ByH3eHOBe rpejajiHue jeAHa Ma;ia npo6a cyncTaHue ca je^HUM KOMaAiiheM cjajHor KajiujyMa nJin HaïïipujyMa BeamiHHe noJiOBHHe 3pHa coiHBa, Koja ce Hcnpecyje H3Me^y JIHCTOBS (j)HJiTapxapTnje. ripn TOMe AOJia3H AO pa3JiaraH>a npH qeMy ce cyncTamja oôojn MpKo. UeBHHiia Koja je npea Kpaj 3arpejaHa AO upBeHor ycHjaiba ypoHH ce joui Bpe/ia y m3jih nexap y KOMe hms 5 ml BO^e, npH qeiny ce aeB^Hija pacnpcHe, a HenoTpomeHu Ka;mjyM eBeHTya^HO 3anajw (Kanena). B O A C H H ce pacTBop, Kojn y npHcycTBy a30Ta caÄpjKH icajiujyMifujanuMa, npoue^H, Aa 6H ce OABOJ'HO yrajb H KOMaAHhH craKJia, 4>HJITPATY AOAA no 2 KANN pacïûBopa (pepocyjicfraïïia H tpepuxjiopuaa, npoôa K& JIN TeqHOCT pearyje a^Ka^Ho, H ano je TO crcyqaj, 3arpeje 1—2 MHHyTa, npH qeiuy y npncycTBy KajiHjyMUHjaHHAa nocTaje KajiujyMcpepoI¡ujaHua. A K O ce ca^a no oxjia^eity aJiKajiHH patTBop 33KHcejiH COHOM KucejimoM, TO ce pacTBope H 3 A B O J E I M RBOMI^A OKCHA H ( J ) E P O X H A P O K C H A , A KajiHjyM^epouHjaHHA pearyje ca rBomiìexjiopHAOM H a no3Hara Ha^HH y3 CTBapaibe ôepjimacor ünaeor. Y npncycTBy a 3 o T a AOÔHja ce npeMa TOMe n j i a s T A J I O R . A K O y cyncTaHun HMH caMO MaJio . a30Ta, TO ce KaTKaAa y noneTKy He AOÔHja Tajior, Beh caMO njiaB03ejieHH pacTBop. AKO ce OBaj OCT3BH AS cTojn Ay®e BpeMe, eBeHTya^HO np?Ko Hohn, TO ce H3Asaja T3JIOr.

npH

HCnHTHB3H>y

JI3K0

HCnpajbHBHX

CynCTSHUH

Ha

a30T

Tpeôa ynoTpeÓHTH AyJKy enpyBeTy H nycTHTH Aa cyncTaHita Koja ce KOHAeH3yje Ha XJIA^HOM AeJiy BHiue nyT3 cjinje HaTpar h3 Bpeo KajinjyM. K O A cyncT3HiiH

K o j e CBoj a 3 0 T n 3 A B a j 3 j y

Beh npH yMepeHoj

TeMnepaTypH

H3

np. KOA Ana3ojeAHH>eH>a, He MO)Ke ce a30T Aa yTBpAH Ha onncaHH hs^hh. y T3KBHM ce cjiyqsjeBHMa Mopa ce ncnHTS, ^a JIH ce npn caropeB3K>y cyncTSHue es OKCUAOM ôanpa y ueBH Koj3 j e HanyaeHa ymenmoKcuaoM, CTB3P3 T3C KOjH ce He sncopôyje y KajiujyMxiiMpoKcany (ynope^n KBSHTHT3THBH0 OÄpetjHBaHje a30T3). McnHTHBafbe n a c y M n o p : KB3^HT3THBHO HcnHTHBaH>e Ha cyMnop H 3 B 0 Ä H ce Hä HCTH Ha^HH K a o H Ha a 3 0 T . CyncraHua ce mapa y UCBMHUH ca HampujyMOM, no oxjiaijefby pacTBapa y BOAH, H je^Hoj I I O J I O B H H H pacTBops ÄOÄA HCKOJIHKO K3nn pacwBopa HumponpycuwaûipujyMa KOJ'H ce npnnpeMH HenocpeAHO npe Tors MyhKajyhn Ha x^a^HO HCKOJIHKO 3pHaua HBpcTe cojiH ca BOAOM. J b y Ö H ^ s c T O o ô o j e i b e noK33yje npHcycTBO c y M n o p a. riouiTO je HHTppnpyCHAHS peaKunja H3B3HpeAHO O C C T A H B S ,

38

MeToae eaeMemapHe aHajiH3e

h He ÄonyuiTa ce H3BeAe. Ma KatcaB 3aKjbyiaK o ko^hihhh cyMnopa t o ce Ä p y r o j npjioBHHH TeqHOCTH nocjie iíeijeita AQAa pactûBop ojiobo-, aiieïïiaUia

h 3 8 t h m 3aKHceJiH cupheïïiHOM

mcemnoM,

B e h n p e M a TOMe a a j i h

ce cTBapa caMO t3mho 3aMyheibe, h^h Beha hjih Maita KOflH^HHa ojiobocyjKpuaa, 33KJbyqyjeMÒ aa jih je KOJinqHHa cyMnopa Maita h;ih Beha. CyncTaHue Koje jiaKO acnapaBajy BehHHOM ce He Mory HcnHTyjy Ha oBaj HaiHH. Ose ce 3arpeBajy, Kao iiito je HHHce onacaHO k o ä kb3hthTaTHBHor OÄpe^HBafta cyMnopa, ca ûytujbUBOM a30ïïiH0M mcemnoM y 33tonjbeHoj ueBH Ha 200—300°, h pacTBop ce no p336jiajKeH>y ca boaom H c n H T y j e Ha cyMüopny

mcejiuny

ca

ôâpujyMXJiopuROM.

HcnuTHBaifee Ha xajioreHe: X a o p , 6 p o M h j o A Mory ce y opraHCKHM jeÄHfteftHMa caMO y p e t k h m cjiyqajeBHMa Aa AOKaacy Henocpe^HO Ta^OMcefteM ca cpeôpommpamoM, nouiTO xa^oreH BehHHOM HHje Be3aH joHoreHO. Ä a 6h ce AOKa3ao xoMeonojiapHo Be3aHH xajioreH » a p n ce cyncTaHua Koja ce HcnHTyje y jeAHoj He oAßeh ycKoj enpyBera Ha njiaMeHy ByH3eHOBe rpeja/iHue ca bhiiikom xcmhckh qncTor KajiiiujyMOKCuaa, ypoHH joui Bpe^a enpyBeTa y m3jio BOAe, npn l e M y ce oíía pacnpcHe, 33KHcejiH ca x e M H C K H q n c T O M CL30WH0M KucejiuHOM,

iieflH h AOAa

cpeópoHuwpawa.

y jeÄHH>eH>HMa, Koja He ca^p^e a 3 o t a, Mory ce xajioreHH AOKa3aTH » a p e a e M ca HawpujyMOM Kao hito je t o onwcaHO k o a HcnHTHB3H>3 Ha a30T. PacTBop, KojH ce npoue^H Aa 6h ce OTcrpaHHJiH kom3ahHh cTaiuia h npoayKTH pa3iiaraH>a, 3aKHceflH ce rhctom a30íüH0M mcemnoM h AOAa cpeôpOHUwpaïïi.

Bp^o 6p30 h je^HOCTaBHO Mory ce xajioreHH aok333th B e i l s t e i n O B O M n p O Ó O M . KOM3A«h OKCHA3 ÓaKpa BejIHIHHe 3pH3 C0HHB3 HJIH uiTsnwh OKCHAa ay^KHHe 1 / 2 cm oÖMOTa ce tshkom üjiciwuhcicom okuiìom Koja je 3aTonjbeH3 Ha CTSKJieHy ueB, h acspn t3ko Ayro y njiSMeHy ByH3eH0Be rpejs^Hue a ok iuismch He nocTSHe 6eâ6ojaH. A k o ce no oxiialjeiby ÔEKpa OKCHÄ3 CT3BH OA03rO C3CBHM M3JI3. KOJIH^HHS CynCT3HIje K0j3 CaflpJKH xajioreH, h 3arpeje y cnojbH>eM Aeay ByH3eH0B0r nji3MeHa, t o Hajnpe caropeBa yrjbeHHK h 3ana>Ka ce CBeTao njiaMeH. Oßaj ycKopo Hcqe3He a Ha aeroBOM niec-Ty nojaBH ce 3 e a e h hah n f l a B 0 3 e j i e H n;i3MeH kojh je H333B3H xanoremaoM Ôaicpa, KojH ncnap3B3. H3 Tp3j3H>a oôojeita Moace ce 33KJbyHHTH Aa jih cyncT3HU3 caApMCH caMO TparoBe xajioreHa h^h BHiue. 3a H3B0^eH>e Beilstein-OBe npoöe Moace ce ynoTpeÔHTH h kom3£ ôattapHe ocuife Koj3 je yHBpuiheHS y n^yTeHOM 3anyuiaqy. y H Ê H c n a p J b H B H M c y n c T a H U 3 M a Mory ce x a J i o r e H h c y m n o p Aa yTBp^e ca BejiHKOM CHrypHomhy t o n j b C i b C M c a ui3ji h t p o m. H3Meni3 ce 5—10 mg MSTepnje (He BHuiel) C3 100—200 mg KajiujyMHumpama y MajiOM 3 X 3 T h o m 3BaHy, h mcuisbhhs nsacjbHBO 33rpeBa y MaJioj enpyBeTH Ha m3KaH3eM yno3Ha ibHXOBy MaTepnjajiHy 0C06eH0CT. T p e 6 a Äa OBOM

o JI a K o

ce

e

T H M

JI

e

Ä

a

T

npenapaTHBHHM p e 6 a

paTHBHOM

npHÄaßaTH

paÄy.

KOJH 3

HCTH

036HÄHO

njiOÄOBe n p H p e m a B a i b y n a Ma, Koja c e

a

Cy H

a

Q

cxBaTaite

3aÄaiaKa

aj

Kao

Koje nocTaBJba

H

ce

noMohy

BOÄOHHK

OÄpeijHBaibe

ejieMeHaTa

eaeMenTapHe

OÄpeijyjy

H3-

O B H X O T -

npena-

ÄOHehe

aHajiH3a

CBoje

no

rpy-

y n p H K j b y q K y Ha n p e n a p a T H B H H Ä e o .

H3BOÄH

KßaHTHTaTHBHo

HHHCe

H HHCTO

onoMeHe

KBaHTHTaTHBHa opraHCKa eJieMeHTapHa

BpiiiH

y

H3Boijeii>y

oße

He

K o j H c JI y XC e

H3B6ACHH

ynyTCTBHMa.

Tora

3 6 o r

npHM epH o r a e ^ a ,

y3My

U H Jb y ,

H3CT3BHOM

H

oco-

peaKunje, Äa TeMejbHHM ekcnepHMeHTajiHHM nocMaTpaiteM

jeÄaH n o p e Ä

HeKe

aHajinse. Äpyror,

anajinsa opraHCKe

Opn

ÄOK

cyncTaHue

TOMe c e yrjt>eHHK

j.e 3a O Ä p e i j H B a i t e

CBHX

ocTaJiHx e ^ e M e H a T a 3a CB3KH n o T p e Ö H a 3aceÖHa aHa;iH3a. OßÄE

aHa«H3y Pregi-0B0r 1

onHcaHe

y3HMa

Me30-aHajiHTH?KC

20—30

mg,

pa3paÄHO

je

MeTOÄe,

Dr

F.

KOÄ

Hölschner

Kojnx Ha

ce

3a

0CH0By

MHKponocrynKa.1

F. Pregl. Die quantitative organ. Mikroanalyse, Springer-Berjin; ynop. H. Berger, J. pr. Chera. 133, 1 (1932); K. Küsperi, Chera. Fabrik, 6, 63 (1933); E. Sucharda H BBobranski, Halbmikromethoden zur automat. Verbrennung org. Substanzen. Vieweg 1929-

40

M e r o d e ejieMeHiapHe anajin3e

B a r a :

3 a aHajiH3y x o h e

KaA ce

cxBaTJbHBHX pa3.nora Ta^HOCT

HAe

caMO

JiHTHHKa

Bara

no

hjih

cnvmna

H e MOHkhm3ho c h t o ,

cy^wh 3 a Mepeite h ucb 3a Memaifae

CTaajba npaKTHKaHTHMa Ha p a c n o j i a r a t t e

flaôopaTopnja.

npunpeMe K fi n

3a

yrjbeHAHOKCHA

ocjioôoljeH

B a 3 i y x a :

Mepa npejiHjy c e y nopueaaHCKOM laHKy pa30Jia¡KeHOM H C l , rycTHHe 1 , 1 8 + 1 yrjiaBHOM 3aBpuiH,

cywaBafte

caBHjeHa cTaKJieHa

MajiH

KOMa^uhu

Mep-

kucenuHOM (1 3anpeMHHa

3anpenHHa Bone). I I o u i t o c e npHiena a a ce n o n e r a * ôypHa peaKunja

OÄJiHje c e npjbaBtuTHHa Koja c e cKynnjia o a o 3 r o ,

KOMaAHhH MepMepa boaom. MepMepoM;

COHOM

Ca.ua c e HanyiiH cpeÄH>a j o m a

h Hcnepy HarpHHceHH

KnnoBor anapaia

J i o m e nocTHSKe c e KOMaaHMa C T a o a hjih noMohy «Ba

unanHha.

H a yHyipawfoH

npaj ueBH CTäiuieHe

ä o noJiOBHHe nojiyKpyjKHO

cjiaBHHe y i B p m h e H e

y

T y ö y c cpeaii.e a o n i e noMohy ryMeHor s a n y u i a i a , naMa3aHor c a Majio Ba3ejiHHa, HacTaBH c e noMohy icpaTKor

KOMaaa ryMeHor upeBa

C T a o e H a ueB

TaKo a s npn H c n y i i n a i t y ojtHJia3H Hajnpe r a c anapaT nyHH

pasöjiaweHOM cohom

HanyHH joui h noflOBHHa MepMepa TaKo, HCTHCHe Ba3flyx

khccjihhom (Kao r o p e ) ,

r o p a e jiome.

Ta.ua c e

a a c e ohh Ty 3anrane h na KojH j e y coHoj

y oôjiHKy « y n e caBHjeHe

H3 najBHUie

ce

yóaue

T a i n e cpejiite j i o m e . TaKo Aa c e

nopeA

y ueB jieBKa ÄBa

Ha r o p e , 3aTHM c e

ÄOH>e j j o m e

MaH>a KOMaawha

y c a e a jKHBaxHor pa3BHjaH>a yr^eHÄHOKCHÄa

KHcejiwiiH pacTBopeH;

noHOBJbeHHM

oTBapaaeM h 3aTBa-

pan>eM cjiaBHHe obo c e HcxepHBafte Ba3Ayxa y 6 p 3 a B a . CßejKe npHnpeMJbeH KHn .naje no npaBHJiy a o b o a h o

ihct

yejbeHAUOKCuA

TeK n o c a e

CTajaH>a 2 — 3 ÄäHa — Kaaa je Ba3nyx koJh je ancopöoBaH Ha noBpuiHHH cTaKJia h 4yKy n p e u i a o y aTMOC(J)epy yrjbeHÄHOKCHÄa. npeKopHo qHCT h « a c e

Moste ynotpeöHTH

Ha Kay-

Mo>Ke c e CMaTpa™, a a je yrjbeHAHOKCHji 6 e 3 3 a OÄpeljHBaHie,

Kaaa ce

,MHnpoMexypn'

KaaHTHTaTHBHa opraHCKa eJieMeHtapHa aHa;iH3a

41

Kojn ce y a30T0MeTpy neity, CKynjbeHH no BHtue H>HX 3ajenHo, npecTM>Kyhn qecxo jeaaH Äpyrn, Kpehy y BHC paBHOMepHOM 6p3HHOM. flocMaTpaHH noa JiynoM He Tpeöa aa noKa3yjy npee.

cyßy aeB CTaBH ce Hajnpe HeuiTO cpeöpne Byne Tano

y KOHHMHH

6ecmm

AEO ijeBH;

33THM

ce

CTABH

HeiiiTo

Byne Koja ce noroAHHM cTaKJieHHM

JBEHE Ha M I A M E H Y ,

NOTHCHE A O KJBYHA

npenHiuheHe

AA

ce ncnyHH

H yacapeHe

AS-

uiTanoM, nnje cy HBnu,e 3ao6-

ueBH H YMEPEHO

caönje,

ce HA TOM MECTY Aoönje A 3 6 E C T H H qen ACÖJBHHE 2 — 3 mm.

Ta«o

Ha a3Öecr ce

CTaBJba a i o j r p y ö o r oiccuaa öaicpa Ay®HHe 12 cm; ApacehH ueB ycnpaBHo H j i y n K a j y h H ca CTpaHe p y n o M

OKCHÄ ö a K p a

ce yinepeHo

c a Ö H j e ; Hä' HCTH

6H

Metofle

42

eíieMemapne

aHa;iH3e

ce H3HHH ca^a cnna 6 cm 4> HH or « o ^ 0 3 r o 10 cm r p y 6 o r OKCH^a óanpa. OBO „ T P A J H O n y i í > e H > e U E B H " HKCHpa ce #pyrHM a36ecüiHUM neüOM Kojn ce yMepeHO caónje Tano My «uyacHHa H 3 H O C H H C K O ^ H K O MHjiHMeTapa. y TaKO H a n y i t e H y u e B yBO^n ce c a iiiHper K p a j a cmpyja bomohukü Koja ce npeTXOAHO nepe npoBoijeifeeM Kpo3 mcejiu pacüiBop üepMaHraHawa, H n o u i T O ce Ba3flyx noTnyHO HCTHCHe, H3pe,nyKyje ce cjioj C H T H O T OKCHAa óanpa

6

o r

.ayjKHHe

cm

3arpeBajyhH

yMepeHO

ByH3eHOBOM

H

.laMnoM,

ocTaBH ,a;a ce ox^a^H y jiaraHoj C T p y j H B O A O H H K 3 . CBejKe npHnpeMJbeHa ueB „ c a c T a ^ i H H M nyaeiteM'' HjKapn ce y ejieKTpniHoj nehn no u e ; i o j c B o j o j Ay^cHHH y cMpyju yrjbeHMiioiccuMd, H O C T 3 B H fla ce oxJiaAH nofl I I P H T H C K O M y r ^ e H j H O K C H a a H3 K H n a . H KaAa ce H e ynoTpeójbaBa, ueB o c T a j e C T a j i H O y

Be3H

KHIIOM

ca

NOA

NPHTHCKOM

YRJBEHAHOKCHFLA.

n o a y M H K p 0 - a 3 0 T 0 M e T a p : MeTpa,

KOJ'H c a y s K H

cyncTaHue Ha iHua neny

on. 2 0 - 3 0 m g ; ixcBH

ayraiKH

M0ryhH0CT

y

na

aapHe

ueBH

MecTy

ce

KpajeBH ueBH je

y

6jiaro

noa

mijn

na

yrjioM. HMa

KpaK

cnojbHH

ce

npojia3.

TaiHOCT.

joui

TypnHje

UeB

3a

HCTH

KanHJiapHe

ca Majio Hajiewy ueB

yBeK

cyMuopnoM KucenuHOM. TOMeTpoM

Bewe

óyjie

mm

1—2

jeMH

ílpH

Ha a 3 0 T 0 M e i p y . Kpo3

H3HaA H a j e n m e

cjiyac«

noeiHHKa

Tpe6a aa ce

Ha a p y r H .

TyMeHo

c e JKHUOM.

ca Mano Ba3ejiHHa, á30T0Meipa

yHyipaiuHjer

rvmuepHHa;

ueBH

upeoo

TanKe

ripe

Koje

KpymKy

cnaja ce

ymha

H

uefiefteM

M y h K a f t e M ca Kpo3

nyftefta

ueBH

3a

iHcra

3a H3jeniiaqeH,e

xcuBa c B e

yBoljeae

raca.

c y B

IJIHHO c n p a u i e H H M

a cnaBHHa najiwbHBHM nonpeTatbeM nojiyre 3a (Jjhho peryjiHcait>e Tano Aa y a30T0MeTap yjia3e 2 Mexypa y 3 cenyHAe; Tpeöa 6pHacjbHBO H36eraBaTH Ma h KpaTKO npeKopaqeite OBe 6p3HHe. TaAa ce noMohy MpejKHue h njiaMeHHKa y TOKy HAyhnx 5—10 MHHyTa noHOBO jaKO HJKapn H3MËHJbHBn aioj OKCHAa öanpa, yKJioHH njiaMeHHK h nocjie Aajhnx 5 MHHyTa HCKJbyqH ejieKTpHHHa neh. Tpeöa ce MyBSTH Tora, Aa ce ueB 3a caropeBatt>e Aupenrao Ha cJiaBHHa Ha a30T0MeTpy, citHHe ryMeHO ijpeBO ca ueBH 3a caropeBaae, CTaBH Ha OBy ryMeHH 3aTBapaii, h octsbh Aa ce oxJiaAH íioa npHTHCKOM yrjbeHAHOKCHAa. A3oroMeTap ce nocTaBH y HeuiTO xjiaAHnjy npocTopHjy (SapOMeTapcKa coöa) Aa ce ox^aAH, npH qeMy ce noAH3ait>eM KpyniKe ycnocTaBJba hcth hhbo y rpaAyncaHoj ueBH Kao h y cyAy 3a H3jeAHanette HHBoa. nocae 10 MHHyTa npoMHTa ce 3anpeMHHa, AOBOAehn MeHHCKyc y hhBojcKoj KpyrnuH Koja ce najia3u H3a rpaAyHcaHe ueBH t3hho y jeAHy paßaH ca HHBOOM y rpaAyHcaHoj ueBH. npoqHTa ce noAeoK KojH ce HaJia3H y HCToj xopH30HTa^iHoj p3BHH ca AotbOM hbhuom MeHHCKyca. ,H,ajbe ce npoWHTa T e M n e p a T y p a (TepMOMeTap y JieBKy Ha a30T0MeTpy) h 6 a p o MÊTapcKO C T a a e . CpaiyHaßaibe aHajiHse: npoueHTya^HH caApHcaj a30Ta h3hoch:

OßAe 3H3HH: V npo^HTaHa 3anpeMHHa a30Ta y ml, s y3eTa KOJin^HHa cyncTaHue y mg, t TeMnepaTypa, a

273

=0,003663

46

MeToae ejieiueHTapHe aHajiH3e

b öapoMeTapcKo cTaibe, 6 KopeKTypa öapoiweTapcKor CTaita Ha 0°, e TeH3Hja KajiHjyMXHÄpoKCHAa Ha

t°1.

TpaHHua rpeuiKe OÄpei)HBaH>a: 0 , 3 % . « a ßHuie, 0 , 1 %

HH«ce.

Ha

II. O f t p e ^ H B a t b e y n b e H H K a H b o a o h h k s n o J l H ô n r y CyiiiTHHa ce MeTOfle cacTojw y TOMe, Aa ce H3MepeHa KOjmqHHa cyn-

CTaHue OKCHAHiue y ueBH 3a caropeßafbe y cTpyjH Ba3Ayxa hjih KHceoHHKa Ha n^aTHHCKOM KOHTaKTy

min noMohy OKCHAa öanpa h xpoMaTa ojioßa h

Aa ce npoßyKTH oKCHAaaaje y r ^ e H ^ H O K C H ^

h boas

Mepe Ha Barn. YivbeHAHOKCHA ce ancopôyje noMohy

ancop6yjy h

HaTpHjyMXHApo-

K e H a a a BOAa noMohy K a j i i i H j y M X J i o p H A a . A k o ce ynoTpeÖH „yHHBep3a^HO

nyH>eH>ea

Mory

ce

y Hcroj iìcbh aHHJin3HpaTn CBe cyncTaHue,

6e3 oÔ3Hpa Aa j i h OHe nopeA yrvbeHHKa h boaohhk3 caApJKe join a30Ta, xaaoreHa m m cyMnopa.

A30thh

CJiojy yiKapeHor óaKpa y a 3 o r , ByHe, a c y M n o p

okchah

Kojw HacTajy p e A y K y j y ce Ha

x a j i o r e H ce Beate noMohy

noMohy c p e ó p r i e

ByHe h

cpeópHe

oíiOBOxpoMaTa.

3a C, H — OÄpetjHBaH>e noipeöHO je: ließ 3a caropeBafte cymeHa na je^HOM Kpajy (nao 3a o,npeljHBaH>e a30Ta), noroaaH ryMeHH 3anyma'i ca je^HOM pynoM KojH Aoöpo HajiasKe y3 3HÄOBe ueBH, ueB 3a ancopnuHjy ca KajiuHjyMXJiopn,aoM, ueB 3a ancopnuHjy ca HaTpOHa36ecTOM, ÄBa KOMa^a ryMeHor BanyyM upeBa 3a Be3y, ycKor yHyTpauifter npeiHHKa .ayjKHHe 1,5 oähocho 2 cm kojh Tpeöa aa ce HMnperHHiiiy Ba3ejiHHOM y BanyyMy (bhäh Äone), KOMaa cpeöpHe >KHue Aeöjbmie 1 mm, ay>KHHe 8—10 cm, 1,0 g cpeöpHe ByHe,

npeiHiuheHa a3öecTHa ByHa („a3ÖecT 3à ryqeBe" p. a.), KpynaH H cmaH öaKapoKCHA, 1 BpeflHocTH H3pa3a y 3arpa,nH y ropitoj (JiopMyjin 33 pa3JinqHTe BenniHHe oä (b-S-e) h i Hajia3e ce y TaójiHUH Ha Kpajy kwuie. KopwroBafbe ce Mome äa H3BpiiiH ca «oboahom TaHHomhy h TaKO, na ce oa npoiHTaHor ôapoMeiapcKor naita b oay3Me t/8 3a S t/5 3a e. Ha np. npoHHiao b = 738rmm, t = 20°; y TaÖJinixH ce Hafje p = (738—2, 5—4) =731,5 3a jiorapmaMCKo cpaiyHaBatie ynoTpeôMBajy ce TaÖJimie 3a pawyHaite on Küster-a.

47

Oapel5HBaH.e yrjbeHHKa h BOAOHHKa no JlaSHry

6aKapoKCHfl npeByieH OAOBoxpoMaTOM (bhah HaTpoHa36ecT ( „ M e r c k "

Aoae),

3a MHspoaRa^H3y),

o6imHa h Ha 100° cyuieHa BaTa. o a njiaTHiie h caMy

ripeaMeTe

anapaxypy cTaBjha npaKTHKaHTHMa

aaóopaTopHja

Ha

pacnojiOHtefte. ÍIpHnpeMe

nyubeibe raco»eTpa KHceoHHKOM: OTBapaiteM cAaBHHa a h b (cji. 36) noinyHO aoh>h pe3epBoap boaom. HIomto ce o6e cjiaBHHe 3aTBope OABpHe y B y i e upeBO KOje je y Be3H ca 6ouom ca KHceoHHKOM y Tyóyc c, h racoM d a p HanyHH KHceoHHKOM. Houito ce 3aiBapan 3aapHe, HanyHH r o p a a pe3epBoap boaom h 0TB0pe cjiaBHHe a h b crpyja KHceoHHKa H3Jia3H non b¡ 3a nyH>eH>e r a c o M e i p a Ba3AyxoM HHje noipeóaH HHKaKaB ójihwh onnc. ce HanyHH

PeryjiaTOp o6e36e^H H>eroBor

aa

npnTHcaic

KOHCTaHTHy AejcTBa

6p3HHy

OBaj ypefjaj HMa nawaii

CTpyje raca

npHKa3aH je Ha upTeMfy

cyuiTHHH H3 jeAHor

3BonacTor

(bhah cji.

racoMeipa

oh

35);

na

3aAaTaK

3a BpeMe caropeBafta. ce

HaqHH

cacTojn y

Kojn j e ypoH>eH y cyA

ao nojioBHHe boaom Kojoj je AOAaTo HeuiTO h a t p h j y m x hA p o k c h a a, h koj'h noMepafteM y jeAHOM npcreHacTOM Apwaqy oa njiyTe A03B0JbaBa ycnocTaBA)an>e CBanor naTnpmHCKa Kojii ce >Ke;iH, ao oko 15 cm HanyifaeH

B0AeH0r CTyóa. racoMeTpuMa

3boh3cth

kojh

racoMeTpn peryjiaTopa 3a npHTHcaK

c^ywe Kao

Koja cy Kao cea ryMeHa paAH cHrypHocTn 6ii;ia

pe3epBoapH

upeBa npeno

noMohy Ayrnx

koj'hx

ce Be3yje

noABprHyTa '„BernTaiKOM

HoBa ce upeBa

noABpraBajy

rpeBajy y cyuiHHUH Ha

aoboa

BeiuiaqKOM

racoMeTap ca ueBH 3a

kojh

bcHhm

boaciih

pa3MauHMa

npemi3Hy

BpeMeHa, oxnpHJiHKe

racoMeipa no jeAaH Mexyp.

BemraiKH

ocTapejiHM

oaboa

UeBH 3a

Epojan

KajiHjyMXHApoKCHAa y jyM-ueBinna

MexypOBa 3a

cieaajiHiiy

CBaKHX 10—15 H3 3B0HacTHX

uito

ce 3a-

ópojany

h

cyiueite

Mexyposa

Kojw

ce

sa

je

no-

H3Jia3H H3

racoMeiapa Bene ca jeAHe

Mana x a o p K a a u a

HcnyuiTaite

MJia3.

npofla3e Kpo3 jeAHy

3B0HacT0r

KOHueHTpauwja

caropeBaae

ce H36enio

Kpo3 itux cipyjH.

CTapeny

raca H3 racoMeiapa KojH cjiywe nao pe3epBoapn

ryhe

Cn. 36

100—110° (He BHUie!) h ncTOBpeMeHO y Tony o a jeAHor caía CHme

Ba3Ayx noMohy uiMp«a Ha UpeBa 3a Be3y

Bewy ce ca

ryMeHux upeBa

crapeity" Aa 6h

carop.iHBiix cadojaKa cBewer ryMeHor upeBa y rae

ll

H3 jeAHe

EJpojai

KajiunjyMXJiopHAOM.

MexypoBa

U-ueBH ca

je

cnojeH ca

ABa SpyuieHa

wena

HanyfteHa HaTp0Ha36ecT0M h KajiunjyMXJiopHAOM.

OqHuiheHa h ocymeHa anapaiypa nyHH ce Ha cJieAehn HawHH. Kpo3 otbop U-ueBH 6jih>kh ó p o j a i y MexypoBa ct3bh ce jeAaH Behn npaMeH BaTe CKopo ao HajHHwe TaHKe KpHBHHe. BoiHa ueB Koja boah ópojaqy MexypoBa 3aTBopH ce npeTXOAHO KOMaAHheM Baie KojH ce yTHCHe hcahmhom jkhuom. Ha npaMeH BaTe enna ce y3 jiynKaite ao BHCHHe oa V; era oGiMHor, He HapOTHTO cymeHor KaAi^ujvMXAopuna, OBaj ce cjioj yiBpcTH jeAHHM MaAHM npaMeHOM BaTe, h Ha OBaj cana Haw.poHa.36ecm ( „ M e r c k " p. a.) CKopo ao SoiHe ueBHHue. riouiTO ce h O B a j CJioj ynBpcTH npaMCHOM BaTe, 3aMeHii ce KOMaAHh BaTe y 6oiHoj ueBH cacBHM pacTpecHTHM qenoM oa BaTe, h HanyHH ao 6pyuieHor Aeaa KpynHHM, oóhwhhm Kajiifuj'yMXJiopUAOM, 3aTBopn npaMeHOM BaTe, a nouiTO ce ópymeHH Aeo H36pHuie, KojH j e

CTaBH

ce

cTaKJieHH

nen

noAMa3aH Ba3eviHHOM Tano

Aa ópyuieHH Aeo H3raeAa npoBHAaH.

n o M o h y jeAHe H3ByqeHe CTHKJieHe ueBH HanyHH ce npo3 c^oóoAHy MexypoBa

HeuiTo

50 npoif, KonujyMxudpoKcada 6e3 nene,

SoiHy ueBinuy 6pojaqa

TaKo aa Bpx ueBqnue 3a

aoboa

Me-roae e^eMeuTapHe aHaJiH3e

48

TaMaH ypoHH y jiy»HHy; u e B i n u a c e H3HyTpa H cnojb'a 6PH>KJI>HBO OIHCTH B3TOM. CaÄ ce ca d p a H e a p y r o r 6pyuieHor oTBopa y ö o i H y ueBHHuy ciaBH o c y 111 e H, pacipecHT KOMaÄHh B a i e , 33TBopH oBa öoMHa u e B r a u a K a n H u o M OÄ r y M e H o r u p e B a H y3 JiynKaite HanyHH ÄO öpymeHor Äejia KajiifujyMx/wpuAOM BCJIHHHHC 3pHa npoca, KojH j e npeTXOÄHO ocymeH y cyuiHHUH Ha 180—200°. FIOIIITO ce c a o j KajiuHjyMXJiopHÄa yiBpcm c y m S H H M npaMeHOM BaTe noÄMawe ce 6pymeHH a e o Ba3ejiHHOM. B p o j a i MexypoBa Bewe ce 3a TpoKpaKy caaBHHy ryMeHHM upeBOM ÄyjKHHe 25 cm Koje je npeixoÄHo 6HJIO nOÄBprayTo BeuiTaMKOM cTapeity. Uejia anapaTypa 3a cyuieH>e Koja BHCH O jeaHOM H o c a i y OÄ >KHue yiBpuiheHa j e Ha jeÄHOM cTaTHBy ca KyKOM. M o p a ce c i p o r o n a 3 H T H H a TO L A — ÄOK j o w He wae c r p y j a r a c a Kpo3 a n a p a i y p y — 6 o i H a i i e e i H i i a a n a p a T a 3 a c y u i e H > e K o j a BOÄH e a ueBH 3 a c a r o p e B a n e 6 y Ä e c t a j i H . o 3 a i B o p e H a K a n H u o M OÄ r y i i e H o r u p e B a Äa 6H ce KaJiunjyMXJiopHÄ 33IIJTHTHO OÄ ÄOÄHpa ca BJI3)KHHM cnojbHHM Ba3ÄyxoM. AKO j e KaJiunjyMXJiopHÄ Ha MecTy r « e rac H3Jia3H HCupnjbeH — HäTpoHa3ÖecT Tpaje MHoro Äywe — cwna c e ÄO nojioBHHe BHCHHe ixeBH CB«K KajiUHjyMXJiopHÄ. AnapaT 3a c y m e i t e Be3yje ce 3a ueB 3a caropeBan>e noMohy jeÄHe KOHH^HO H3ByeM npeiHHKy 6oiHe ueBH anapaTa 3a c y m e f t e ; OHa ce BeiKe ca 6OIHOM ueBH KOM3ÄOM BanyMCKor upeBa Koje je HaTonjbeHo y BaKyyMy HcronjbeHHM Ba3eJiHH0M, h ocTaje cTajiHo Ha a n a p a i y 3a cyiueibe. KaÄ ce anapaT 3a c y m e f t e He ynoTpeöjbaBa, OHM ce KanHJiapHa UCB yßeK ÄPIKH 3aTBopeHa KarmuoM OÄ BaKyMCKor upeBa ycKor yHyTpauiH>er npeqHHKa. TyMeHa upeBa 3a Be3HBaH>e anapaTa 3a c y r n e a e H ueBHHua 3a cyuiette HaTone c e Ba3e^HHOM y BaKyyMy, Tano Äa ce KOMaÄHhii BaKyyMCKor upeBa ycKor yHyTpaiuH>er npeiHHKa Äy>KHHe 1,5 H 2 cm H a H i m y Ha Könau H n0TnyH0 ypoHe y HCTonjbeHH Bd3ejiUH KojHM j e HanyiteH jeaaH 6ajioii ÄO 2 / 3 cßoje 3anpeMHiie. TaÄa ce 6ajioH 3anymn ryMeHHM 3anyiuaMeM npH neMy KpajeBH KOHua Äotjy H3Metjy 3 a n y u i a i a H BpaTa 6aJiOHa, H eBaKyHiue c e H a T e Mn e p a T y p » B o Ä e H o R n y n a i H J i a noMohy imipna Ha BOÄeHH MJia3. Y noneTuy OÄHJia3e OKJiyÄOBaHH racoBH y3 j a n o nenyiuaH>e; c BpeMeHa Ha BpeMe ycnocTaßjba c e KpaTKoTpajuo o6imaH nptiTHcaK H eBaKyHiue c e ÄOK He noiHy Äa OÄHJia3e caMo joui nojeÄHHa^HH MCxypoBH. He Tpe6a 3arpeBaTH Äywe OÄ 1 / 2 c a i a , jep HHaie ryMa Haöyöpn. HOUITO ce o u e a e H H36pHmy cnojba H H3HyTpa oßa cy upeBa cnpeMHa 3a ynoTpeöy. PaÄH Be3HBaH>a ca ueBH 3a caropeBaite y ß y n e ce KOHHiHa KannaapHa ueB y OTBOP ryMeHor 3anyuiae, Tano Äa Bpx BHpu Hanojbe. J\a 6H ce cnpeiHJio, Äa ce ryMeHH 3anymaq 3ajienH, OBMIKH ce p y n a H cnojbHa noBpuiHHa ca Mano rjiHuepiiHa H yKJlOHH CyBHUiaK 6pH5KJhHBHM 6pHCaH>eM ca BaTOM,

IXCBH

ILYHJEITE

u,een

CTaBH c e

ca

Aa Majio jena

y

BHpa

aa

caropeßaH>e:

rnnper

Kpaja

ueBH

H3 c y a c e H o r A e j i a .

njbocHaTy

cnwpajiy

OHa c n p e i a B a

ueBH.

ueB

3araM

tTaKJieHHM 6nje ce

ce

y

uiTanoM

He c y B H u i e

ca

a3ÖecTHH

OÄ

a3ÖecTa

öaKpa,

qen

Kao

ÄYAFHHE

y3

Tano ä a

5

je

cm,

H

1,5 c m ce

je

oicuiia A e 6 Ä > H H e 1 m m Ha CBOM Ä p y r o M y

Kpajy

ueBH.

Kao

cyße TaKO caBH-

Äoöap

Aa c e B o a a K o a n e H a y j e y cyjKeHOM R e n y

npaineH

cpeöpne

HBHuaMa

ByHy

no-THCHe

cyaceHor

CJIOJ" Ä y J K H H e 0 , 7

a3Öecw.a

3a

Ha

OKCÜW

ryneße

OBO

3aBpmeTKy

öattpa Ä0^a3H

H

noroAHHM

Äe^ia u e B H h cm.

H Ma^o

TaKO Ä a Äy^KHHa c j i o j a

CHTHOT

no

Byne,

äo

c e ÄOÖHje

npeTxoÄHH.

KOJH

c y a c e H H AEO O«IHIIJHEHE H

CTOJ'h « i b p c t o

CBeace H>KapeHor cpeöpHy

cnna ce

UITO

aa

3aoßjbeHHM

CTaBH M3JIH n p a M e H

Ha

CT3BH

ibpcto

CTaKJieHHM u i r a n o M

>K«ua

Tano,

npoBOAHHK TonjiOTe

Y

cpeöpna

Ha T O

TO

caönje

6yÄe 2

mm.

CTaBH

qen

c ^ o j CHTHor

nyaefta

ca-

Ha

owcuaa

ueBH p e Ä y n y j e

y

h boaohhks

OapefjHBafte y r j b e H H K a

JlH6Hry

no

49

cuipyju BOFLOHUKU (b. AOJie). U[eB ce ap>kh ycnpaBHO, a chthh OKCUM 6anpa c e JiynnaibeM pyKOM ca cTpaHe Hadnje h y ^ B p c r a msjimm qenoM o a a36ecTa. JX& 6h ce cnpennAo Aa npw HeH36e«HHM npoMeHaMa 6p3HHe caropeBaita Ao5)e h a o Haivie npoMeHe 6p3HHe cTpyjaiba h thmc HacTaHe onac h o c t a a Hecarope^e nape npoljy Kpo3 HanyiteHy ueB, ctsbh ce c s a i e n o a aadecuia koj'h AejcTByje Tano A3 Kpo3 OBy 30Hy 3a h c t o BpeMe npoJia3H yBeK HCTa KOJiH^HHa raca. y Ty cBpxy ct3bh ce H)KapeH 336ecT Ayrwx BJiaKaHa y 3 Maxa npH qeMy ce cb3kh nyT Majio ca6nje CTaKJieHHM mTanoM, TaKO a a ce Ao6Hje a36ecTHH Men ny®HHe oko 7 mm; TpeSa H3^eraBaTH cyBnuie jano ca6njaihe. OBaj qen o a a36ecTa Tpe6a a a Aaj'e T3K3B o m o p CTpyjn raca, Aa npn HampHTHCKy o a 7 — 1 0 cm BOACHor CTy6a y p e r y a a T o p y npHTHCKa npo;ia3H y M H H y T y 10 ml raca K p o 3 n p e ceK ueBH. Ko^HMHHa raca noja npo;ia3H Kpo3 ueB oApe^yje ce noMohy 6poja«ja MexypoBa koj'h ce npnjiHKOM noAeinaBaita a36ecTHor nena y Ty CBpxy 6awAapH Ha MOJie onncaHH HaqHH. riouiTO je OTnop a36ecTrior qena Ha TonJioTH 3H3THO Behn Hero Ha xjiaAHo, t o ce HcnHTH8aH>e H>eroBe nponycTJbHBOCTH Mopa Aa Bpinn KaAa'je HanyaeHa ueB 3arpejaHa. U.eB 3a c a r o p e B a i t e ca ca6HjeHHM rneibe, —

a36ecTHHM q e n o i i

npHKJbyqn c e Ha anapax 3a c y -

yKjbyqH r p e j a a e , noAecii p e r y - m o p npKTHCKa Ha HarapHTHcaK o a 5 — 7 cm, h OApeAH

mhm ce TeMnepaTypa ycTaJinaa — noMohy caTa 6 p o j MexypoBa y 10 ceKyHAH. TpoKpana

cjiaBHHa

j e npn TOMe Tano

ncmiyHO

j e OTBopeHa.

6ouom (bhah Ao;ie)

OKpeHyTa, a a ycnocTaBJba

3aTHM c e B e w y

n OABOAHa ueB c n y i m a AOTJie,

y 10 ceKyH.nn.

CaAa c e jeAHOM

OABOAHe

MapHOTOBe

ueBH

cymeHH Aeo

mbjiom

6oue

Men3ypoM

fipojaiiy

aok

c e ca.ua nawjbHBHM ca6HjaibeM

ca pe3epBoapoM

3a Ba3Ayx h

caropeBaH>e ca MapHOTOBOM

c e He A o 6 n j e

MepH

3anpeMHHa

TaiHO 3a BpeMe o a jeAHe

6 p o j a MexypoBa H3pa>iyna ce . K O H C T a H i a " nena noAecH

Be3y

ueBH 3a

hcth

6poj

Boae noja

MexypoBa hcrime

MHHyTe. H3 T p a j a i t a

hs

orneAa h

6 p o j a q a MexypoBa. n p o n y c T J b H B O d a36ecTHor y3 CTajiHy

K0HTp0Jiy

(JipeuBeHue

MexypoBa TaKO, Aa y MHHyTH npojia3H Kpo3 npeqHHK ucbh 10 ml

c e ca 6pojeM Ky6HHX caHTHMeiapa HAe paAHje

raca.

HeuiTO Ha BHtue ( a o 12 ml)

ueBH BOje AOJia3H n o c a e a36ecTHor qena Aaje TaKol^e H3BecTaH

MexypoBa y FIp« TOMe

nouiTO n y i b e i t e

MaJiH o m o p .

KonaiHO 6a«£-

jiapeH>e 6 p o j a n a MexypoBa Bprnw c e Ten no 3aBpuieHOM nyH>eH>y ueBH.

H3a H36HjeHor a36ecTHor qena AOJia3H c ^ o j cpe6pne Byne Ay>KHHe 2 cm KOMe ce y jeAHoj cTapoj iteBH 3a caropeBaite Beh yHanpeA Aa o6^hk, Tano Aa ce caMO y3 npnjiHMHo T p e a e mojkc Aa ct3bh y ueB mhmc ce •cnpenaBa Aajfae c36njaHje a36ecTHor nena. FIoiiito ce Ha cmj' cpefipHe syHe ctsbh m3ah pacTpecHT ct36ecuiHu neu, cnna ce y ueB y3 CTa^iHO OKpeT3K>e h jisko yAapatt>e ca CTpaHe (He Ha6Hj3ft>eMl) c.aoj okchas SaKpa, iiojn je npeByqeH onoBoxpoMamoM, Ay>KHHe 14 cm h yhbpcth jeAHHM pacTpecHTHM qenoM o a a36ecTa. BanapoKCHA n p e B y i e n o/ioBoxpoMaToM npnnpeMa c e o a KpynHor 6akapokcup,a

hhhhh, uito

c e SaKapoKCHA

nyBajbKOM no

TaHKOM

p a c n p o c T p e Ha

MofyhcTBy a o cBeTAor

j'cahom

ycwjaiba h n o c n e

(Jihho cnpameHH

c a o j y ; o^oBoxpoMaT Kojn c e oAMax Tonu n p e B y q e

npHjaH.a, npH weMy c e r p e r a p a Ha

hcth

Ha Taj

MajioM rB03AeH0M aHMy, 3 a r p e j e 0 A 0 3 r 0

okcha

oAOBOxpoMaui

6 a S p a cjiojeM

kom8ah Heuno c a e n e . T a a a c e CTon^eHa Maca onpeHe, h Apyra IIouito c e Maca oxjiaAH, 3Apo6w c e Majio y aBaHy, h cejafteM

CTpaHa

Ha^HH.

oABojH

:npax o a cacBHU KpynHiix KOMa.ua. flpaKTOKyM opraHCKe xeMHje

y

koj'h hbpcto

4

50

Meiojie opraHCKe ejieMeHTapHe aHa;iH3e

noiiiTo ce cnna c;ioj 6aKap0KCHA-0Ji0B0xp0MaTa h yqBpcTH jcahhm pacTpecHTHM a3ÓecTHHM qenoM, ^ h c t h ce ueB Bp^o ópnJKJbHBO je^HHM BejiHKHM KOMa^OM BaTe HaMOTaHHM Ha Mcrniy, aok ce BaTa BHiue He óojn oa npaxa 0Ji0B0xp0MaTa. Ha caoj 6aKap0KCHA-0Ji0B0xp0MaTa AOJia3H cJioj cpeópue Byne AyacuHe 1,5—2 cm, 3araM M&JIH pacTpecHT a36ectüHU neü, h nao 3aBpmeTaK cnoj pacTpecHTor üJiawuHCKor asóecüia AyíKHHe 2,5 cm hjiu ffipyóuiia oa üJiaTüuHCKe Mpeotcuife Ay^KHHe 3 cm. nocJieAH>H cjioj cpeópHe ByHe oÓHaB./ba ce nocjie 5 y3acronHHx carQpeBafta jeAMbeiba noja c a a p » e x a j i o r e H a HJIU c y M n o p a . TaKO HanyH>eHa ueB HcnHTa ce ca^a — Kao i i i t o je r o p e oriHcaHO — jorn je^HOM Ha nponycTJbHBOCT h ópojan MexypoBa ce ^ccJjhhhthbho 6aiKAapH. noiiiTO ce aeB H>KapH no cbojoj' uejioj AyiKHHH y crpyjH c y B o r Ba3Ayxa, oahocho KHceoHHKa, oHa je cnpeMHa 3a caropeBaibe jeAHH>eH>a K o j a He c a A p « < e a 3 0 T a . CaropeBaH>e cyncraHUH 6e3 a30Ta h3boah ce y CTpyjH k h c c o h h k 3 yMecTO y CTpyjH Ba3Ayxa. 3 a caropeBatte cyncTaHijH n o j e c a A P ^ e a 3 0 T a p e a y K y j e ce c;ioj 6aKapoKCH^a oa 5 cm Ay>KHHe y cüipyju BOAOHUKÜ Ha HaqHH Kojn je ormcaH koa OApei]HBaft>a a3ora. n o c j i e peAyKOBas>a aa. U,eB 3a caropeBaibe, ano ce ca k>om 6pn>KJbHBO nocTyna, MO»e Aa Tpaje t o j i h k o Aa ce ca h>om h3bpiiih 1 0 0 h bullíc aHa;iH3a. A n a p a T H a a a n c o p n u H j y h h>hxobo nyH>eH>e: 3 a ancopnuHjy b o a e h y r j b e H A H O K C H A a , Kojn ce cTBapajy npHJiHKOM caropeBaita, ynoTpefijbaBajy ce CTaKJieHe u e B H H i x e 3 a a n c o p n u H j y t3hkhx 3haob3 ca no ABa ópymeHa qena KojH cjiyiKt nao cjiaBHHe (no Blumer-Berger-y, CJI. 37). BoHHe neBUHue Tpeóa Aa ce tsmho noAyAapajy y CBOMe cnojbH>eM npe^HHKy Kano Mei^ycoÓHO TaKO h ca cytfceHHM AejiOM uébh 3a caropeBaH>e. JeAaH oa ópyineHHx qenoBa ueB^Hije ca KajniHjyMx^opHAOM (JiopMHpaH je Kao ,,p e3 e p B o a p 3 a b o a y" • OBaj i e n HMa aho ca jeAHHM (J)hhhm otbopom Ha KOMe ce Hajia3H jeAHa Kannjiapa. O^HiiiheHa h ocyuieHa x a o p K a j i u H j y M - u e B q H u a nyHH ce t 3 k o Aa ce Hajnpe ópyuieHH wen ca KanHjiapoM noAMaace ca Ma^o Ba3e^HHa, npH qeiuy ce ropifcH Aeo Mena y mnpHHH OA 2 mm He noAMa3yje, OAHOCHO Cn. 37 Ba36JiHH ce ca Tor Ae-fla i e n a oópnme KpnoM, Aa Ba3eJiHH npn cTaBjbaiby i e n a He 6 h H3auiao Hanojfae. BpymeHH Aeo Tpeóa Aa je npoBHAaH; nen Tpeóa Aa Moate Aa ce OKpehe caMo y 3 3HaTHO>

OFLPELJHBAH>E YRVHEHHKA H BOAOHHKA

51

no JlH6Hry

T p e i t e . CyBHIIIHH c e B 3 3 E J I H H 6pH)KTT>HBO yK^OHH H3 OTBOpa C J I 3 B H H 6 H H3 6 o q H e ueBHHue KOMaAnheM BaTe. H a 6 p y m e H H q e n c t 3 b h c e c a ^ a MSJIH upaMen Banie, CHna Hajnpe Kpymo3pHacuiu KajiifujyMXJiopua y B H C H H H O A 1 cm, y i B p c T H c ^ o j ApyrHM npaMeHOM BaTe h c a a a CBe AO S p y m e H e n o BpniHHe CHna y 3 JiaKO J i y n n a i t e KaJiifujyMXJiopua BejiHHHHe 3pHa n p o c a KojH j e npeTXOflHO ocytuen Ha 1 8 0 — 2 0 0 ° . I I O I I I T O c e H O B a j CJIOJ" y i B p c T H jeAHHM c y LU e H H M npaMeHOM BaTe, H S p y u i e H a N O B P U I H H A ueBH 6pH)KJbHBo H36pHiiie, CT3BH c e 6 p y m e H H q e n Kojn c e n a o H r o p e noAMaace Ba3eJIHHOM. UlynjbHHa i e n a ncnyHH c e J E A H H M pacipecHTHM ocyuieHHM npaMeHOM BaTe. nawTO Ka^uHjyMXflopHa ca^p»H 6 a 3 H e cacTojKe, TO ce canpucaj ancopnuHOHe ueBinue npe H>eHe ynoTpe6e Mopa «a 3acnTB yrjbeHflHOKCHAOM. y OBy CBpxy npHKJbyiH ce 6oiHa ueBwHua Koja boah na „pe3epBoapy 3a Boay" npeno je.nHe UCBH 3a cyuieite Ha K H I I O B anapaT, npoBojiH y TOKy on 10 MHHyTa jana cuipyja yeJbeHduokcufla h ociaBH aa CTOJH 1/2 caTa 33TBopeH0 noil IIPHTHCKOM KOJH flaje K H I I O B anapaT. nouiTO ce noMohy MapHOTOBe 6oue npoayBa npo3 U.CB 200ml cyBor aaspyxa ueB je cnpeMHa 3a ynoTpe6y, JEAHOM 3A

15

HANYHIEHA

u e B q n u e ca

XJIOPKA^IIHJYM-UEBHHUA

H>eH c e c a A p » a j HaTpoHa36ecroM.

AHAJIH3A;

O6HABJBA

MOJKC

AA

HCTOBpeMeHO

C^YJKH

KaA

H

HAJMAITE

caAp)«aj

O^HinheHa H o c y m e H a U E B Q N U A c a H a T p o H a 3 6 e c T O M nyHH c e TaKO, Aa c e H a j n p e nponHCHO nocTaBH noAMa3aHH 6 p y m e H H Hen HHja ce myn^jHHa HcnyHH J ' C A H H M pacTpecHTHM KOMaauheM Bauie. H a OBaj c e CT3BH JEAAH M&JW N P A M E H B A T E , 33THM c e Y 3 JiaKO J I Y N K A I T E ca cTpaHe HanyHH A O 2 / A nauipoHa36eciuoM ( „ M e r c k " ) H C J I O J ' noKpnje A P Y R H M M S J I H M 1 N P A M E H O M B A T E . 3 A T H M ce C T A B H c ^ O J O A /2 cm oSnqHor KcumujyMXJiopiim K O J H HHje H A P O I H T O cyuieH, N O H O B O n o n p H j e pacTpecHTHM N P A M E H O M B A T E , H 33THM HanyHH CBe AO 6 p y m e H o r A e a a KajiifuiyMXJiopuaoM BejiUHUHe 3pna upoca Koju je cyuien H3 1 8 0 — 2 0 0 ° . C j i o j c e c3Aa 3aBpniH npaMeHOM c y m e H e B A T E H C T 3 B H ce 6pymeHH qen N O A M A 3 A H B A 3 E J I H H O M . U , E B H H U A je O A M A X cnpeMH3 3a y n o T p e d y . O B O nyfteibe MO)KE AA caywH HAJMAITE 3A 15 oApeijHBaiba. Y oHoj Mepn y K o j o j HaTpoHa36ecT a n c o p 6 y j e y n b e H AHOKCHA M E it a M y c e H 6 o j a, H O A npjbaBO C H B C n o c T a j e C B E T J I A , Te c e H3 OBe npoMeHe 6 o j e Moace Aa 3aK;byqH Aa m ce H C T O nyn>eH>e Moace Aa y n o T p e 6 n j o m H 3a c a e A e h y aHaJiH3y. M H M c e HaTpoHa36ecT T O J I H K O y T p o n i H Aa n p e o c T a j e caMO j o m C J I O J ' O A 1 c m nyH>eH>e c e O 6 H O B H . r i o m T O j e T e H 3 H j a B o A e H e n a p e H3HaA HaTpoHa36ecTa Maita H e r o ;IH H3H3A A o 6 p o H c y m e H o r Ka^UHjyMX^opHAa, TO c e Mopa H3Meljy o 6 a OBa a i o j a Aa CTaBH HemTO o i a q H o r K a ^ u a j y M X ^ o p H A a K O J H HHje HapoHHTO c y m e H . U,eBHHije 3a a n c o p n u n j y B e m y c e M e ^ y c o d H o KOMaA«heM BaKyyMCKor M a i o r y H y T p a m i t e r N P E N H H K A A Y » N H E 2 cm; U P E B O KOJHM c e ueBHHaa B E A C E 3 A ueB 3 A c a r o p e B a i b e A y r o j e 1 , 5 c m . O B H c e K O M 3 A H iipeBa npeTX0AH0 HaTone Ba3e^HHOM y BanyyMy ( y n o p . CTp. 4 8 ) . r i p w Be3HB&H>y c e na3H H A T O A A n p a j e B H 6 O H H H X U E B H H I T A , K O A K O J H X c y UPEBA

4*

52

MeToae

ouiTpe j e

HBHue

na)KJbHBHM

M o r y h e

6 o j b e

H e n o A y A a p a a a HOM c e

y

ryMeHa

KBauieH Aa

ce

Ha

ca

Taj

UITO

CB3KH

o t n o p

jtJopHÄOM

6ou,a:

B e 3 y j e 3a c y w e H H

BeJiHKoj M e p H a o B o a n »HXOBe

nouiio

HCKOJIHKO cm

oa

.anapaTH 3a a n c o p n u w j y ,

Kpo3

OTBop

rviHiiepHHa

3a y

crpe;IHRA

npaBixy.

H3HyTpa

npoByqe

tu T O

eaeHTya^Hor

Be3HBaH>e

TOM

ca

6H

cacBHM

KOMa^nh

HeonxoAHo

6pn>KjbHBo

y

HanyH>eHe u e B q n u e

Boaenor

Ma.no

BaTe

je

Ha-

noTpeÓHO

yKJioHH

aeo

ueBH

npoTHBMepa

3a c a r o p e B a i t e ,

BJiaaa npHTHcaic

onacHOCT

KBaHTHTaTHBHo

cacTojH ce y

M a p H O T O B e c M a H> e H H

KOMaAHheM

n p n T H c a K

KO]H M o w e

(He r y M e H o r )

Ma K o j H n o j i o » a j . H a

a aa ce

3anyuiana

ix e B H

3a

ueB 3a a o B o l } e H » e

y

raca

•4Hua

KajiUHjyMxaopnaoM 3aTBopn

M e p e i t e : JIOKH

ce KannuoM

oa

c r i o j a

B a i a r e ,

UHjy

TpeTHpajy

Aa

ce

cnoHAeHTHHM

t:a

CBHX

a

33THM

KpriHue npeKO BaH>e, heM

ca

noJia3ehH noBpuiHHe Mopa

AA

ueBHHue

ce

Haj-

Be3HBaH>e,

npn

Y

y

AA

M O » e

ancopnunjy

Koje

Ty

AA

Kpaja

no-

caBHjeHa

MapHOTOBa

ca

y

noa 6oua

ryMeHHM

KajiUHjyMXJio-

yrjioM. K o a

aHa;IH3E c e

HaTp0Ha3óecT0M;

Kaa

HA

TA^HO

H36pnuie

ueBce

He

AO

CKHHC

Hajnpe

Ha

H36pHiijy

y

ancopn-

OBHM

H

Aa

„Kope-

H

AA

6 p n » j b H B o

O A

Taj

y3

HAQHH

jano

noBpuiHHe

napoM

ce

npeB^aqe IIPHTHCKHKOM3AH-

yjia3e

Ba3e^HHa.

jeAHHM

UITO

HHCTHM

TaMaH

H

4 ) J i a H e ^ a ,

o6pTaH>e

ó p y m e H e HCIIITO

Meiba

3a

HAQHH,

rioA

H36pHiiiy

Tano

jano

HCTH

n p n a

NOROTOBO ce

ce

Ae4)HHMCAHA. ce

npnTHcaK

» H u e

a n c o p n nocTojafteM

cyAOBH

cawo

K O K C .

ueBqane

KOJ'H

cacBHM je

OB^a»eHHx

AO^e

H

MOpajy

noniTo

3a

yc/iOBjbeHe

CTaK^a

Tpjbart>e,

jeAHOM

a n a p a i a

CBpxy

6JIar

y3

He

ca

cy

AHA^H3e

rB03AeHe

JIAKO joui

Ha u e a

j e ^ e H c n e

ce

c e ywBpcTH

u e B ; OÓHMHHM

u e B H

npaBHM

Mepeity

jeABa

BOMHE

OKO

Ha 0 6 a

oaBoaHa

MaaoM

TOKHHH

cyBHiiiHO

H3ÔerHe.

ueB

c e u e B MO>Ke a a a o B e a e

upeBa.

BpeMeHa,

cpeAHHe

CTaK^a;

na3HTn

HHane 3a

OA

h3MOT3hhm

Tpeóa

NOUITO

ce

y

aóor

c a r o p e B a i t a

fioche

nâpoM

Koja j e

KOJH HM3

HaTp0Ha3ÖecT0M

Kpne OA

H

PA3JIHKA

ca

jeAHHM

ABE

B a T e

HHiJiy;

ueB

cTpaHa

caMO nan

caropeBaita, jep

cjiaBHHa K o j a o M o r y h y j e a a c e

noBpiuHHy

HCTor

CTAHSHMÂ"

raca,

rpemaKa

ycJiOBa.

npe

nocrce

Hanyft>eHa

THMC c e

T o c e n o c T H u c e npmeM

T3KO a a

6oue,

anpeKTHO

noKpHBa

criojbHHX

TaqHO

npHKJbyqe

MeH>a.

ca jeaHOM

TeuiKoha

Kojn

OA

Mepe

ce

r a e c e Bpiun

O a Bo a H a

ryMeHor

H3ÓeraBaH>y

33BHCH0CTH

ce

caBHjeHe n o a

npHKJbyiH

DiaBHa

y

npo.na3y

H>HXOBHX r y ó m a K a .

Ha M e c i y

Ty6yc

HBBOÌjeH>e

U H j y

npoay«aTa

aa aol)e a o

yHyTpa

aa

aTMoccJjepcKor.

H3 u p T e w a .

noJio»aj

KOJH HMa a B e 6 o H H e u e B i H u e

jnoTpeÖJbaBa

MO»e

y B o l j e n e

;p H a 0 M ca

xBaiahbe

ce

jiano aa

npoH3jia3H

He Metta oapetjeHH

upeBOM Be3aHa j e

cjiyiajy

oa

n p i i i H c a H .

n p a B H M y r j i o M Ha a o j i e , Hajia3H c e c T a n a e H a HCKJBYQN.

y

Beh»

n p y w a j y npw

r a e c e ueBHHua c a K a j i u H j y M -

K o j a ao3BOJbaBa a a c e y a n c o p n u H O H H M a n a p a T U M a y c n o c T a B H o a p e J j e H

y p e l ^ a j MapHOTOBe 6 o u e njiyTeHor

TOMe a a

a t M o c i j i e p c K H

6 o u e

3a a n c o p n u H j y

c T y ß a , TO Ha M e c T y

Mopa a a

ycnocTaBH no M o r y h c i B y

ce

ce

rjiHuepnHa;

B e j i H K e K O H u e H T p a u H j e Ha OBOM M e c T y

ei})HKacHHja

Mohy

ce

yBen

O B ^ a « e

3ao6^>eHe,

M y n a j y

upeBa

npHKjbyqyjy

KOJIHHHHOM

cyBHiiiaK

ce

y

BATE. MapHOTOBa

raca

HannH

6;iaro

ApyrH.

o6e;ie>Ke

H

aHa;in3e

naaMeHy

Ha

HaBJianHJia

MHHHM3^HOM

noTOM

CYBE

raca

Pianine

Ha

je^aH

U6BH,

CTpyjaita

upeBa

emiiepuna,

3arpeBaH>eM

H a ^ o n y

npenHHKa

npaBuy

opraHCice e j i e M e H T a p H e

H a

y

ueB-

c^aBHHe, Kpajy

cyBHX

ce K p-

53

Ojipel]HBaH.e ynbeHHua H BOAOHHica no .TlHÖHry íiHua

OA

jejieHCKe

Koje

k o jk e

Tpeöa

Aa

KJiH3e

npeKo

noBpuiHHe

JiaKO h HecMeraHO. T a ^ a ce ueBHwja, He A O A H p y j y h n j e npcTHMa, no^oiKH Ha c T a j i a n on, Ä H i j e

(cTajiaK 3a Apacajba 3a n e p a ) HenocpeAHO

nopeA

Bare; BpeMe KaAa c y ce ueBqnae ocTaBHJie t 3 h h o ce 336ejie>KH. H a HCTH ce HaqHH npwnpeMH 3a M e p e i t e h ueB ca KanunjyMx^opHAOM. 3a BpeMe a o k ce iteB^Hue x ^ a A e Mepn c e cyncTSHija (b. A o a e ) . CaAa ce OApeAH h y j i t a T a q K a a3ôecroM,

Koja

ce

noc^e

ßpHcaita

Bare. O h a s c e ueBHHua ca HaTpoHBHiiie

yxBSTH cyBOM KpnoM OA jejieHCKe n o m e , HaiH h

npHTHcaK

noMohy

m hue MajiH

oc;iaH>a

Ha

Aße

oa

nojiojKH

JK h h a h h

npcTHMa,

KpaTKHM OTBapaibCM c^aBHHe,

b h jb y in k e

( c a . 38)

He CMe a o a h p h b 3 t h H3jeA-

h o c a h, Taqne.

3JiyMHHHjyMCKC

Ha

JieBH

Ha

Tac

KOMe

Bare,

ce

V

Ha

l

aeBHHua

5

33thm ce ct3bh Tapa (3a

a

— — i r ^ w ^ .

^ — ^ — * —

T a p y ynoTpe6^.aB3TH yBeic « e r e T e r o B e ) h OApeAH,

—r^

"

10 MHHyTa n o c ^ e öpncaiba ueBqnae, n p h 6 Ji h hc h a

Ca. 38'

T e >k h h a, npH qeMy ce CT3BJbaH>eM c^-TeroBa t 3 k o noAecH

Aa

jeAaH

no^y3H

Bare,

jaxsq

AoJje no MoryhcTBy

y

MHHyiy

15

H3

noieiaK

cnajie

OApeAH c e TsqH3 t o k h h s .

Ha

HenocpeAHO

n o c j i e OBora OApeAH ce tchchhe ueBqHije ca K3;mnjyMx.nopHAOM. r i o 33BpmeTie, K o j e he caAa HeuiTO 3yje

pa3^HMHTO

jaxaq.

Moine

Aa

yc;ieA

OTCTynaibs TejKHHe TeroB3 o a OHe K o j y

Thmc ce nocTHJKe H3BeAe

caMo

ca

Aa ce Mepes>e n o c ^ e H A y h e r

jaxsqeM,

KojH 6h T p e ó s j i o Hajnpe Aa ce CyncT3HH3 XHrpocKonHe

ce

Mepn

qyHHh

caropeB3K>a

He AOAajyhn npw t o m HOBe TeroBe

óa^KAape. y

cyncT3Hue

ÍIji8thhckh

óhth noKa-

ce

OTBopeHOM Mepe mhcth

ce

y

ii^isthhckom 3aTBopeHoj

t3ko,

Aa

qyHHhy; iieBiaii«.

ce npoKyBa y

pa3Ö^3-

JKeHoj a30TH0j KHceJiHHH y enpyBeTH, KpaTKO H » a p n h3 njiaTHHCKoj jkhhh Ha 6e3Ô0jH0M

njiaMeHy h n o c j i e

HHKJIOB3H 6 a K a p H h

xjiaijeiba

1 / 3 MHHyTe

oko

c t s b h h3 no-

6ji ok.

ripa3aH ce qyHHh c t s b h nHHueTOM Ha Tac Bare h ópnmjbHBo H3Mepn ca TaqHomhy

o a 0,01 mg.

CT3BH H3 iJHCT

KOM3A

f l o c j i e cnnaita cyncTSHue npn qeMy c e qyHHh

X3pTHj'e,

OApeAH npnpacT t o k h h c

H36pHUie

Ce

CnOJb3

ca T3HHoiuhy o a 0,01 mg.

(})HHOM

KpnHUOM H

3a C , H-OApeljHBatba

y3HMa ce 2 0 — 3 0 mg. n o c j i e Mepetta c t 3 b h c e qyHHh i i o h o b o Ha 6aKapHn 6 j i o k h OBaj n o K p n j e msjiom cTaKJieHOM iuojbOM.

54

MeToae

opraHcne

eaeMemapHe

aHajiH3e

CaropeBaH>e Join 3a BpeMe xjia^eaa anapaTa 3a ancopnunjy yKJbyqn ce e ^ e K T p H i H a n e h , npn qeMy ce Kpo3 ueB nponyuiTa CTpyja B a 3 A y x a HCTOM 6p3HHOM Kao H 3a BpeMe aHajiHse.1 A K O ueB npeTxoAHO H H j e 6HJIa Hapo^HTo cyuieHa, UJIU ano je Ay>Ke BpeMeHa erajajia HeynoTpeôjbeHa, TO ce npe n o t e r a s jeAHe cepnje ananma, noiiiTO je neh Beh AOCTHivia CBojy TeiwnepaTypy, » a p n npa3aH Aeo nesn KpaTKo BpeMe y c T p y j H B a 3 Ä y x a ByH3eH0BHM njiaMeHHKOM npeKO u h j i h h a p h h h c M p e Ä H u e , T3KO A& ce noHHibe Ha 1 cm O A ryMeHor 3anymaqa K O J ' H ce 6pH>KJbHBO 33UITHTH 3 3 K J I 0 H 0 M ofl 3 3 6 e c T a. KaA ce ca rpejaiteM E>yH3eH0BHM nJiaMëHHKOM A O U I J I O A O e^eKTpHMHe nehn yKJiOHH ce nJiaMeHHK h noByue UHJirtH^pnqHa MpejKHna HaTpar,Ha Kpaj neBH, m 6u ce Aeo u , Ê B H Kojn je ÓJ1HMH ejieKTpHHHoj neh« H y K O J ' H ce CTaBjba MyHHh ca cyncT3HUOM, noHOBO oxjias.no. noniTO ce a n a p a T H 3 a a n c o p n n n j y H3Mepe, HaByqe ce ryMeHO npeBO 3a Be3y Ay®HHe 1,5 cm AO nojia Ha OHy 6oMHy ueBiHuy ancopnuHOHe ix e B H c a K a j i u H j y M X J i o p H A O M Koja B O A H A O pe3epBoapa 3a BOAy, AOK ce ôoiHa ueBinna Ha ApyroM npajy npHKJbyqn noMôhy ryMeHor upeBa 3a Be3y Ay>KHHe 2 cm Ha OHy óo^Hy neB^Huy ancopnuHOHe Il e B H c a H a T p O H â 3 Ô 6 C T O M ' KOja ÄHpeKTHO BOAH A O CJIOja HaTpOHa3ÖecTa, T 3 K O s a KpajeBH neBH no MoryhcTBy Aoöpo Hajiemy je^aH Ha Apyrn, H CBe ce npn^BpcTH Ha C T S T H B . Ca^a ce, rJieAajyha na caT, K O H TpojiHme $ P e K B e H y a M e x y p o B a Ba3AymHe CTpyje y TOKy OA 10 ceKyHAH, H 3KO je noTpeÔHO Meas nojiojKaj p e r y ^ S T o p s n p H T H c n a , T3K0 Aa ce nocTurHe 6p3HHa CTpyje OA 9—10 ml Ba3Ayxa (OAH. KHceoHHKa) y M H H Y T Y , I I I T O ce B H A H H 3 ôpoja MexypOB3 HA 6 A « I A A P E H 0 M 6pojaqy MexypoBa.

Pa3Jior „OTKa3HBaH>a" ópojawa MexypoBa jiewH necio y TOMe IUTO pacTBop XHapoKcwaa nocTaje npn aywoj ynoTpeön KOHueHTpoBaHujH; y TOMe ce cjiyqajy aocne C B O K (eßeHTyaJiHO pa36fla>KeHHjH) pacTBop xnapoKCH.ua, am ce ôpojai MexypoBa npH TOM Mopa noHOBO Aa ôaHcaapH; apyrn H3Bop rpeuuaKa noTHne oa cJienjbHBaHja I:ajmHjyMx;iopHfla KOJ'H ce na;ia3H y anapaiy 3a cymeite, OÄHOCHO y ueBH 3a cyiueite Ha 3BOH3CTOM racoMeipy. Mopa ce Haj6pH>KJbHBHje na3HTH, aa TeMHOCT H3 ôpojaqa MexypoBa ne aocne y ryMeHO upeBO KOje je cnojeHO ca TpocTpyKOM cjiaBHHOM. CaAa ce npnKjbymi neB ca Ka^UHjyMX.iopHAOM HenocpeAHO h3 cy«eHH Aeo i x e B H 3 a c a r o p e B a H > e , H neB ca HaTp0Ha3ÔecT0M Berne ca neBH ca KajiUHjyMx^opHAOM M a p n o T O B e 6 o n e. Ha TO ce CKHHe ryMeHH 33nymaq ca ueBH 3a caropeBan>e, noByqe C T 3 T H B ca anspaTOM 3a cynieite HA3AA, A A 6 H ce A O Ó H O c^oôoAaH npocTop, noAurHe ôaiopHH 6 ; I O K ca 1

xypoBa

npn y

TOMe c e

ôpojaiy

a36ecTHH nen y jbeHo

ueBH

noBehaaeM

npHMehyje

MexypoBa, cnpeiaBa

TeMnepaType.

Ha

Ma a a

noneTKy

3arpeBäH>a

pery^aTop

MOMeHTaHo Cb3KH

H3jeÄHa>jeH.e

nopacT

BaH>e ( J j p e K B e H u e M e x y p o B a , UITO j a n o o ^ a n u i a B a

3HaTH0

npHTHCKa

npHTHCKa

He

cMaH>HBan>e a

noBehaH.a y

ueBH

CBoj

noao>Kaj,

npHTHCKa yc^oB^aBa

Koje je aaKJie

K o a aHaJiH3e T a q H o npaheH>e TOKa

Me-

nouiTO ycJioBCM3H>H-

caropeBaaa.

OflpeJjHBaifae yrjbeHHKa HyHwhcM AO roAHHM

OTBOPA

qHCTHM

I^CBH,

no JlHÖHry

H BOAOHHKS

55

CT3BH nyHHh nHHUCTOM y ueB,

CTaKJiCHHM

uiTanoM,

na3ehH

Aa

ce

He

noTHCHe no-

H

npeBpHe,

ao

Ha

4—5 cm A O ejieKTpHMHe n e h n . C a A a c e C T 3 b h y u e B O B ^ a u i r y M e H H 3 a nymaH, eBeHTyajiHo oBJiajKCH c a B P ^ O Ma;io IVIHUEPHHA, H yByqe y3 JiaK npHTHcaK KOHHHHO H3ByqeHa Kanw^apHa ueB anapaTa 3a cyiueite y OTBOp Ha 3anymaiy, T 3 K O Aa Bpx jeABa B H P H H3 sanyuiaqa yHyrpa y uèBH.

yHDuieft.e cyncraHue

Mopa

ce

H3BPIHHTH

CITO

M o r y h e 6pace, Aa

je

He 6H BJiara H3 Ba3Ayxa AOuiJia y ueB. CaAa c e O T B o p e c a a B H H e H a a n c o p n u n o K H M anapaTHMa H CJISBHH3 HA MapHOTOBoj 6 O U H H n p o B e p n A a JIH c e A o ö w j a c r a p a , paHHje y T B p ^ e H a , ( J ) p e K B e H u a 6poja

M e x y p o B a

MexypoBa

noHOBo ueBH

paHHja

XBaTa

» « U È

KOJH

cy>KeHH

AGO

xjiopHAOM,

TO, A a

NYAEH

CMera.

BoAa

Koja

Kanjbe

H npeHOCH

TONJIOTY

caropeBatte

Meiaji

BOAE y

OTCTynaite AKO j e

MexypoBa cnyuiTaiteM

OA 5 0 0

3a

Aa

öpojany; He

M e H3 y p y

OABOAH

TaKo

ce

y

y

ceKyHA«

6oue.

ce

ueBH

K0HAEH30BAFT>E

CaAa

10

(JjpeKBeHua

MapHOTOBe

aHajin3e

Ha

y

H Ha

AOAnpyje

H3

T ^ a

OBHM A E ^ O B H M a

ce

ejieKTpHHHe

öoiHy

ueBqwuy THine

ce

B33AYXOM

(OAH.

r a c Q„M e T a p KHCCOHHKOM),

jeAHHHue

ycnocTaBH

6oue

KOM3A nehn

ce

OABOAHC 3a

Bpeiue

6 a Ka p H e nojioma

ueBH ca

na

Ka^uHjyM-

noy3AaHO

H3ÖeraBa

ueBH.

y cTBapH noHHH>e ca c a r o p e B a i t e M .

3 B O H 3 C T H

1—2

HJIH n o A H 3 a i t e M

MapHOTOBe

ml.

craiíJio;

OA

noTpeÖHO,

6YAE

3A

BpeMe

TANO AA CBAKHX

Tpeôa Aa 3H3JiH3e 10

AO

ce

cTajiHo 15

H33H Ha-

CEKYHAH

OAH^ia3H no jeAaH Mexyp. MHM ce ueB y yHyTpauiibocTH nehw ytfcapwjia AO upBeHor yaijatta, noMaicHe ce yHanpeA U H J i H H A p u í i i a M p e a c a u a A y r a 5 cm, Tano A a CBojOM npeAffcOM HBHUOM A o n w p e CKopo A O nyHHha H CT3BH nyH 6e3ÓojHH n^aMeH ByH3enoBe rpejajiHue Ha 3aAft>H Kpaj Mpe>KHue. 4>peKBeHua MexypoBa Koja ce y no^eTKy ycjieA 3arpeBaii>a ÖHJia CMaHjHJia, nocjie KpaTKor BpeMeHa oneT c e noBehaBa. O Ö H ^ H O he cynCTaHua, Koja c e Hajia3H y 3aAH>eM Aeay QYHHHA, n o q e T H n o c ^ e HCKOJIHKO MHHYTA A a c e ToriH, HJIH AA AecTHJiHuie, OAHOCHO AA cyô^HMHiue. H e Ka ce y 3 M e K a o n p a B H J i o , A a c e U H J i H H A p n i H a M p e >K H u a H B y H 3 e H o B^ N J I A M S H H K n o M e p a j y y H a n p e A T C K o H A a, K a A C B Ë n p o M e H e K o j e c e Ha c y n c T a H U H A e i u a B a j y n o i n y n o HUIi e 3 H y . TaAa ce noMepa ompHjiHKe CB3KHX 2 MHHyTa uHAHHApH^Ha MpeJKHITA 3a 2 — 3 mm yHanpeA, H 3a H>OM noMepa njiaMeHHK, T 3 K O Aa OBaj CTOjH CTSJIHO HcnoA 3 3 A f t > e r A e j i a M p e > K H u e . ripa TOM ce ( J j p e K B e H u a M e x y p o B a y öpojaiy MexypoBa npHBpeMeHO CMa&yje; noiuepafbe yHanpeA ce T3KO noAecH, Aa ce 6poj MexypoBa IUTO je Moryhe MaH>e cM3u>yje, Aa 6H ce yBen «Mao Ha p3cno;io>KeH>y BHIIISK KHCCOHHKS; N O M E P S A E Y H A N P E A npeAy3HMa ce H 3 HCTH HSMHH TCK O H A 3 I O A ce NOHOBO AOCRARHE N P ß O Ö H T H A (JjpeKBeHua MexypoBa. O C H M TORA UITO ce N O C M A T P A K 3 K 0 ce n o H a i i i a c y n c T a n u a , T P E Ó S C T S A H O n p O M a T p a m H 6 p o j 3 h M e x y p o B 3 . Tpe6s H3öeraBaTH cyBHiiie 6p30 noMepaae yHanpeA, jep ce HH3He nape Bpahajy Harpar y ueB; 6pojan MexypoBa He

Mexoae opraHCKe ejieMeHTapHe aHajiH3e

56 Tpeóa

HH y

KOM c j i y n a j y

A a n p e c T a H e AA p a A H HJIH AA M y c e QAK TCHHOCT

noBpaTH HaTpar y ueB. y HajBHiue c.rcyiajeBa oópa3yje ce y ueBH Henocpe^HO jb

HcnpeA

Hua

miaTHHCKor

TCIBOCTH;

TO

npoueca caropeBHH>a,

qyHHha y c a e A K0HAeH30Baft>a

BSJIHK3

K a N-

y BejiHKoj Mepn oyiaKiuaBa npaBHJino Bo^eite

noniTo ce AejcTBO pery;iHcaH>a TeMneparype MO»e

Bpjio oiiiTpo Ra nocMaTpa Ha npoMeHaMa Kanjbnue. CBa BeniTHHa caropeBaita cacrojH ce y JiaraHOM, C T p r r j b H B O M H c n a p a B a H > y K a n j b H Q e , npH neiuy Tpe6a HM3TH Ha yMy Aa ce npeHoc TonjioTe j a n a noBeha, »IHM ce ca miaMeHHKa AOTJE AO iuiaTHHCKor qyHHha; npeMa TOM& Ty Tpeóa noMepatte HOCTH HcnapHJiH,

BPIIIHTH cnopHje.

3arpeBa ce ueB Ha

HHM c y H noc,fleAH>H ac;IOBH Teq-

OHOM MecTy Ha KOMC

Jiescn

N^ATHHCKH

nyHnh ByH3eHOBHM njiaMeHHKOM 6e3 inpe>KHue, AOK ce ueB H nyHHh ynpaBO He y a t a p e ;

Ha HCTH ce HamiH H ACÓ

ueBH

AO

ejieKTpnqHe

nehn

6p3HM

3arpeBanbeM yjKapH AO TaMHoupBeHor ycnjaita. y r a jb, Kojw ce IIPHJIHKOM pa3Jiaraft>a c y n c r a n u e H3ABOJ'HO, O6H4HO Ha oBaj Ha^HH aaK0 caropH;

ana

je noTpeÓHO ynepn ce njiaMeH H o A 0 3 r o na ueBH. AKO ce npHJiHKOM p a 3 •naranja c y n c T a H u e

CTBOPHO

TeniKO

npHjaita y 3 3HAOBC

ueBH,

ce cacTojw y TOME,

Aa ce yra;b

qeMy

OH a n c o p S y j e

KuceoHum

TpeÓHO

caMO

KHCCOHHK H npn

IIOHOBHOM

Bpjio TeuiKO

BpiiiHJio y CTpyjH KHceoHHKa,

KOJH

HBPCTO

BeuiTHHa

Koja

ox^aAH,

npn

}Kapeii>y 6p30

caropH,.

OBO he MeljyTHM 6HTH no-

caropjbHBor

TO ce,

npeGauH Be3a n0H0B0 Ha cüipyjy

Majia

TeqHHx AeJiOBa npeóaun Be3a Ha

HCTe (JjpeKBeHue MexypoBa.

KOA

yrajb

jeAHa

OCT3BH Aa ce npHBpeMeHo

HapoMHTo KaAa ce nooie ncnapaBaita cmpyjy

c a r o p ^ H B H

TO qecTO noMaiKe

yrjba.

AKO ce c a r o p e B a a e

IHM je yrajb caropno 6es

Bü3nyxa,

ocTaTKa^

Aa ÓH ce npHHyBao peAyKOBaHH

caoj 6aKpa. Meció ce onama joui 3a BpeMe caropeBaH>a, aa ce y ópojaiy MexypoBa npiunmHO peKBeHua MexypoBa; pa3Jior xoMe je Taj, IUTO ycjiea JKHBC ancopniuije HacTa^or yrjbeHAHOKCHfla y ueBHHtw ca HaTp0Ha3óecT0M HacTaje c M a H> e H H n p a m c a K ; HCTOBpeMeHO nonymia 6p3HHa Kanaita H3 MapHOTOBe 6oue, HJIH naK 3a H3BCCHO BpeMe KanaH>e cacBHM npecTaje. OBaj je nopeMehaj 6a3 3Haqaja. floayme nocrojH onacHocT oa ycHcaBafta Ba3,nyxa y cjiywajy HenoinyHor 3anTHBaiba Ha cyjKeHOM «ejiy ueBH; ajw H orcTynaH>a Koja cy THMe yc^OBJbeHa HeMajy npn npaiKOM Tpajatty nojaBe HeKH 3HayajaH-yinuaj Ha oape^HBaH>e. CaMO ce no ceón pa3yMe, ja ce Tpe6a y s i p a t a m o¡x CBaKor ,HauHaaHor pery^ncafta" MapHOTOBe 6oue 3a BpeMe Tpajaita OBe nojaBe; noc^e «painor BpeMeHa ycnocTaBjba ce cTapa 6p3HHa Kanan.a oneT caMa oa ce6e. noBeha

MHM c e

iiiTa

je

c a ByH3eHOBHM N^aMeHHKOM

O6HHHO n 0 T p e 6 H 0

cyncTaHixH AO 3 0

15—20

MHHyTa, a

Aol]e AO ejieKTpHHHe nehn, 3 a

caMO

KOA TCUJKO

caropjbHBHx

MHHyTa, noMaKHe c e UHJiHHApnqHa Mpe>KHua H njiaMeHHK

oneT Ha Kpaj ueBH H noMepa ejieKTpnHHa neh yHa3aA TO^HKO Aa p e A y CJIOJ óaKpa HajBehHM ACJIOM 6 Y A E H3BaH n e h n ; THMC c e n o c T H ^ e A a c e OBaj p e A y K O B a H H c^oj c a q y B a 3 a c j i e A e h y aHa/tH3y. P a q y KoBahH Hajyhn Aa

OA O B o r T p e H y T K a

6H c e

H3Bpuinjio

n p o B O A « c e jorn

180 m i

B a 3 A y x a

npo3

ueB,

anapaTe 3a a n c o p n u n j y y noTnyHOCTH. 3a BpeMe npoBoljefba Ba3Ayxa HJKapw c e npa3HK NPEBOÍ]EH>E

npoAyKaTa

caropeBafta

y

Oape^HBAFTE YRJBEHHKA H BOÄOHHK3 no JlHÔHry

57"

«eo U6BH joui jeAHOM KpaTKO ca njisMeHHKOM H MpeacHijOM, noqaityhH c a HcapeifaeM Ha yA3JbeH0CTH OA 1 cm OA ryMeHor 3anymaqa. KAA je HCTCKJIO 150 ml Büße,

HCKJbyqn

ce

ejieKTpnqHa

CTpyja, a no 3aBpiueTKy npoBO-

Ijeita Ba3Ayxa 33TBOpH CJI3BHH3 Ha MapHOTOBOj 6OUH.

3aTHM ce 3aTBope

cyAOBH 3a ancopniiHjy H CKHHy ca ueBH 3a caropeBaae, a OBa 3aTB0peHa KariHUOM OA ryMeHor upeBa OCT3BH noA NPHTHCKOM racoMeTpa ca Ba3AyXOM, TaKO Aa

je

npn

cjieAehoj

CyAOBH 3a ancopnuHjy ce

nocjie

aH3JiH3n

OAMax cnpeMHa 3a ynoTpeöy.

OAroBapajyher

npeTxoAHor TpeTHpatba

(B. AO^E) H3Mepe. TeHHe cyncTaHue:

M e p e i t e ce BpiiiH y IÍCB^HUK

(„cBHitqe

3SL

M e p e t t > e " ) OA cynpeMaKC-CTaKJia1 AyaiHHe OKO 4 cm Koja H3 OTBOPEHOM Kpajy

HMâ CTaK^eHe

HOJKHue, H Koja ce 3aTBapa ôpyineHHM qerioM.

Ha

33TB0peH0M Kpajy HajieMÄ.eHa je cnojba CTSKJieHa KyKHua noMohy Koje ce ueB^Hija jeAHOM caBHjeHOM JKHUOM Moate Aa noicpehe y ueBH 3a caropeBart>e. Y oqmuheHy KOJ'H ce

pama,

ueBqHuy

33rpeje

HaA

CT3BH ce jeAaH MSJIH KpHCTa;i

KamjyMXJio-

MS^IHM n^aMeHOM H I H M ce HCTOÌIH, oAMax

H3M3KHe H nycTH Aa noHOBo oqBpcHe. TaKO npunpeMjbeHa aeBqHijs, n o u i r o ce ox;iaAHJia, H3MepH ce uà noroAHOM CTajiKy OA ainne mg, H y

0,01

H>y c e CHna H3 j e A H e

(J)HHe K s n n j i s p e

ca TaqHomhy OA.

20—-30

mg

TCHHOCTH

Koja Tpeôa Aa ce anaJiH3Hpa. Jlano HcnapjbHBe cyncTaHue inepe ce y ueBHHUH ca öpyuieHHM qenoM. KOA caropeBaaa craBJba ce HanyiteHa neBHHua y ueB 3a caropeB3H>e TSKO, Aa Aoije Ha yAaJtenocTH OA 7 — 9 cm OA ejieKTpHHHe nehn; OTBopeHH Kpaj ueßqHue OKpeHyT je npeMS HcnyiteHOM Aejiy ueBH.

AKO je Mepeite BprneHo y UCBIHUH ca qenoM,

npeA yHoiiieibe qnuoM craBH

qen ce HenocpeAHo

ueßqHue y ueB 3a caropeBSite CKHHC, H 3ajeAHO ca ueB-

y ueB 3a caropeBaibe.

H a qeny je TaKoije HafleMjbeHa CTa-

M e H a KyKHU3. KOA caropeBait>3 TCHHOCTH, 3Ôor H>HxoBe Bebe NCNAPJBHBOCTH, yonniTe he ce

NOICTH

ca

3ARPEBAH>EM

na^KJbUBHje,

H e r o JIH IIITO j e

TO

onHcaHo pSHHje 33 HBpcTe cyncTSHue. Mepeite anapaTa aa ancopimujy; Mepeae anapaia 3a ancopnmijy BpuiH ce Kao IIITO je onncano Ha cip. 52 Ta>IHO Ha HCTH iianiH, a nocjie HCTe npeTXOÄHe nptinpeMe. 3a BpeMe ÄOK ce UEB 3a caropeBaH>e xjiajiH, H3 H>e ce H3Byie nyHHh noMohy n^aTHHCKe >KHue Koja je caBHjeHa y oßjiHKy KyKHue, wapn KpaTKO y ByH3en0B0M njiaMeHy KOJ'H ce noaecH LANO aa He CBCTJIH, H noc^e xjialjeaa (Ha òanapHOM ÓJiony) H3Mepn cyncTaHua 3a cjieaehy aHajiH3y. He Tpeöa nponycTHTH na ce ojmax, HHM ce ÄCCJWHHTHBHO yTBpjiH Te>KHHa cyaoBa 3a ancopnuHjy, aoaa y3 Tapy OHOAHKH 6poj eg TeroBa KOAHKO o^roBapa nopacTy TewHHe, n nouiTo ce jaxaq noMaKHe Ha oaroBapajyhH 3ape3 Ha noqeTKy no^e^e Ha no^y3H Bare, oapeair CKpeiaH>e 3a HOBy Tapy.

Ü3paHyHaB3H>e:

NPOUEHTYAJIHH

caApacaj

YRJBEHHKA H BOAOHHK3

Aa ce H3paqyH3 no cJieAehHM (J)opMy^aMa : lo 1

A. Friedrich,

—

H^eHHCOg

300

cyncTaHU3

11

Z. Ang. 45, 477 (1932).

»

Moace

Meiose opraHCKe

58

ejieMemapHe

aHajiH3e

0/ Lj «a^eHa H20 201.6 /o — * • cyncTaHua 18,016 H3paqyHaBaH>e ce BpiuH noMohy KHCTepOBHX JiorapHTaMCKHX TaÓJiHua.

rpaHHua rpeiuKe h3hoch 3a yrjbeHHK -)-0,3°/o> 3 3 boaohhk -f-0,2 h ^ o 6 p e aHa^H3e Aajy oko 0 , 1 % C Man>e h 0 , 1 % H BHuie. III. O A p e ^ H B a i t e xaJioreHa, c y M n o p a H j i p y r n x

eueMeHaTa

AKO Heno je^Mfeeibe ca^pjKH OCHM yrjbeHHKa, BOAOHHK3, KHceoHHKa h a30Ta joui h Äpyre ejieMeHTe, t o ce paAH ibHxoBor OApe^HBaita cynCTaHua OKCHÄHiue ujm 3arpeBatteM ca upBeHOM, nymjbHBOM h30thom KHceJiHHOM y 3aTonjbeHoj aeBH (Carius), hjih y CTpyjH KHceoHHKa Ha KOHTaKTy oa nJiaTHHe (Dennstedt). XajioreH ce OApeljyje nao c p e ó p o x a j i o r e H H A » joui noroAHHje h nao j o A n a K H c e J i H H a , cyMnop nao ó a p w j y M c y ^ 4>aT, (J)oc(J)op Kao M a r H e 3 H j y M r i H p 0 ( } D 0 C ( j ) a T . 1. QflpeijHBaH>e x a j i o r e H a n o 3a

ojipe^HBaite je

ueBH s a 3aTanaH>e 2 , 5 cm;

.neöjbHHa 3 H n a

nyiuJbHBa

•jßpcTH

cpeópoHHTpaT;

ueBMHua

ca

noTpeôno:

oä TeuiKO TonjbHBor

upBena

a30THa

1,2

KHcejiHHa ( D .

j e n c K o r craKJia (ayiKHna 3 5

h

cm,

yuyipaimfcH

npeiHHK

mm);1 1,5);

u e l j e i b e c a jcHCKOM n 0 p 0 3 H 0 M

a.iKoxoji 6 e 3 x a ^ o r e H a

Kapnjycy

CTanjicHOM

Bojia, Koja caapiKH

a30Tne

ü y i t e i b e ijeBH s a s a T a n a i t e :

nJiotjHUOM 3 a u e f j e f t e ( 1 3 f Q

khcgjihhc

Li,eB ce

2).

(1:100).

Hajnpe

o h h c t h ÖHxpoMaT-

cyMnopHOM KHcejiHHOM, HcnjiaKHe boaom h ocyniH Ha upnKH Ha boachh Mjia3 y3 ö j i a r o 3arpeBatt>e.

CyncTaHua ce H3MepH y Ma^oj u e b mhu h 3a M e p e a e ca apuikom Ay>KHHe 8 — 1 0 cm Kojy momìcmo c3mh a a hsihhhmo oa noAecHe CTaKJieHe ueBH; npn Mepeity OHa ce nocTSBH Ha iua;m a fl CTajiaK oa JKHue (ca. 39). noiiiTO ce oap^äh

XJ

n p H Ô J i H J K H a TemHHa ueB^Hije 3a Mepeite, H3MepH ce 3a oApeljHBaibe xajioreHa 2 0 — 3 0 Cj,. 39 m g cyncTaHue ca TanHomhy o a 0,01 m g h yHece ueBqHua 3a Mepeit>e ca cyncTaHuoM iiiTO je Moryhe A y ô ^ e y ueB 3a 3aTanaii>e Koja. ce a p j k h y xopH30HT3J1HOM nojiojKajy. ycnpaBjbajyhn i;eB Hcrpece ce y ft>y cyncTaHua, ueBHHua 3a Mepeite noHOBo naaubHBO BpaTH Ha Bary, h OApeAn iiohobhhm

MepeaeM T a n h o TejKHHa y3eTe cyncTaHue. CyncTaHUH ce AOAaje, Beh npeiua H3MepeHoj kojihihhh, 60—90 m g •CHTHOcnpauieHor cpeôpomiïïipaïïia (Hajöojbe 172" CT Py Ka iKHBO

ce

npn

ueBK

H

ÄOÄ«P

ca

KOÄ

OKO

ueBH

ce

0,8

6 o Ua

Heno-

cyncTaHijH, CTABJBA

cm

ca

na^KjbHBO

6PHÄ^>HBO

ce

OKpy-

nycTH

H3öeraBa

Äa

KHcejiHHOM.

o ö p a Ä e TeuiKo TonjbHBor c r a K J i a n p H K J b y q H

KOMnpecopa H « e j i n r a a

cyncTaHu»

KHCCJIHHOM,

umpHHe

qeiuy

KOÄ

KHCCJIHHOM,

icucemne.

HarHyToj

NPH

H

a30TH0M

a30TH0M

cm

ÖJiaro

y

Äolje

ca

6

33TanaH>e,

PaÄH

3 a T a n a i b e ijeBii:

OKO

oneKyje),

ca

a30üiHe

pearyjy

cacßHM

3a

KOJ'H c e

pearyjy

üyuiJbiiBe

Äy>KHHe

BpeMeHa

TIOPEÄ Ba3Äyxa m

xaJioreHa

nojiaraHO

ml

ueB^Huy

ÄHOM,

CKJIH3HE

caMO

1—1,5

H

KHcejiHHa tjihm

caAp>Kajy

xjia^HO

59

ejieMeHaia

ca

ce

ÄysajbKy

Ha

KHCCOHHKOM.

U e B 3 a 3aTanaH>e yxBaTH c e n o cpeÄHHii jieBOM pyKOM, ÄP>KH ce n o MoryhcTBy KOCO « a r H y T a , npw neMy ce na3H Äa a30THa KHcejiHHa H3 u e B i H u e He Ä o c n e ÄO c y n c i a H u e , H 3arpeBa Kpaj ueBH y 3 jiaraHO OKpeTaH>e Hajnpe qaljaBHM, a 33THM 6e36ojHHM naaMeHOM, H HA Kpajy

y 3 noMoh

Heimo

KHceoHHKa

CBe ÄOK

ciaoo

uiTaiiHh CTonn ca yHyTpawH>0M CTpaHOM ueBH,

Taaa

He OMeKiiia.

ce jejiaH

CTOJIH H ca OBOM, A O B e j e y TanaB n o j i o w a j aa ;ie>KH y OCOBHHH ueBH. Cana HenocpeÄHO HCÜOÄ

craKJieHH

H npHByqe Ä p y r o j CTpaHH ueBH, H n o u n o

o ß o r MecTa r ^ e j e j o i n UHJiHHÄpHiHa,

ce

c e ueB 3arpeBa

n a j n p e cjiaßo laijaBHM njiaMeHOM,

a 3aiHM y 3 y i i e p e H o Ä0B0tjen>e iuiceoHHKa, CBe ÄOK CTaKJio ne OMeKiua. Y 3 CTaJiHO OKpeTaH>e H cacBHM c j i a ö o npHmcKHBatt>e

nycTH ce Äa ce CTaKJio Ha OBOM MecTy CKynn;

MHM j e jaKO

3AÄE6JBAJIA, ueB ce H3BaH ruiaMeHa H3Byqe y K a n m i a p y Ä e 6 e.a H x 3 H Ä o B a Koja ce ycKHM, ouiTpHM

KKceoHH'iHHM

njiaMeHOM 3 a T o n « .

CTaBH y T B 0 3 Ä e H H

3AUJTHTHH

Kannaapa ce

oxjiaÄH y qaljaBOM

n^aMeHy h ueB

0 M O T a 4, TaKO Äa KanH^apa BHpH HeKOJIHKO caHTHMe-

Tapa n a n o j b e ; eBeHTyajmo c e MeljynpocTop ii3Metjy ueBH H rB03ÄeH0r o M o i a i a HcnyHH necKOM, JIOK T a i a

je

HHTH

s p m e

UEB

ÄATONJBEHA,

H 3 H C T H

o n e p a u n j e

H3 n o a

3arpeBaH>e u,eBH: neh

Tano,

KOME

ce

MO>KE

ÄA

HAJIA3N

3arpeBaTH

N O C T E N E H O

OKO

CAAP>KE 300°.

KOÄ

QACOßA

Hä^aBHM

H neh

h

njiaMeHOM y

OKO

TeHHOCT n^aMeH

KOJ'H c e

Hajia3e

H3B3ÄH

ce

n3

ueB

3arpeBa.

AKO

lieBH

Taj

aKo ce

je

craBH

3aTBopn.

peryJiHinyhH

3A

y

CNEUHJA^NY

c e

na ce

H neh

MacoBHor

JEÄHFT>EFT>A c e

NPOÄY«H

3arpeje

iviaBHy

(H

3—4

noc^ie

3HÄ}7

HCTOBPEMEHO

C^IABHHY.

(H M H o r e

A P O M A T H H H E

cy^4

CYNCTAHUE ) 0 K H C E

3arpeBaita

'

, I H H E

)

NOMYHO

3arpeBait>e

jom

u,eBH:

n o a i e

n o T n y H o r

He-

HCTepa 3arpeBaK>eM ca

Koja

HaJia3H

ce

MOJKA^

Äyßa^Ke

(3aiiiTHTHe

npHTHCKOM

npoöyiuHJin ce

eßeHTya^HO

noTpeÖHO,

n0TnyH0

KanH/iapa

Äa

Hajnpe

Kanunapn

ueB ce

3aTonH

oTCTpaHH ce 3aTonn

M3JIHM yHece cy

Kanw^apy,

cyncTaHua

oneT

n0H0B0

H

nouiTO

OMeKina^y

ce

JIH

pacTBopn^a

y

Hao^apHl).

H npoBepn

ce

ox^ial]eK.a

OMOT3H H a n o j b e ,

noÄ

ä3

OMO-

K o j o j

npeMa

3ana;ie

RUIAMEHNUN

X A ^ O R E H C K A JEÄHAEIFCA

250°,

ce

OKPEHYTA

oMOTana

cyncTaHua

HaiHH

ce

U

ce

TeMnepaType

npaHitteibe

ouiTap

H3

y

Tora.

racoBH

pacTBopn^a;

CBH

UEBH.

H3 n e h n r B 0 3 Ä 6 H H

Kann^apa

Ha

KPXOTHHA

APOMATHIHHX

OTBapan>e «3BaAH ce

NOÄHRHYTA

CYNCTAHUH c e

npeKO

B a Ä H T H

c a UEBH

HeuiTO

A^HC|)ATHQHA cyMnopa)

c e

n p o c T o p H j e

N p H T H c K o M.

ÄEJBEHE

BehHHa

OKCHAHUIE; KOJIHKO

BHine

ÄO

O ß a H 3 H O C H 3A Koje

XB3TAN

CMe

FBO3ÄCHH 0M0TAQ

KanHJiapa

je

He

c n e u H j a . « H e

n0TnyH0 h

n0H0B0

ropan

H TaAa

Äeo

OÄMax

Meiose opraHCKe efleMemapHe aHaflH3e

60

Ma^o HHHTE, rAe je UEß joui uHflHHApHqHa, ynpaBH ouiTap KHCGOHHH3H N^aMett. npeMa ueBH, Tano Aa ce oHa HA OBOM MecTy HaAyje H npoöyuiH. CAAA ce OIIlTpHM KHCeOHHqHHM nJiaMCHOM pa3MeKUia CT3KJIO ÖOqHO y3 H3CT3JIH OTBOp, H JE^HHM CTHKJIEHHM MTANNHEM noßyqe y CTpaHy Tano Aa HacTaHe uiHpoKa nyKOTHHa noja ce npouiHpH yHa0K0Ji0 a o 2/S o6«Ma ueBH. FIomTO ce ca^a pa3MeKiiia jotu H npeocTa.no cnojeHo MecTO, noßyqe ce CTaK^eHa nana y CTpaHy H CKHHe npH qeMy ce HCTOBPEMEHO H3MHHH H je^aH Ma^H n H n a K. U,eB ce Hajnpe OHHCTH c n o j b a H caAP^KHHa UEBH na^KJBHBO pa3ö;ia)KH

ca OKO 10 ml BOAe. Majio eraKJieHue Koje je cayÄHJio Aa npnMH a30THy KHcejiHHy H Koje nJiHBa Ha noBpniHHH yxßaTH ce K0iiiTaH0M nHHueTOM H Hcnpa3HH y nexap ca OKpyrJiHM AHOM (Ay>KHHa 15 cm, niHpHHa 3—3,5 cm) H Hcnepe AecTH^OBaHOM B O A O M . n o n i T o ce xanoremn cpeöpa no MoryhcTBy CHTHO 3ApoÖH CTAK^ieHHM mTannheM, npeöaun ce caApJKHHa ueBH KB3HTHTaTHBHO y nexap y3 BHiuecTpyKO HaKHaAHO Hcnnpsae. CpeöpoxsaoreHHA KOJH TBpAOiviaBO npHjaita y3 3HAOBe ueBH yKJiaiba ce CTAK^eHHM uiTanHheM, a nac^eAHiH AejiOBH y3 Han3MeHHqH0 Hcnnpaibe ca Ma;io amoxom (6e3 xajioreHa) H Majio BOAe. IJeijeH>e H c y m e i t e c p e ß p o x a j i o r e H H A a : Ta^or KojH je caieH.e ijeBH c a îjHHtjyBaMa:

y ueB

ca

^HH^yBaMa

Koja je

TÊMejbHO oMHiutieHa y c H c a ce n p e n o je^He u e B H H u e H a n y a e H e BaTOM, Koja ce npniobyiH Ha i^eB, 5 - n p o u e H T H n npe

cBane

cepHje

BOflomiHcyUepottciifía Kojn ce üepxiwpojia, y fleo ijeBH

pacTBop

aHa;iH3a CBe>Ke n p n n p e M H H3

HanyiteH JjHHljyBaMa AOK TCMHOCT He OBJiajKH CTaKjieHy cnnpajiy; Ta^a ce a n c o p n u H O H a TCHHOCT o n e T n c n y C T H .

KOJHMHHA

TEQHOCTH OA 2 — 3 m l KOJ'OM

je H a K B a m e H cjioj ipHljyBa n o m y H O je AOBOJbHa. KOJH je HcnyHbeH Ha

cTajiaK

3a

IjHHJjyBaMa

caropeB3ite.

ilpeno OHor Aejia u e B H

H a B y n e ce HHcra enpyBeTa, H I ^ B ce CT3BH

TA^a

IUISTHIICKE

ce

n p e T X O A H O HCKyBajy pa36^a>KeHOM O.30WHOM

KOHT3KTH,

icucemnoM (1:1)

H

KOJ'H

ce

jano HJKape,

yrypajy y u e B TaKO AA npaj n p B o r a 6yn;e OKO 6 c m y^ajbeH OÄ cnnpajie OA T B p A o r CTaKJia, a H3Mel]y K O H T a K T a ocTaHe MeîjynpocTop OÄ OKO 2 c m AyjKHHe. U ^ B ca i]HHljyBaM3 nocTaBH ce TaKO Ha nocrojbe 3a caropeBaae, A a Ä,eo Hcnyft>eH IjHHljyBaMa H join OKO 5 c m npa3Hor A e a a uiTpqe H3BaH NOCTOJBA. /I,eo u e B H

KOJ'H UITPMH

HANOJBE

noAynpe

ce

BHJBYIIIKACTHM

p a A H TOIL/IOTHC H30JiauHje H a B y q e ce n p e K O ueBH

CT3THB0MJ OA a 3 6 e c T a

KOJ'H HajiOKe y3 3HAOBC ijeBH. T a ^ a ce jeAna

M e n u e caBHjeHa y T p y ô y , Ay^cHHe 2 0 c m , HaByqe n p e K O

OA T B 0 3 A e H e

Aejia u e B H ca riAaTHHCKHM K O H T a K T O M KojH ce rpeje J'CAHHM nJiäMCHHKOM,

H Ha

ueBH

joui

AyraMKHM

O B O M M e c T y nocTaBH Ha n o c T o ^ e 3a c a r o p e B a a e

Kao TOnJIOTHH H30^aT0p K p O B OA Í K H i a H C M p O K i , npeKO

3aKJioH

MpejKHLia

jeAHa

UHJiHH^pHqHa

»HiaHa

H Haj3aA HaByue MpeatHija

Ayra

5 c m 3a n o K p e T H H njiSMeHHK (ynop. cn. 41, cip. 64). 3 a OApel)HBatt>e xsjioreHa H 3 M e p n ce Ha yoÖHHajeH h s ^ h h 2 0 — 3 0 cyncTaHue 6—7

cm

y OA

mg

HA3THHCKOM

q y H w h y , H OBa yHece y u e B TaKO A a A O ^ e Ha

Kpaja

aHJiHHApnqHe MpejKHue. C a A a ce u e B 33TBopn

Ay^e

r y M e H H M 3anyuiaHeM H n a n n ^ a p o M H3ByICHHM y TaHaK B p x H Be>Ke n p e K O ópojaqa

MexypoBa,

XHAPOKCHAA,

ca

KOJH je HanyiteH 50-npoii. p a c T B o p o M

r a c o M e T p o M

ca

Ka^njyM-

KHCCOHHKOM.

3a 0Äpel)HBatt>e xajioreHa y LEIBOCTHMA H3Mepn ce cyncTaHua nao UITO je onucaHO KOÄ ojipe^HBafta C, H, H yHece ueBqnua ca cyncTaHUOM y ueB 3a caropeBatte Tano, aa Äolje Ha yaajbeHOCT OÄ 8—10 cm OR npeaiter Kpaja jiyre uujiHHflpimHe Mpexnue. KOÄ BPAO TeuiKo caropjbHBíix TCIHOCTH y3HMa ce yMecTo KAJIHJYMXJIOPATA aMOHujyMHumpaui. H3Bol)eifce c a r o p e B a H > a ; ropeBaH>e, peryjiHine ce OHHKa

OÄ 7 — 9 ml

MapHOTOBe

y

I l o m T O ce cyncTSHixa yHece y u e B 3a ca-

noMohy n p e i i H 3 H e C T e 3 a j i H u e CTpyja KHce-

MHHyTH

(6a)KAapeH>e

6oue, BHAH CTp. 49)

dpojana

MexypoBa

niaTKHCKH

noMohy

KOHT3KTH MHM ce

TO

nocTHrHe, n p H B y q e ce K p a T K a uHJiHHApnHHa MpeacHixa AO Ha HCKOJIHKO

mm

Ayra^KHM y 3 njiaTHHCKH

IUISMSHHKOM

H 3arpejy

qyHnh,

AO

CBeTAoupBeHor

H nonpeTHH ByH3eHOB

ycHjaaa.

n A a M e H H K , iHjw ce njiaMeH

n o A e c H TaKO A a He qaljaBH, CT3BH HCIIOA 3aAK>er Kpaja UHjiHHApnqHe M p e -

0.npetjHBaH>e

ÄHiie. Koja

Ca.ua c e

ce

NOMAKHE

nojiaKo

UH-IIHHAPHIHA

cyMnopa

H nocTeneHo

MPE>KHUA

H

AecTHJiHiuy

ce

nocTynnTH

c e /jecTHJiaT Koja c e

H3Mehy

uyHHha

KOHTaKTa,

H

na>KJbHBO

CTaHue

£a

n^aweHHKa

Tpeöa

jeMiHTH 3a

n0TnyH0

JIH

OÄHrpajy, RUIAMCHHK

MAJIO

r a a a

ce

Y H A N P E Ä ,

He n o ß e h a ß a . qyaHh,

NPH

ce

npa3HOM ce

M H M

caqeKa

npHMeTHOM

HajMaibe 3 0

Hajnpe

KanjbHije y

ÄecTHJiaT

caropeBaite

cyncTaHUOM

c a

H t e K

o 6 a 3 p H B o ;

BH^y

BHiue

HcnapaBa

Äa T p a j e

He

BeoMa

nif(aTHHCKH

nocMaTpa

ByH3eH0B0r

63'

ejieMeHaia

H

KOÄ cyncTaHijH K o j e n o c a e Tonjbeit>a

CKynno y

n ^ a M e n a ÄOÄHpHe

H O ß O R

H

Mopa

apyrHX

B Y H 3 E H 0 B

TO CBaKHX 2 MHHyTa 3 a OKO 2 — 3 mm.

Ä O K

h

a o k c e n p o M e H e Koje c e A e m a B a j y

npHnena,

caropeßa,

xajioreHa,

ce

HenpoMeiteHOM

MHHyTa noJio)Kajy

CaropeBaHbe

noniTO

H KBaHTHTaTHBHy

aeBH

ByH3e-

HBHUOM

HCKOJIHKO

6p3HHOM.

MHHyTa,

caneKa,

J;EJIY

ce

HHaqe

He

cynMO)Ke

ancopnunjy.

npHJiHKOM caropeBaiba T C M I I O C T H npHMHie ce Maaa umiHHiipHiHa Mpeaama npe ncmeTKa caropeBaH>a, Beh npeMa ncnapjbHBocTH cyncTaHue, HajBHuie ä o Ha 1—3 an y3 ueßi n u y H qeica ce, IHM TaiHocT rroiHe na .necTHJimue H3 ueB'imie, Ha MeH>ajyhH no^oHtaj Byn3eH0B0r n^aMeiiHKa, ÄOK ce aecTmiamija He 3aBpwH| TeK rana ce Ha onncaHH HaqHH nojiaKo Kpehe nanpea. M c n n p a i f e e u , e B K h T H T p a u , n j a : r i o c j i e o x j i a i j e i f c a OTCTpaHH c e q y H H h , ueB

ce

n o c T a B H y BepTHi K a j , y n B p c T H n o M o h y CTaTHBa H y M e c T O

enpyBeTe

ct3bh

cHna

UAJBKE

3HÄOBe u e B H ca

1 0 ml

no

y3

e p j i e n M a j e p

1 0 ml

B O ß E ,

ncnepe

Elpe T H T p a u H j e ca

y

3a

cjiaöo

oapel)HBaH>e

0,01-npou.

aJiKoxo^Hor

yTpa^iHHM n/50—n/40 NOÄEJIOM

OÄ

OH c e

Q E B H

ce

jaiHHa

ycjieA

xJiop-joHa pacTBopa

CBe B e h n M ce

Mexa

Kpo3

H

caÄP>Kaj

enpy-

CTBopeHe MHHepajme KncejiHHe Tano

ÄOÄa

Äa

ce

HAJEÄHOM

HE

pearyje

KHCejiHHe.

pacTBopy

5—10

H THTpnme

H3

Kann ca

He-

M H K p o Ö H p e T e c a

nonasyje

npHÖ^HHOBafteM

na»jbHBO

pacTBop

cnpheTHe

MUXJiopcpÄyopecqeuna THTpaunje

noneTKy

Ta^a

uiTp-

u e B j o r n TpH n y T a

npecne

ocjioöoljeHe

cpeöpoHümpama

ca

H3

yHyTpaimte

p y w H o r

H

iiampujyMaiiemaüia,

cpeöpoxajioreHuna

oöojeHe

Aeo

Ma;ior

ce

T O M E

HaiHH n c n e p e

y

jaKO 3 a M y h y j e . COJI

ce

paculBopoM

0 , 0 2 ml.

o n a ^ e c u e H u y ;

noMohy

Ta^a

npn

6a;IOH.

yö^amn

K H C C J I O

ml).

cnnpajyhH

HCTH

H3ByqeHH

H e i < o ^ H K o K a n n paciüBopa

caMO j o r n

Ä O K

Ha

ncnnpafte

(100—150

ueß

noTHCHe

epjieHMajep.

HAKHA^HO

y

B O ^ E

H Te^HOCT

c j i o j l}HHl]yBa y BeTe

4hct

OKO

p a c T B o p caMO c ; i a 6 y Ta^KH

eia n p e A

HÄyhe ce

KanjbHue npn

HHTeH3HBHO p y > K H q a c T e

jaKOM 6oje.

Kpaj

noeraje

OÄpe-

pacTBop

MyhKaay

H3-

64

Metofle opraHCKe eJieineHTapHe aHajiH3e

Tpe6a t h t p h c s t h npHJiHiHo 6p30 npH Äiiaiba cyBHiiiHor € p o M a m p a b jb o m k h c e j i h h o m a o a s ce pacTBopy K a j i H j y M j o A ^ Ä _H THTpHIIie H3ABOjeHH j O A H 3 T p H j y M T H O C y J I ( J ) a T O M . IlOIIITO j e KOJiHHHHa joAa Koja c e THTpnuie 6 nyTa Beha o a OHe Koja j e caApataHa y cyncraHUH, t o MeTOAa Aaje Bpjio TanHe p e 3 y j r r a T e . 3a OÄpeljHBaHje je noTpeöHo: .ueB 3a caropeßaibe (cn. 41) oa cynpeMaKc-ciaKJia (yHyipamH.ii npeiHHK 0,9 cm, AywHHa 5 0 — 6 0 cm; AymHHa 0AB0AHe ueBH 18 mm, yHyipaiuibH npeiHHK 2mm; neB HMa Ha npajy nenocpeaHo ncnpeA oaboahc ueBH jeaHO cyweae); 10-npou. pacTBop MHCTor HaipHjyMaueiaTa y 96-npou. cnphemoj KHce^HHH; 6poM (6e3 joAa);

80—100-npou. MpaB.ta KuceJiHHa; KajiHjymjoAHA h n/10 pacTBop HaipHjyMTHocy;i4>aTa. H s ß o l j e H j e O A p e i j H B a t b a : y ö p i m j b H B o o ^ n u i h e H y h o c y i u e H y ueB CTaBe c e 6nmy a o cyaceHor Aejia ueBH k o h t 3 k t h o a n j i a T H H C K e w p e > K H u e Kojn ce npeTX0AH0 omhctc HCKyBaBaiteM y pa36ji. asomno} KucemHU (1:1) h j a n o n a c a p e ; 3aTHM ce Ha

OBO

MeCTO

ueBH

CT3BH

UHJIHH-

A p h h h a r B 0 3 A e H a M p e ® H u a AyjKHHe 2 0 c m , h Kao Aajba TOiuiOTHa H30JiauHja KpoB oa rB03ÄCHe M p e a t e Ha c t s t h b 3a c a r o p e ß a i f e e . OaBOAHa ueB c e ypoHH a o AHa peuniiHjeHTa HapoHHTor oßjiHKa Kojn je ripeTCTaBJbeH Ha c a . 41, h y KOMe c e Ha.na3H 1 2 — 1 5 ml pacTBOpa nampujyMaifemawa y cuphelünoj mcemnu, KOMe j e AOAaTO 1 0 — 1 2 Kann öpoMa. 3 a oApeljHBaifce joAa H3Mepw c e 2 0 — 4 0 mg cyncTaHue y ü m t h h c k o m qyHHhy h caropeßaK>e c y n c T a n u e h3boah Ha h3hhh o n n c a H k o a O A p e i)HBaH>a x a j i o r e H a y ueBH ca IjHH^yBaMa. Bp3HHa c T p y j e KuceoHum p e r y j i H i i i e ce Ha 3 — 5 ml y MHHytH. 1

Th. Leipert, Mikrochemie, Pregl-Festschrift CTp. 266 (1929). — W. Münster, krochemie 14, 23 (1933).

Mi-

OflpeljHBafte xajioreHa, cyMnopa H apyrwx ejieMeHata

65

nouiTO ce ueB ox.naAn.na, H3B3Ae ce qyHHh H KOHT3KTH H y ueB Koja ce Ap>KH Koco CHna O K O 4 ml pacUiBopa âpOMa y cupheUìHoj mcenunu, Aa 6 H ce O K C H ß H C A O joa K O J ' H ce H3ABojno Ha cyaceHOM A C J i y ueBH; pacTBop ce H A O B O M MecTy 3AAP>KH. riocjie 10 MHHyTa cnepe ce ueB a 3 3 T H M H peuHnnjeHT KBaHTHTaTHBHo y M H C T epaeHMajep, y KOMe ce npeTxoAHO n o T n y H o pacTBopH 2 g HaülpujyMaLiemawa y M S J I O BOAe. J\a 6a ce yKJiOHHo C Y B H U I H H 6poM A O A A ce H C K O A H K O K A N N ( A O 0,5 m l ) MpaBJbe mcenme HH3 3HAOBC epjieHMajepa, C H 3 ) K H O npoMyhKa A A 6 H ce ancopóoBao H 6poM Kojn ce Haji33H y racHoj tyam, H caqeKa H C K O J I H K O cenyHAH. MHM je HacTynK.io o6e36ojeite pacTBOpa AOAa ce neuiTO pasôn. cvMûopnè mcemm H 1,5 g KajiujyMjoaum, OCT3BH noc/ie M Y H K A I T A A A C T O J ' H 5 M H H Y T A , H 3 3 T H M T H T P H U I E H 3 A B O J E H H joa ca nj 10 pacïïiBopoM naüipujyMwuocyjKpaûia H3 M H K P O Ó H P E T E Koja je NOAEA>eHa y 0,02 ml, Hajnpe A O myTe 6oje, a 3 3 T H M noaie AOAaTKa cupoôa A O o6e36ojen>a, TpaHHaa rpeuwe oApeijHBaiba: + 0 , 3 % 4. OflpeijHBaH>e cyMnopa no Carius-y OApeijHBatbe cyMnopa n o K a p n j y c y BpuiH ce Ha H C T H H S I H H n a o H OApei^HBaiie xa^oreHa; HaMecTO cpeôpoHHTpaTa Aoaa3H OBAe 6 C 3 B O A H H Ö A P W J Y M X J I O P H A .

0Äpet)HBaH>e

3a

cy

noxpeôHe:

ueBH 3a 3aTanaH>e o a TeuiKO TonjbHBor

cianna;

upBena nyiujbHBa a30THa KHce.iHHa ( D . 1,5); 4BpCT ÓapHj'yMX^OpHa;

nopueJiancKH JioimnhH ca nopo3HHM H H O M

3auiTHTHHM waHieTOM

H

qaHMHhH 3a uetjeibe A . 1, BHCHHa: 2,7 cm,

3anpeMHHa 6

(BepjiHHCKa M a H y ^ a m y p a , ml).

IlyHseifee p e a K i j i i o H e u , e B n : 3 a oApeljHBaite c y M n o p a H3Mepn c e Ha onHcaH

HAHHH CT3BH

y

UEB

N P E T X O A H O

H

KOA AOAA

OAPEJ]HBaH>a

c e npeMa

06e3B0AH>eti0r

1 — 1 , 5 ml ifpBeHe

ûyuiJbUBe

CKjiH3He

UEBH

HE

AO

A H 3

xajioreHa 2 0 — 3 0 mg cyncTSHue

KO^HHHHH

ôapujyMXJiopuaa; a30WHe

Koja c e

3aTanaft>e, 3arpeBan,e

H

Kucemne,

APJKH

Aoije n p e BpeMeHa y A O A « P ca

Koj3 c e

H3MepeHe cyncTSHue 1 3 0 — 2 0 0 mg

KOCO,

33THM

c e y M3Jiy

cnna

U E B I H U Y

H naacjbHBO nycTH AS u e B i H u a npn

HEMY

ce

NA3H

AA

cyncT3Hua

KHCCAHHOM.

noHOBHO OTBapaH>e

ueBH BpiiiH c e Kao

UITO

je 0riHC3H0 KOA OApei^HBafta xajioreHa. npa>KH>eH>e u,eBn H oflpeljHBaH»e ôapHjyMcyjiiJjaTa : E I O I I I T O ce aeB cnojba OMHCTH, npecne ce c3AP>KHHa ueBH y3 BHinecTpyKO H 3 K H 3 A H O Hcniipaibe ueBH AecTH^0B3H0M B O A O M y oónnaH M3jih nexap; ôapujyMcyjKpaïïi K O J ' H ce 3a^enHo 3a 3HAOBe ueBH yKJi3tt>a ce ciaKJieHHM in T an H h e M 6e3 ryMHue. noc-rceAitH OCT3TUH Ö3pHjyMcyji4>3Ta npeôaue ce y nexsp HaH3MeHHqHHM HcnnpaibeM ca Majio amoxojia H Majio BOae. Elpe Hero U I T O ce Ö A P H J Y M C Y J N J J A T oueAH, 6pHJKJbHBo ce O I H C T H nopuejiancKH ji o H q H h 3a u e ïj e K> e (ryq) ôuxpoMaïïi-cyMUopHOM mcejitiHOM, Hcnepe A S C T H J I O B S H O M B O A O M H npoiiycra Kpo3 J I O H Q N H B O A A C H OpaKTHKyM opraHCKe xeMHje

5

66

M e i o s e opraHCKe ejieMeiixapHe aiia;iH3e

iiiyhn nyMnoM Ha boachh MJia3. JIoHqnh ce Ta^a H3ÔpHiiie hhctom KpnoM, CT3BH y 3 a u i T H T H o n o p u e f l a H C K o q a h q e Ha T p o y r a o o a H e r J i a 3 H p a H o r n o p u e a a H a , cyiuH Hajnpe Mauiyhn oao3ao mhjihm ByH3CH0BHM n^aMeHOM. a 33thm jiaraHO 3arpeBa h TeMnepaTypa nocTeneHO noflHjKe ,50 TaMHoiipBeHor ycnjaiba. f l o u i T o ce acapHjio 2 0 MHHyTa, oct3bh ce Hajnpe 5 MHHyTa aa ce xjiaA« Ha Ba3Ayxy, a 33thm ce JioHqnh 3ajeAH0 ca 3auiTHTHHM JiOHqeTOM CT3BH y e K C H K a T o p . nocjie je^HonacoBHor XJiatjeiba y eKCHKaTopy JiOHiHh ce M e p H ( ô e 3 3 a n i T H T H o r qaHqeTa). ao

IÎouiTo ce c a a p J K H H a n e x a p a 3arpeja •noHqah. y 6oue

cneunjajiHH

3a u e ^ e & e

nexapa

y

jieBaK

h

Ha BanyyM,

JiOHqnh;

3a

ce

ctebh

AeaoBH

ce H 3 M e p e H H

HaMeuiTeH

6apujyMcyji(païïi

npeôaijH

nocjieAH>H

Kjbyiatba,

aeijeite, npeôaue

y

rp^nh

HenocpeAHO

oneT

h3

HaH3MeHHqHHM

anttoxojioM h boaom. H a K p a j y c e jiohhhîî joui j e ^ H O M H a n y H H boaom, Bo^a oiieAH h jioHHHh npHnpeMH 3a Mepeae t3MHO Ha hcth hbihh

cnnpaH^eM Kao

ca

u i T O je r o p e TpaHHua

onncaHo.

rpeuiKe

OApeljHBaiba:

5. O s p e ^ H B a a e OÄpe^HBaH>e

cyMnopa

y

±

0,3%.

cyMnopa

caropeBaiteM

h3boah

d,6bh c a IjHHijyBaMa

aHa^orHO

ce

OÄpe^HBafty xajioreHa (b. cTp. 61). Cfloj cum

IjHH^yBa ce H a K B a c H

Kojn

eBeHTya^HO

HacTajie

5—10 HH)Ke

-npou.

pacïïlBopoM BodotuiKcyüepoK-

OKCHAauHOHe

npoAyKTe

cyMnopa

cyMüopny mcejiuny. Floche nyft.ett>a u,6bh caropeBaH>e ce cyncTaHue h3boah Ta^HO OHaKO, nano je onmHpHO onacaHO koa ,OApel)HBaH>a xsjioreHa. FIòiiito nomyHa ancopnuHja cyMüopmpuoKcuaa 3axTeBa AyroTpsjHH AOAHp ca ancopnitfiOHOM Te^Homhy, caropeBaae Tpeôa BpinHTH y c n o p n j o j CTpyjH KHceoHHKa ( 3 — 1 ml y M H H y T H ) , h n p e M a T O M e h nonpeTHH ByH3eiioB n j i a M e H H K Tpeöa noMepaTH Ha OAroBspajyhn HaqHH c n o p h j e. C a r o p e B a i t e cyncTSHue Tpeöa Aa Tpaje oko 1 caí. rio 3 a B p u i e H O M c a r o p e B a i b y c n e p e c e u e ß , K a o iijto je o n n c a M O koa O A p e ^ H B a f t > a x a j i o r e H a , y MaJiH mhct n e x a p h T O M e AO,a,a h c a ^ p a c a j e n p y B e T e K o j a c e TaKotje c n e p e . T a A a c e aoas ö w c T p o n p o u e ^ e H a MeinaBHHa oä 2 äo 3,5 ml pacüBopa óapujyMXJiopuaa (1:10) h 1 0 K a n n pa3ÖJi. cone Kucejime, nòKpÌHje hhcthm c3X3thhm ctskjiom h 3 a r p e j e ao K J b y q a K > a aok c e H e 3 a B p u i H H3ABaj3it>e óapujyMcyjKpama. flouiTo ce c a A p a c H H a n e x a p a o x j i a A H C T a B J b a i b e M y x j i a ^ H y BOAy, 3 a B p n i H c e O A p e ^ H B a a e hcto K a o h npeBOflH y

koa

npeTxoAHe

MeTOAe

OApeljHBait,a.

6. J e ^ H O B p e M e H O Ako

y

oflpeijHBaH>e x a j i o r e H a

H e K o j cyncT3HijH T p e ö a j e A H O B p e M È H O

H

cyMnopa

A a 'ce o A p e A H

h c y M n o p , to c e H a j n p e OApeAH x a j i o r e H n o K a p t o ah. $ H ; i T p a T oä T a l o r a c p e ö p o x a j i o r e H H A a x B a t a

xaJioreH

H j y c o B o j ce y

Me-

6ph5kjí>hbo

67

OAPELJHBAHIE OPRAHCKHX RPYNA

OQHIUHEHOJ

6OUH

3A AE^ENBE HA BAKYYM,

ÒJIAACH HA 1 2 0 — 1 5 0 TYPH

KJBYQAKBA

H CYIANOPHA

ml

CA

1-NPOU.

PACTBOPOM

ANCOJIYTHO HE CME AA CA^PHCH 3A

HCNNPAIBE

TALORA

CME A S CAAPSKH COHE

7.

NPEHECE Y JEHCKH

KHC6JIHH3

Y

ÓAPNJYMHHTPATA

A^KAJIHH

KOJ'H

YNOTPEÔJBABA

CE AECM/IOBAHA

BOM

KOJA

HE

KHCEJIHHE.

OFLPE^HBAIBE

OCTA;RAX

EJIEMEHATA

PACTBOPY

3AKHMEJBEHOM

330TH0M

H BEMHOAJIKAJIHH

METANN

HEOPRAHCNE

KHCCJIHHOM,

OPRAHCKA CYNCTAHIIA OKCHAHUIE NO K A P H J Y C O B O J

Y

PA3-

XAAOREHA.

BEHHHA OCTAJIHX EJIEIUEHATA O A P E I J Y J E CE NO METOAAMA A HAA H3 E

NEXAP,

TAJIOMN HA TEMNEPA-

NONITO

CE

M E T O A H-

OAPELJYJY CE NAO

CYAKE HA

OBAJ CE NOCJIEAH>K

CYBHIUKOM

BRJ +

2

Y

METOKCMIHE

NPEBOAH

CE

BR2 =

CHGBR +

H

3

CYBHUIAK ÔPOMA CE PEFLYNYJE

H

2

0 =

HJ0

KJBYIAJIE

(Zeisel),

A OBAJ CE

6 P O M J O A:

BRJ;

6POMA OKCHAHINE Y

BR2 +

RPYNE1

AEJCTBOM

METH^JOAHA

SAKHJIÓPÒMHA

B O A O H H K, H HAJ3AA NO AOAATKY JOA

RPYNA

OPRAHCKHX

OAPEIJHBAITE

CHGJ +

HCNAPW H

YCHJAITA.

0#PELJHBAH>E

1. B O A Y W E T P H C K O

HJIH OHHX CYNCTAHITFI KOJE

CYMNOPHE KHC€JIHH€, NAJKJBHBO

3

+

JOAHY 5

KNCEJINHY:

HBR.

M P A B JB O M K H C C A H H O M KAJIHJYMJOAHAA

Y

6 P O M O-

THTPNUIE N3AB0JEHH

TH0CYJI(J)8T0M. NOUITO CE NPH TOME OCJIOÔOAÊ

KOKCHJI, OAPE^HBAFTE CA BEJIHKOM

6

EKBHBAAEHAIA

JOAA

3A 1 AJI-

CE AA H3BECRA H KOA HAJMAIBHX KOAHQAHA CYNCRAHUN

TA^HOINHY.

3 a OÄPE^HBAH>E JE NOIPEÔHO :

5 ml jOÄOBOÄOHHmie KHcejiHHe (D. 1,7; ,3a oapeíjHBafte MeTOKcmia") ; 10-NPOU. pacTBop wHCTor HaTpHjyinaueTaTa y 96-NPOU. CHPHETHOJ KHCCJIHHH ; 6POM Y KOMe HeMa JOAA (HAJÔOJBE l y B a T H y 6 O U H 3A KANATTE) ; 80—100-NPOU. HHCTA MPABJBA KHCE/IHHH ;

HaTpajyMaueTaT, aHajiHTHMKH HHCT ; Ka-iHjyMjOÄHa H 0,1 n-pacTBop HaTpHjyMTHocyjHjjaTa. ANAPATYPY 1

F. Vieböck

(CA. 4 2 )

AAJE NPAKTHKAHTHMA

H A. Schwappach

JIAÔOPATOPNJA.

B. 63, 2818, 3207 (1930). 5*

Merode opraHCKe eaeMemapHe aHa;iH3e

68

C K J i a n a i b e H nyH>eH»e a n a p a T y p e : H a j n p e ce CT3BH y H c n n p a (W) 3 m l cycneH3Hje O Ä OKO 150 m g ifpßeHor (poceHy pa3Ön. pacüiBopoM onoBoaiieülaüla h CT3BH Ha ryineHO upeBO, Koje cnaja K n n o B anapaT ca anapaTOM 3a OÄpel)HBaii>e MeTOKCHJia, npeiiH3Ha CTe3ajiHua.

3 a OÄpe^HBaifce m c t o k c h m H3Mepn ce Ha Ha^Htf onHcaH KOÄ o a p e 1)hb3h>3 x a ^ o r e H a n o K a p H j y c y (cTp. 58) n o M o h y neßquije 3a Mepetbe 2 0 — 3 0 m g c y n c r a H i i e , H CT3BH y ö a j i o H y K O M e c e B p u i H p a S a a r a ii>e (K), n o ^ a pacTBOpy c y n c r a H i j e HCKOJIHKO KpHCTa^nha (penojia H 0,5 m l aHXUflpiiMa cupheüiHe Kucenune (HJIH rjiayujajiHe cuphetüHe Kucemne) H AOÄa Taaa j o r n OKO 0,2 g c y B o r ifpßeHor (poc(popa. H s B O ^ e i b e o ß p e i j H B a i b a : n o u i T o ce cyncTaHna CT3BH y öa-noH y KOMe ce BptuH pa3^araK.e, Beate ce u e m w u a 3a yBotjeibe raca ca KnnoBHM anapaTOM H HenocpeAHO npe Hero UITO ce n p H K J b y i H Ha a n a p a T y p y , CTSBH ce y öaJioH 5 ml joaoBoaomiHHe icucejime ( D . 1,7). A n c o p ö e p ce 3auiTHTH o ä T o n ^ o T H o r 3paMeK>a • a 3 6 e c T H o M n j i o i o ü , a H3 HCTor ce pa3Jiora y3HMa UITO j e M o r y h e Matt>e r J i H u e p n H C K O KynaTHJio ( n e x a p ) Koje cayscH 3a 3arpeBaH>e joaoBOÄOHHMHe KncejiHHe. n o u i T o ce CTpyja raca p e r y j i H i n e n o M o h y CTe3a;iHue TaKO Aa yBeK caMO n o j e A a H M e x y p npo;ia3H Kpo3 a n c o p ö e p , 6p30 ce 3 a r p e j e r ^ H uepHHCKO KynaTH^o H OApacaBa 3a BpeMe 0ApeljHBaH>a Ha 140—150°. f l p o jia3HO noBehaK>e 6p3HHe npoTHuan>a raca He y3HMa ce y oÖ3Hp; HHM j0Ä0B0A0HHHHa KHcejiHHa npoKJby^a ycnocTaBH ce npßoÖHTHa 6p3HHa raca. n o c ^ e jeÄHoqacoBHor 3arpeBait>a caB MewujijoauA j e CHrypHO npeAecTHjiHcao y a n c o p ö e p ; Ta^a ce Hajnpe yKJiOHH a n c o p ö e p , a 33THM cKHHe ryMeHO upeBO K o j e Be3yje öajiOH ca KHnoBHM anapaTOM. Ca J'OÄOBOAOHHHHOM KHcejiHHOM K o j a ce Hajia3H y öajiOHy M o r y ce öe3 AajbH>er Aa H3Bpme j o m TpH 0Äpe^nBatt>a. KOÄ pa3jiaraH>a C T O K C H J I H H X J E ^ H N E I I A yKJbyHH ce Mann K0HÄeH3aT0p H 3arpeBa noaa caia Tano «a ce K O H j e H 3 a i B p a h a , Taaa ce K0HÄeH3aT0p HCKJbyiH npn •ieMy ce H BOM HcnycTH H o.apx:aBa KAyiaae y 6aaoHy joui jeaaH cat.

O i i p e í j H B a i i e opraHCKHX

nouiTO

ce

cKHHe

ancopSep,

cana

ce

69

rpyna

y

ueB

3a

yBO^eite

HeK0JiHK0

e p j i e H M a j e p 3 a n p e M H H e 250 mi, y K O M e ce npeTX0AH0 pacTBopn 1,5 g hhctot HampujyMaifemania. A n c o p 6 e p c e H c n e p e bhluc n y T a , t8ko a a c e A o 6 n j e oko 100—150 mi tc^hocth. C a ^ a h npoMyhKa. c e hh3 3 H A O B e c y ^ a c w n a 5 — 1 0 K a n H hhctc .upaBJbe mcejiune

mi

a

BOfle

Koa

T a m o r

CHaMHHM y

caApataj

H3^Hje

H3Bol)eft>a 6 o j a

ce

MyhKaiteM

racHOM n p o c T o p y .

3HaiH

Aa

y

HHje

6nno

06e3Ó0jeH0M

6poMa

Ako 6 o j a aoboaho

pacTBopy

hcko^hko c e i c y H A H ; h ópoM K o j n c e H a a a 3 H n o c j i e hékojihko M H H y T a ,

Hcne3aBa Beh

nocTuace,

Aa ce

6poMa

nocae

ancopóyje

He n c n e s H e

HaTpHyMaiieTaTa.

AOAa

ce

HeuiTO

pa36jia)KeHe

cyMüopne

mce-

Jiune h oko 1 g ttaJiujyMjoAuaa, oct3bh Aa ctoj'h noKpHBCHO 5 MHHyTa h THTpniiie

H3ABojeHH

jofí

H3

MHKpoÓHpeTe

ca

n-pacüiBopoM muocyjKpaüia H a j n p e ao J K y T o r jaTKa pacwBopa capoda a o o6e36ojeHia. 1

mi

0,1

n pacTBopa

THOcyji(})aTa

oa

noAejioai oóojefta,

oAroBapa

0,02

mi

33thm

a

0,51706

m g

ca

0,1

nocne

ao-

MeTo^a c a a p M c e

ce

MO>Ke

c y i a n o p a ;

Aa 3a

npHMeHH jiaKO

6e3

h

Aajber

H c n a p j b H B e

Ha

oah.

OCH3

0,75067 m g

OC2H6. k o j e

cyncTaHije

cyncTaHue,

Mopa

ce

OHa

H3MCHHTH. rpaHHua

2.

rpeuiKe

OflpeijHBaifae

CyncTaHua KHcejiHHOM

c e ji h h a

3arpeBaft>eM

nape)

h 6eHSOHJiHe

KyBaiteM

ycnpaBJbeHHM

ca

a^KOKCHJia.

r p y n e

50-npon.

y3

A n a p a T y p y THKaHTHMa

1

c y M n o p H O M

K0HAeH3aT0p0M,

h

Haerajia

kh-

6 e H 3 o e B a

THTpmne

X H A p O K C H A O M

3a

ca

iie./i0KynH0r

c e noc^te AecTHJiaiíHje ( y C T p y -

BOAeHe

50-npou

au,eTHjiHe

canoHH(})HKyje

oahocho

c n p h e T H a

j'h

ce

+ 0 , 5 %

oApeljHBaH>a:

^

h a t p h j y m-

(J)eH0^4)Ta^eHH. (cji. 4 3 )

Aaje

npaK-

jíaóopaTopHja.

oapel^HBaibe j e cvMnopHa

noTpefiHo:

KHcejiHHa;

0,033

n-pacTBop

HaTpHjyMXHJipOKCHfla. M8Bo^eH>e j a n

50-üpoi¡. 6e3

OApeijHBaH>a:

M e x y p o B a

HanyHH

pacuiBopa

neHe,

U-ueB

ce

ca

5 p o HeuiTo

KajiujyMXUApoiccuaa

h

a e

b

3a

c y u i e n e

Koja

3a

k>om AOJia3H

HanyHe

ce

KajiifujyMXJiopufíOM. 3a HHue

ctsbh

0Apei}HBaH>e

3a

Mepeae

ca

y

ó a a o H

y

A e H 3 3 T o p 1

a i í e r a j i a oahocho 6 e H 3 0 H J i a H 3 M e p n AyroM apiukom (b. C T p . 5 4 ) 2 0 — 3 0 ie.

n o c t a b h

/?. Kuhti h H. Roth,

y c n p a B H O ,

B . 66, 1274

npn

(1933).

neiviy

ce

ce m g

noMohy

riomTO

OB;ia}KH

ueB-

cyncTaHue ce

ópyiueHH

h

kohAeo

C

ananme

Me-roae opraHCKe ejieMemapHe

70 jeÄHOM

ixH3H6

Tano,

Kann

BOfle

fla

C T e 3 a j i H u e fla

6H

floöpo

6p3HHa

KOJH

Ba3^yxa

30 Mexypoßa y

H3HOCH

3anTHBao, MHHyTH.

ôaaoHa

ce

Tafla

noMohy

Kpo3

anapaTypy

A

fleo

n p e-

3anraBa

ce

B HHJ'H c e ó p y m e H H 2 — 3 ml 50-üpoii. cyMüopne icu-

Ha

y

Caflp»HHa

npo;ia3H Kpo3

JieBaK

HCTH HHHHH c a n a c e c a f l a óajiOH, n o c T a B H CTaKJieHH niTan s H y

3anTHBa

cejiune

ce

BpymeHH

pacKBauieHüM (poccpopueHiïiOKCuaoM. fleo

noflecw

3arpeBa

AO ó j i a r o r

ueBH

JieBaK

CT3BH -1 mi BOfle.

Kjbyqaita.

CanoHH^HKauHja O-a u e T H J i - j efln h> e k> a j e y B e h u H H a i y n a j e B a 3aBpmeHa nocjie 60 MHHyTa. Kofl N - a u e T H ^ H H X H N-6EH30HFLHHX jeflHHjeiba 3 a n o T n y H y canoHH(J)HKai;Hjy n o T p e Ó H a c y 3 laca. Mojíce ce OCTABHTH fla ce c a n o H H ( J ) H K a i í H j a H3BpniH H npeno Höh« ca H e i i r r o KOHU. H 2 SO 4 . n o ca

3aBpmeTKy

10—12

mi

BOfle;

K0HfleH3aT0p0M

CTH;

ano

je

floflajyh«

no

7 ce

ca

3a

H cJieflehy

7—8

He

ceKyHflH ofl

nojaBH

flpyry

Ha

flOJie

AOK He o c T a H e

ce flo

ôpHJKjbHBO

nocTaBjbeHHM 5

Kjbyqaita

flecrajiyje OKO 7

H oflMax

o ö o j e i t e ce~2—3

Teqfao-

JI,ecTH^aT

Ha n p n c y c T B O

n/30 NaOH1

ca

mi

3a Kjbyqaft>e.

HaKHaflHO j o u i T p n n y T a .

öapujyMXJiopuaa

p y » H q a c i o

caMO j o u i

KonfleH3aTop

CT3BH HCKOJIHKO n a n n ^ a p a

0,02 mi

THTpaunjy

TrçTpaunjy

npHMep 3a

HeuiTO

ce

KOCO

ca

KBa p u a

flecTHJiyje ca

noflejioivi

AOK c e

ceKyHflH.

ofl

óajiOH c e

BOfle

HcnHTa

3arpeje

KpoÖHpeTe ynpaBO

ml

y

ncnepe

flecTHJiyje

epJieHMajep

noTpeÓHO

(OKO 20 mi) KHcejiHHe,

y

canoHHe

„

0,040

1 m/n/30

p a c T B o p a HaTpHjyMXHflpoKCHfla

TpaHHaa

rpeixiKe

Y

rope

onHcaHoj

Be3aHe

3a

MeTOfle

R. Kuhn

3.

,

C-aTOM

OßpeijHBaibe

.

1X7 » » 0,040 „ THTpauHje He Tpeöa jia ce yTpouiH BHuie o a

—

n/30 N a O H

oflroBapa 1,434 mg— C O C H s OÄH. 3,5033 mg — C O C 6 H B

0flpel]HBaH>a: + 0 , 5 % . anapaTyp«

OKCHflauHjOM a

0 , 0 5 ml

2

H F. L'Orsa.

aKTHBHor

c e o f l p e l j H B a T H H MCTH^IHÊ r p y n e XPOMHOM KHCEJIHHOM n o n p H H u n n y

Mory ca

BOflOHiiKa

i

no

HyrajeB-U,epeBHTHHOBy3

5

y3 20 ml anu30Jia (aMiuiewpa , KCUJIOM) flecmnoBaHor npeno nawpujyMa, 7 g MeJüunjoaufía H 2 g Mame3ujyMa npnnpeMH ce, y3 flOflaTaK 1

^aKTop

XHApoKCHAa

ojipetjyje

c e ca OKcajiHOM KHceJiHHOM KOÄ npHÔJiHJKHo HCTor

pa3ÖJia)Ken>a. 2

Z. a n g e w . C h e m . 4 4 , 8 4 7 ( 1 9 3 1 ) ; B . 66, 1274 (1933).

s

B. 40, 2023 (1907).

*FLO6HJAH.EBHÄH VI, 2 5 AoôHjatbe B HÄH I, 7

OapefjHBaibe opraHCKHx rpyna

3 p H a u a joaa,

HEKOJIHKO

o H H C a HJ e

pacïïiBOp

NOCTABJBËHOM

K 0 H A 6 H 3 3 T 0 p 0 M OB^e

c^yjKH

KOHAeH3aTa). He K p e H e

BpahaH>e

AKO

peanunja

OA c e 6 e ,

Ha K p a j y

HA

50°,

H

je

y

ô a j i o H y

OABOAHA

3a

p a K U H-

CHAÔACBEHA

I í e B

MSJIUM

TO

c e OHa 3 a n o H H e K p a T K H M RPEBAIFAEM

qnja

(KO]'«

3a

caMa

Bo Ppuwapy

KOCO

71

3a-

AOBPIIIH

jeAHoqacoBHHM

3a-

r p e b a a e M H a BOACHOM K y n a THJiy.

Ta^a

ce

(JjpaKaHOHHcaHbe HOPMAJIAH

3arpeBa

3a y

NOJIOHCAJ H N O H O B O

nojia

npoBOAehn

MeMujijoauaa.

OCT3T1ÍH

HeyTpoiiieHor K Ji e H H

pacTBop

0APEÍ5HBAK>e

A n a p a T y p a J l y H r e o B HeAocTaje ripejia3

ca

KpaK d n o M o h y

c y ^ a

KojH

cnycTH 90°

cyA

enoja

ce

naaobHBHM

3A

3a

cyA

H3jeAHaqaBaibe

KynaTHJia,

nycTH

y

HHTpOMCTap

H3JEAHAQABAH>E

ca

cyA

H ryMeHor

ypOHH

Ha c a .

qnja

ca

ce

nexap

OAHOCHO

cnna

y

Apyra

Ba3Ayx

cyBHM

MHCTor neBH

ryMeHor ca

CJiaBHHa

Ka;i-

npeTXOAHO

TeMnepaTypa

ce

HHBOS,

H a3Ä>HM

cyncraHue

TOKHHH H

c a BOAOM 3 a r p e j a H O M Ha

paCTBOpOM

CaAa

ce

ocynieHor

0hu30ji0m,

noMohy

upeBa

com. KpaTKe

H3MepH

MOJienyjicKoj

ce

44.

H HB o a

KyxHK.cKe

HcracHe

3aTHM

pacTBop

je

yiueTaiteM

TaAa

HHBO3.

6 H p e T O M.

ml

c Aoôpo

npejinje

5 M H H y T a , AOK c e

npnqeKa

cyA

npeMa

pacûlBopa,

H H T p o M e T p y

6OUH.

oApeijHBanbe

Kpan

MyhKaiteM.

peaKiiHOHH

3anTHBa

Ha

b. 3 a

Beh

3aTBopeHoj

pacTBOpOM

Ay»H

OA

cía-

5

ce

ce

cymeH

npHKasaHa

cnpenaBa

y

rpuwapoBor

peaKUHOHH

PEAKUHOHH

H3 B O A C H o r

cyA

Kpo3

OKO

H

nocjieAH>H

OAJinje

H3jeAHaqaBatbe

cyncTaHue1,

rpyna

CJI3BHH3, H H a r t y H H c y A

3a

ce

Aoôpo

OBORA

3acHheHHM

Mepeae

H Beace

Aoôpo

TeMnepaTypy,

AHHCYHN

ce

c y A

OKO 0 , 1 — 0 , 2 g ,

(HeonxoAHo!)

nOCT3BH

3a

n n n e T e 5 ml

U H j y M X J i o p H A O M

coôHy

qnjH

OA

y

aKTHBHor

K a j i i i H j y M X J i o p H A O M

H pacTBopn

H3B3AH. C a A a

ce

pacTBop

npoueA«

AS c a q y B a

peaKUHOHH

XHAPOKCHJIHHX

sanyinaqa

a

HanyHH y

ueBHHiie

p e a K U H O H o r

aMUJieiïipoM,

MOHce

YNOTPEÓJBABA

nape

noMohy

a30ïïi0M

ce

AecTHJiHiuy

TpHaapoB

óojbe,

3a O A p e l j H B a i i e

Ha u p T e a t y ,

BOACHe

caApJKajy

44

a30T n p n qeiuy

AOÓHBCHH

H;IH,

H H T p o M f i T a p

ueBHHiie Ta^HO

«IHCT c y B

TaKo

MarHe3HjyMa

H y H;

CB3KO

ON.

c a T a Ha BOAG-

HOM K y n a T H J i y

3 a

ôajiOH nocTaBH

H3jeAHanH,

KYXHHACKE

CJIABHHA

COJIH

OKPEHE

oKpeTaiteM

cjiaBHHe

c e PEAKUHOHH c y A

Aa Teqe

3A

no90°,

3a

H3B3AH

y rpnitapoB

pa-

C T B o p , n p e c n e HCKOJIHKO n y T a T a M O aMO H M y h K a CBE A O T J i e AOK c e MEHHCKY.c y

ÓHpeTH BHiue

1

He c n y u i T a , AAKJIE, A O K c e He 3 a B p u i H

pa3BHjaH>E

Memana.

O Ä jeaHtbefte, Koja ce Aoönjajy y npaKTHKyMy, Mory ce ynoTpeÔHTH TpH({)eHH;iKap-

6HHO;I, ß-HaTO.n, XHAPOXHHOH, 6eH3ocBa KHce^HBa.

MeTOÄe opraHCKe eJisMemapHe anajin3e

72

PeaKUHOHH c y A c e bpsth H a T p a r y boacho Kyn3TH;io,; «iena c e 10 MHHyTa AOK

He npHMH

TepM0MeTp0M),

HCTy

TeMnepaTypy

h npoHHTa

Ha

Kao n p e n o ^ e T K a

yoÖHqajeHH

MeTaHa. HcTOBpeMeHO c e OApeAH mm.

H3paHyHaBaH>e:

üo

RH„ +

(noHTpo^a

KOJinmiHa

6ap0MeTapcK0

TepMOMeTpa koj'h bhch Ha Ö H p e ™ , p e a y K y j e Ha 0° h 7 6 0

h3hhh

oivieAa

CTßopeHor

ciaibe,

T e M n e p a i y p a

h

je^HaqHHH

n CHS • MgJ -> R • (MgJ) „ +

n CH4

p a 3 B H j a j e ^ a H r p a M - M o a c y n c T a H u e n X 2 2 , 4 JiHTapa MeTaHa,

npH qeMy

0 3 H a q y j e 6 p o j 3 k t h b h h x H-aTOMa, a g c y n c T a H i j e = — MOJiOBa ml

M

,

„„ CH4.

. . Koja j e H3paqyHaTa

Q

3anpeMHHH

aKTHBHH H-aTOM ( n =

... (V

n

pa3BHjajy

M

n-22400-a

noMohy

r a c a . 3anpeMHHa ce

. H3p,)

3a

je^aH

1) Mopa Aa 6 y A e j e A H a i o npoMHTaHa h p e ^ y K O B i H a

V

3anpeMHHa ( K H3lj.), hjih sko hm3 BHiue skthbhhx H-aTOMa, t o

V

Aa 6yAe yMHOiKaK oa

H3p. • P e 3 y ^ T a T

ce

H3pajKaBa

Hai). M o p 3

skthbhhx

öpojeM

H-aTOMa n p e M a OAHOcy V Halj./V H3p. • T p a H H u s r p e a i K 3 h 3 h o c h

5—10%.

4. O f l p e ^ H B a i t e M O J i e K y j i C K e T e > K H H e M h OB^e He H3BOAHMO n o j e A H H e MeTOAe, n o u i T O c e OHe n o npsBHJiy y q e y (J)h3hmkom hjih ^hsh^ko-xcmhckom npaKTHKyMy. nocTynan

Tpeöa

yßeK

npemocTaBHTH

kojh c e H a j M e i u h e y n o T p e ö j b a ß a j y j e c y heTHa

KHcejiHHa,

KpHocKoncKH

e6y./iH0CK0ncK0M.

6eH30Ji

H3j6oJbH s n a p a T j e BeitManoB

PacTBapaMH

h r./iauHjajiH3

cnp-

33TBopeHH 3 n s p 3 T C3

ejieKTp0MarHeTCK0M MemajiHijoM. B p ^ o e ^ e r a H T a H h jeAH0CT3BaH n o c r y n a K

n o KOMe MOJKe a a c e

p e A H MOJieKyjicKa TeacHHa opräHCKHX cyncT3Hi^H y 6 3 ^ 0 H q n h y Rast1.

Ban>e T3HKe T O i u b e i b s A a o j e K. KaM(})op aeroBy

Taqny

HMa

Bpjio

Tonjbeiba

CTBOpeHe,

OKpyr.nO

E KaMijjop =

40.

To

8

BHCOKy jano

nyTa

3Ha«iH

Aa

oa-

3 a OApeijH-

KOHCTaHTy

'raiKe

Mpaibeita,

CHHHtaBajy M a T e p n j e K o j e c y y H>eMy p a -

ja^e ce

Heru HeKH

jih k o a | 6 e H 3 0 J i a . g-MOJiapHH

£6eH30Ji =

pscTBop

y

5,1,

K3M(J)opy

T o n n 33 4 0 CTeneHH hhjkc H e r o jih p s c T B s p s q , HaHMe csm K3Me n o m y H o AOBOJbHa oceTJbH-

boct j e A H o r

oÖHHHor

TepMOMeTps

Ha

KojeM

Moxce

Aa

ce npo^HTa

1

/i

2

CTeneHa . U e B i H u e 33 OApe^HBaH>e T a n K e T o n j b e i b a n p a B e c e Kao iiito j e a s t o h3 CTp. 3 4 H3 jeAHe iHCTe e n p y B e T e ; yHyTpamibH npe^HHK T p e ö a Aa h3hoch 4—5 mm, AyJKHHS oko 5 cm; OHe T p e ö a Aa c e csmo Majio CMeKtuajy 1

B. 55, 1051, 3727 (1922) Abderhalden, Arbeitsmethoden, Abt, III, Teil A d p 754. HacynpoT HawHy paaa no Rastu, no MeranH Koja je HHwe onwcaHa, a Kojy je pa3paAHO IV. Münster, He OÄpeljyjy ce Tawe TonjbeH>a, Beh i a « e oiBptuhaBaH>a. 2

73

OapetjHBafte opraHCKHx r p y n a

npeMa A n y Koje Tpeöa Aa HM3 IIITO j e M o r y h e T3H>e 3HA0ße, H Aa j e paBHOMepHO 3aT0n^.eH0 IIITO ce nocTHJKe 0Ay3HMaH>eM OMeKiuajior CT3KJI3 ca CTpaHe. 3 a yHoiueite cyncraHiie H K a M ^ o p a CJiyniH ueBqnua K o j a j e rope nponiHpeHa y o ö ^ H K y j i e ß K a . UeßqHiia 3 a OApe^HBaite TaqKe T o n j b e i t a K o j a CTOJH y n o c T O J b y OA njiyTe r a p n p a ce 3AJEAH0 ca ueBqnaoM c a jieBKOM Ha o Ö H q H o j aHa^HTHHKoj B a r n , c w n a OKO 10 mg cyneraHue y3 noMoh

cTaioieHor

ce

uiTanHha

Kojw

TaqHO

o^roßapa

aeBHHUH

ca

JICBKOM,

TaqHOiuhy OA 0,1 mg, craBH 33THM 1 0 0 — 1 2 5 mg KciMipopa Ha HCTH H8MHH y UCBIHUy H nOHOBO H3MepH. M3Mepn

ca

n o u i T o ce JießaK H3B3AH, iießqHija ce 3aTonH Ha cacBHM M3JIOM njiaMeHy, npn qeiny c e He H3BJiaqH cyBHiiie TaHaK KOHaii. Ta,n,a ce C3AP>KHH3 X 0 M 0 r e H 0 H C T O H H y KynaTHJiy ca KC>HixeHTp0BaH0M cyMnopHOM KnceJIHHOM 3arpejaHOM Ha 180°. I l o c j i e x.nal)ett>3 yqBpcTH ce ueBqHija ca CBOJ'HM CTAKJIEHHM KOHueM noMohy ryiueHor npcieHa Ha TepMOMeTap, 3arpeBa y öajiOHy 3a OApefjHB3tt>e TaqKe Tonjbeiba (CJI. 30) CBE AOK ce ÖHCTPO He HCTonn, nycTH Aa ce OXJISAH, H TaKO H3Jje N P H 6 J I H « H A TaqKa oqßpmhaBaita. J\& 6a ce OBa TaqHO yTBpAHJia, nOHOBO ce 3arpeBa, oßora nyTa BPJIO NA>KJBHBO ca M H K P O N J I A M 6 H O M q«jn ce Bpx Ha^a3H OKO 4 cm HCIIOA öajiOHa, CBE AOK ce c a ^ p ® a j ueßqHite He HCTOIIH ÖHcrpo H3y3eB HeKOJiHKO cacBHM MAJIHX KPHCTAJIHHA 33;IENJBEHHX 3 3 ÄHO. TeMnep3Typs Kojs ce C 3 Ä 3 nocMaTpa JIOKH OÖNQHO 2 ° H3HAA paHHje TAQKE oqßpmhaßaft.3. CMAIBHßAHJEM MHKPONJISMEHA pery^Hiue ce CA^a x j i s ^ E I T E , TAKO Aä T E M N E P S T Y P S ona^A y MHHyTy 33 OKO 1°. flpn TOMe ce BHAH noMohy Jiyne ßPJIO j a c H O

KSKO n p e o c T 3 ^ N

KPHCTSJIH NOQHH>Y AA p a c T y .

Y

TOME c e

Tpe-

npoqHTa TeMnepaTypa. P S A H KOHTPOJIE MOIKE ce onepsuwjs N 0 H 0 BHTH H KOA 6PH)KjbHBor P3AA HAHN he ce TOTOBO HCTS TAQKA oqBpiuhaBaifca. KOPHCHO j e AA ce MIAMEH 3 3111 T H T H jeAHHM UHJIHHAPOM NPEQHHK3 8 cm OA CTAKJIA HJIH OA x s p r a j e KOJH Tpeöa Aa Aonnpe AO ÖA^OHA 3a OApeljHHYTKY

BAK>E TAQNE TORUBEIBA.

Hs HCTH H3qHH K30

UITO j e TOpe OriHC3HO yTBp^eHS j e npeTXOAHO K A M ^ O P A KOJW C J I Y » H 3 3 0APEIJHB3H>E. T p e ö s Aa ce ynoTpeÖH CSCBHM qacT npensp3T. AKO T3KAß He CTOJ'H Ha pacnojioKeH>y, TO ce HS nojeAHHHx KOMSAS OAaöepe OHOJIHKO KOJIHKO j e noTpeÖHO H CTONH AA 6 H ce AOÖHO cnrypHO XOMOREH MaTepnjaA. TAQKA

OIBPIUHAßAIBA

Pa3flHKa y nopetjeity ca TaqKOM oqBpinhsBaifca KaM^opa (177°) j e A, .. 4 0 • a • 100 a MOJieKy^cKa TejKHua M = ; a = KOJiHqHHa cyncTaHue, b = TeJKHH3

KaM(J)Op3). TpaHHua rpemKe npeMa npaßoj

HOCH +

ßpeAHOCTH MOAeKyjicKe TeacHHe H3-

5%.

JeAHHbeK>3 Koja cy TeuiKo pacTBopHa y K3M(j)opy, Koja ce Ha TeMnepaTypn Tonjbeiba p33^ajKy HJIH Koja p e a r y j y es K3M4)opoM, HapaßHO, He Mory Aa c e OApei)yjy no OBOj MCTOAH. Y TaKBHM CAyqajeBHM3 ynoTpeöjfa3B3 ce Kao „pacTßapaq" yrjbOBOAOHHK K3M(J)eH1 KOJ'H ce Tonw Ha 49°. 1

Pirsch, B. 65, 862, 865 (1932).

OpraHCKO-npenapaTHBHH Äeo

74

B. OPrAHCKO-nPEnAPATHBHM

flEO

3auiTHTa npoTHB HecpeTHnx c j i y n a j e B a Ko 11 O K C

Heonpa3HO

JI

aK o KOA

H

Koje

Hecpehe

A A I O C T

j e A Ha K o

öopaTopHCKor c T a H CBOJHX

je

3 a in T H T a

ca jaKHM CT3KJIHM3

BaKyyMOM

c B o jHM

onacHoeTH.

CBAKH H O 3

Ha-

Q JI a H JI a -

6 H JB H O c B e-

jpyroBHMa.

o q H j y . COJIHAHC s a u i T H T H C

Mopajy

H npHTHCKOM

JA

6y A e N O M Y H O

npeua

UITETY.

aaßopaiopHjaMa

3 A X T E ß A J Y

KOJICKTHB3

Ä Y ® HO C T H

HajßaiKHHja o^apH

o A CBaKe

ce y XCMHCKHM

A EM a B a j y

P A A Y

pa/ia ^A n p e T p n «

A JI H H O H a j K o j H n a 3 H H H j e o c n r y p a H TeiuKe

npncTyna

HENPOMHIUJBEHO

npenapaTHBHor

j a c e Hoce K O A CBHX

Ha-

paAOBa

ca

A3KJie KOA H3BoljeH>3 B3KyyMAecTHJi3iiHje,

KOA n p ß o r eBaKyHcatba Hoßor eKCHKaTopa, n p « p a A y ca 3äTonjbemiM u e BHMa, öouaMa noA npHTHCKOM, ayTOKJiaBHMa. J U j b e , npn H3BOi)eiby a JIK

a JI H H x

Tonjbeita

MaTepnje CBera

Koje

npn

o n e p a u n j a , K O A KOJHX Mory

H CBHX

HarpH3ajy

p 3 A y ca

HJIH

MeiajiHHM

P a ß c a MeTajiHHM

Koje

HJIH

HJIH

HaTpHjyMOM n p o y s p o K O B a o

ca HSTpnjyMOM, n o c T y n a

ö a u a j y y CJIHBHHKC

Aa HcnpcKajy

3 a n a j b H B e . TaKo npe

HaipnjyMOM

T e u i K y Hecpefey y j i a Ö o p a t o p n j a M a . pynyje

cy

3 6 o r Tora

K

a JI H j y M O M.

je B e b no

HeKy

HeKa ce y B e K , KaA c e

Bpjio öpniKJbHBO,

KO(J)e 3a OTnaTKe, H Hena

HeKa ce ce He

oraaTUH He

ocT3Bjbajy

Aa

c T o j e Ha 0TB0peH0M, Beh HeKa c e oAMax cTaBe HaTpar y c B o j y 6 o u y , HJIH Hena

ce

ca

yHHMTe

15—20-CTpyKOM

P e a K u n j e ca MeTajiHHM H3BOAe HA KJbyHaaoM y3Me yBeK

KynaTHJiy, Beh T p e ö a

Aa ce

HJIH y Jb a H O K y n a m r a o , qaK H npn AecTHjiOBaiby

eTpa H3H3A HaTpHjyMOBe

mwue, KOJOM j e 6HO

cyiueH.

NPH

TpHjyMOM H Ka;iHjyMOM T p e ö a ce öpHHyTH y TaHiHHe o anapaType,

SJIKOXOJIS.

HaTpHjyMOM HJIH KajinjyMOM He T p e ö a Aa ce

BOACHOM HJIH napHOM

nem q aHo

KOJIHHHHOM

p a A y ca Ha-

caBpiueHOCTH

H T p e ö a HMSTH CTajiHo n p e A oiHMa nocJieAHae Koje Mory

Aa HacTaHy y c j i e A Tora IIITO eBeHTyajrao OMOTaq K0HAeH3aT0pa He 3 a i m i B a , HJIH naA öajioH npcHe. y B e K T p e ö a CTaBHTH s a u i T H T H e HeKa paAH

ce

6e3

ca

eKcnjio3HBHHM

3aiiiTHTHHx

cyncTaHaaMa

HaoMapa,

H HeKa ce

Haoiapn! HHkaAA

Heno3HaTe

He

MaTepHje

yBeK Hajnpe HcnHTajy ca MajiHM KOJiniHHaMa Ha MeTajmoj mnaTyjiH, KaKO c e noHamajy AA c e

y

n JI 3 M e H y .

CKJIOHH Ha

H a 6H c e OKO c n JI o 3 H j a 6H CBAKH HaoH3pe,

n p e n a p a T Mopa

npn TOMe

npeTX0AH0

3auiTHTHJio

H OA

AejcTBa

HenpeABHtjeHHx

e K-

K o j e HHK3A He Mory Aa ce CSCBHM c n r y p H o H C K J B Y I E , T p e ö s j i o j e 3anocJieH y

KOJH

6e3

CaM

CTpaHy.

oÖ3Hpa

jisöopaTopHjn Aa

Ha y n o T p e ö y

HOCH

33IIITHTHHX

craJiHO

OÖHIHE

Haoiapa

y HaBe-

AeHHM cjiyqajeBHMa. üpn JbHBHU

PAAY

ca e T p O M

TeiHOCTHMa

H

APYRHM

HcNap jbHBHM,

MOp3 Ce CT3JIHO n33HTH Ha TO,

jiaKo y

3ana-

ÖJIH3HHH

3aoiTHTa npoTHB HecpetHHX cjiyiajeBa rie r o p a

njiaiaeH.

A k o Aolje a o noMtapa, t o T p e ô a npe CBèra

y K ji o UH TH C B 6 i i i T O M 0 2 c e Kpnaiia,

cnnaiteM

Hajôojbe

cpe^cTBo

75

c e 3 a n a ji h.

TeipaxJiopyrjbeHHKa,

3a

rameite

je

Maaa

o^Max

Taßa ce raen BJiaacHHM He

ana

boaom.

C02 - 6 o M6 a

noAecHa

Koja

T p e ô a a a ce Hajia3H y cbskom pa^HOM O A e ^ e i t y , A k o ce noacap jaqe parnnpH,

BaTpa ce racH cnnaiteM

y3eTH

BeJihKy

Koa 03JieÄa Tpeôa

Hajnpe

KapöoHaTa

ca

6oiiy

necKa;

KHccjiHHana

TeMejbHTO

h OBAe bcííhhom

ha h Kaycthihhm

HcnpaTH

Ta^a ca

boaom,

oah. p a 3 Ô J i a H c e H 0 M

cnpheTHOM

jiaKHX oneKOTHHa onaaKHe ce oneqeHO MecTo Baia

3a Koa

3aBoje,

3aBojH,

T p a » H T H HajÔJiHMcer

3a

6 h-

khccjihhom.

Koa

oneKOTHHe.

4>;iacTepH

t em k hx HecpeTHHX

aJiKajiHjaiua

pacTBopoM

a j u < o x o j i o m , h Ta.ua no-

KpHje. Ji a h e h h m y j b e M hjih t.3b. M a m h y npnnpeMH.

papuje

Tpeóa

yrjbeHjiHOKCHAOM.

yBeK Aa cy y

Mopajy

c^yqajeBa

T p e ô a OAMax no-

senapa.

A k o je Ha KOJKy A o c n e j i a

HeKa

cyncTaHua

opraHCK'a

Koja je

h a r p h 3 a h^h Ha A p y r n HaqnH ApajKH, t o je npaite b o a o m BehHHOM 6e3 AejcTBa.

OHa

ce

OTKJiaita

hckhm

noroAHHM

pacTBapaqeM,

Kao

u i t o je

a ji K o X o n HJiH 6 e h 3 o ji, o a K o j e r ce 3a Hcnnpaibe OAMax y3Me o 6 h ji h a KOJiHHHHa.

Mopa

ce

y

y3eTH

oÔ3Hp Aa opraHCKH pacTBapaq caM no

ceÔH nocneuiyje n p o A H p a i t e iiiKOA^nBe MaTepnje y K O » y

h 3Ôor Tora ce

Mopa Aa H3ÖerHe CTBapaite KOHiieHTpoBaHor pacTBopa Ha Hboj. H a p o q H T a ce npeA0erp0)KH0CT ynoTpeÔJbaBaHHM (J)03reH0M, XJOpOM,

MaTepHjaiua :

AHMeTHCyJI(J)aTOM,

6 p O M O M,

HajiajKe npii p a A y ca cJieAehnM m h o t o

unjaHOBOAOHHMHOM

330TM0H0KCHA0M

yrjbeHMOHOKCHAOM,

khccjihhom,

npOCTHM X ^ O p H A H M a

HaTpHjyMOM

h

H

KHCejIHHa,

33 0TAH0KCHA0M,

KajinjyMOM.

A k o ce OBe

y n o T p e ô j b a B a j y y bgîihm p a 3 M e p a M a , t o o n e p a i i n j e ca obhm T p e ô a A a ce H3BOAe

y HapOMHToj npocTopHjH,

HHaqe yBeK noA A o ô p o M

KaneaoM.

Hepa36jia}KeHa xajioreHCKa jeAHH>eit>a ajiH(J)aTCKor p e A a , Kao ÔpOMHA, y

Ha np.

AOAnp

j y m o m,

XJIOpO(j)0pM, cyuiHTH

6pOMO(J)OpM ca

MëTajiHHM

H CJI. H e

HaTpHjyMOM

nouiTO npn y A a p y Moace Aa A o i j e a o

n JI o 3 h j a

CMejy

b p ji o

e t h ji-

ce AOBeCTH hjih

hccctokhx

k a ji he k c-

(Staudinger), npBa

onpeMa

I. nocyuE 4 a m e no jeAHa o a

100, 500, 1000 ml.

B h p e T e1.

1 npaKTHfcaHT Mopa aa je y CTaity, aa y cBaKO no6a Oiwax MOHce na H3Bpuin yo6nlajeua Bo^yMeTpncKa oapef)HBaita. F l p a n p a B K O C T 3a T m p a u H j y y opraHCKoj JiaöopaTopHjH HH|e Ha HapcwHTo Hceaenoj H noTpeôHoj B H C H H H .

OpraHCKO-npenapaTHBHH jieo

76

npaBe, 3 KOMa^a.

H6BH ca K a j m H j y M x a o p H Ä O M , B a ji o H H 3 a

ÄecTHiiOBaite

oóm^hh H no Claisen-y,

n o je^aH o ä 25,

50, 100 ml. EpaeHMajepn

n o 2 OA 50, 100, 250, 500 ml.

E T H K e T e. Typnnje,

Mame

no je^Ha OKpyivia H TpocTpaHa.

o A JI H B 6 H o r CTHKJia 3a u e ^ e i t e no 1 OA 500 1000 ml.

riJiOHHiie 3 a u e i j e f b e o A n o p u e j i a H a

OA 1, 3, 5 cm.-

X a p T H j a 3 a u e ^ e & e, HCKOAHKO TaôaKa. C T a K J i e H e u e B H , npaBe H caBnjeHe. C T a K J i e H e u e B H , H3ByqeHe nao nHneie (ueB 3a Kanake, crp. 1 1 ) . C T a K J i e H a A y r M a A 3a ueijeite Ha BaKyyM, 2 KOMaAa. CTaKJieHH

l U T a n H t i H , 20 pa3^inmiTe AeöjbHHe H AyflíHHe, Ha o 6 a Kpaja

O K p y r j i o 3aTonjbeHH, ajiH He H 3a#e6jbaHH. TyMeHa

apeBa

H ryMeHH

lenoBH.

neuiKHp. PyqHa

Bara

(HOCHBOCT 5 0 — 1 0 0 g , ouiTpnue 3 3 u í t h t h t h B33ejiHH0M n p o -

T e r o e a oA

THB pije 1 y 3 T O c a o r Cjior

3 a 6 y in e h> e

HenoBH

oa

CiaK^eHe BaKapHa

njiyTe mojbe

»Hua

Barn

Ha

AO

12

pa3He BejiHMHHe. 3a K p H C T a j i H 3 a u H j y

3a n p o 6 y

(^HCTOBH

KoHAeH3aTop cm

g).

0,02—50

qenoBa.

OA

no 1 OA 3, 5, 7 cm.

HaxajioreHe.

K a p TOH h

3a

Mepeite

KapTOHa).

n o Liebig-y

A y r OKO 60 c m ;

A Y J K H H E . Dimroth-OB

HCTH TanaB

HJIH 3MHJACTH

Kpahn OA 10

K0HAEH3AT0P.

M e H 3 y p e 10, 100 ml. MeTajiHa

uinaTy^a.

H y h, UH^HHÄpHqaH OKO 8 cm. riJiOHHue 3a M H K p o c K o n n p a f t e riHneTe

3 KOMa^a^

OA 5, 10, 20 ml.

EnpyBeTe

3a n p e n a p a T e ,

riopuejiaHCKe

rnojbe

pa3JiHMHTe Bejin^HHe.

1 5 , 20, 25 c m npe^HHKa.

riopixejiaHCKe

i u n a T y j i e , 3 KOMaAa.

nopueiaïCKH

aBaH.

E a j i O H H n o 2 ÔA 50, 100, 250 H 500 ml. E n p y B e T e , HajMait>e JINX.

O Ä

Tora

50 K O M a . u a H o p M a .t H e b s a h h h h s ,

n o j i o B H H a y B e K ^ a je q w c i a

H

20 M a -

cyBa.

I l l T H n a j b K e 3a e n p y ß e i e . HHÄHKaTopcKa

xapTHja,

H TO JiaKMyc,

njiaBH H u p b ë h h , KypKyMa

H KOHro. KajiHjyMjoAHfl-CKpoÓHa x a p T n j a . Boue

3a u e ^ e i t e

KaMeHiHhn

Ha B a K y y M

100, 500, 1000 ml

3 a K Jb y h a k> e, rjiHHeHH KOMaAHhn OA OKO 3 m m npe^HHKa.

U , e B H 3 a B a K y y M , n o 3 A y r e H KpaTKe. J l e B a K 3 a o A ß a j a i t e , 500, 1000 ml.

ripßa

M a

77

onpeMa

&3 e.

K

UeßtiHue

3a

oApe^HBaibe

TaiKe

Ton^eita,

a,

no

TaHKe (HanpaBHTH

C3MH).

Taj JI

e

a

T

B

a

H.

K,

KOMa^a c a c

2

U E B H H I I E

B H M

Kanaite,

3 A

M

a

A

HAJMAITE

caÄP®HHe 2 ml 6a>KAapeHa Ha 3a

J l e ß a K

Kanaae,

AyroM

33THM

OA

ml

2 5

6 1

1

cpeAft>e

KOMAAA;

Y3

TO

BEJINQHHE AO

joui

JEAHA

12

cm.

iimpa,

/ }0 ml.

ca

ijeBH,

K p a T K o M

OA

1 0 0 ml ca

UCBH.

HcnHTaH,

T E P M O M E T A P ,

3a

TaHKe

OAPE^HBaibe

Tonjbeiba,

join

2,

OA

Tora 1 KpaTaK, 3a y n o T p e ö y . CaxaTHa

c r a K a a , yrjiaBHOM Marta.

B A K Y Y M E K C H K A T O P N ,

2

BEJIHKA

(16

H

18

c m

npe^H.).

H c r u f p a j i H u e , 2 komsas. K

e

III T

a. II.

AueTOH,

1 0 0 ml.

ETap, ancojiyTHH ETap,

O Ö H H H H ,

n p e K o HaTpwjyMa 1 ,

1

JiHTap.

1

JIHTAP.

A J I K O X O J ,

9 6 % ,

A ^ K O X O J I ,

ancojiyTHH,

BeiiaoJl,

P A C T B A P A 4 H

i

1

/2 JIHTpa.

/ 2 JiHTpa.

V2 -nuTpa (H3HaA naTpHjyMOBe >KHII.e).

X.aopocJ)opM, r^auHja^Ha CwplieTHH

100 ml. CHpheTHa

ecTap,

MemJiajiKoxo^, IleTpoJieTap, jyMOBe

ca

KHceJiHHa,

1

/ 2 JiHTpa.

1 / 4 jiHTpa. 1/4 ^HTpa. HHCKOM

TamcoM

LOBYNAFBA,

1/4 JiHTpa

(H3H3A

HaTpu-

MiHue).

1

fla 6H ce ÄO6HO a n c o j y i H H e T a p c y u i H ce Hajnpe 1—2 jimpa KynoBHor e&pa naa KdAqujyMxnopußOM MHja K O J I H H U H S H3iiocH OKO 1 0 ° / 0 T O K H I I C eipa 1 — 2 Heveae, 3aTHM c e 6p3o npoueÄH Kpo3 Ha6paHo ueÄtuio OÄ xapiwje y c y ß y 6ouy y Kojoj c e Hajia3H HatüpujyMOBa Dwaifa. C ß e ÄOK ce pa3BHja B O Ä O H H K cTaßjba c e l u i y i e H H 3 a n y m a < i c a C a C l 2 ueBiHuoM Ha Kojoj ce Hajia3H KpaTKa ueB H 3 B y q e H a y Kannaapy, na 6H ce orpaHHinjio OTnapaßaH>e. Anco^yTHH ce eiap Mo>Ke BehHHOM ÄHpeKTHO na ynoTpe6n. Hajöojbe je na ce eTap qyßa y MpaKy. ripw HcnapaBasty Behwx KOJiHHHHa HeqHCTor eipa, KojH je 6HO ayjKe BpeMeHa y ÄOca Ba3ÄyxoM, Tpe6a aa ce BOÄH paiyHa ca MoryhHomhy na Ha xpajy ÄOJia3H ÄO « e CTOKHX eKcnji03Hja Koje Haciajy OA n e p o K C H . u a Koje ca,np)KH OBaj eTap. OßaicaB eTap HMa o in T a p MHpwc H ocjio6al)a joä H3 3aKHcejbeHor pacTßopa KJ. /U 6h ce n e p o K CHÄH p a 3 0 p h JI i< M y h n a ce ca MemaßHHOM 6ucyji(ßauia H KcmueHTpoBaHor pacmtiopa (pepocyjiipama Ha MyhKajiHUH HCKOJIHKO caTH, c>ÄBojH y jieBKy 3a OÄBajafte H OCJIO6O.HH KHcejiHHe ca Majio jaicor pacüiBopa 6a3e. Ta,na ce 1—2 nyTa Hcnepe ca uano Boae H cyuiH H3Haa KiiMiujyMXJiopuß,a. ÄHpy

OpraHCKo-npenapaTHBHH uto

78

n e T p o J i e T a p , ca BHCOKOM TSHKOM Kjbyqaiba, 1/2 jiHTpa (h3H3a jyMOBe « n u e ) . KCHJIOJI (H3H8A H3TpHjyMOB6 JKHIje).

H3TpH-

III. PEAKTHBH, CPEflCTBA 3A CYIIIEHjE K a i H j y M X H Ä p O K C H Ä , TeXH. H qHCT. Ka^uHjyMX^opHAy r a j b 3a o 6 e 3 0 o j a B a i t > e . R ^ H U E P H H ( 6 o u a ca LENOM OA NJIYIE H CTAKJIEHUM niTannheM). MeTaJiHH HaTpnjyM. H ATP H j y M X HAP o K C H Ä OKO 14 n ( = 4 0 % ) . P a c T B o p co «e. Be3BOAHHHaTpHjyMcyji(J)aT. H o p M a j i H H p a c T B o p n : n/10 HCl, n/10 N a O H , n/lQ pacTBop N/10

joAa,

THOEYA^ÄT-

A 3 0 T H a K H C E J I H H A KOHU. (1,4) H nyniÄ.HBa (1,5). COUS

K H C C J I H HA

KOHU.

C y i a n o p H a K H C 6 J I H H 3 KOHU. qHCTa. C p e ô p o H H T p a T , p a c T B o p 5%. IV. ÄHEBHHUH (WyPHAJIH) XI H e B H H K 1 . C ß e c K a 3a J i H T e p a T y py. I. C y n c T H T y u , n j a XHApoKciuia H BoßOHHKa x a n o r e H O M . AJIKOXOJIH. OJiecJniHH 1. ETHJIÔPOMHFL H 8

ETHJIAJLKOXOJIA

KO^HHHHH OA 200 g (110 ml) KomieHwpoBcme cyMüópne mcejiune *koja ce HaJia3H y ôaaoHy 3anpeMHHe 1 jiHTap, y 3 H e n p e . K H A H O M y h K a a e yjiHj'e ce 6p30, He xjiaAeha n p n TOM, 110 ml (99 g) amoxojia (95-npoij.), 33THM AOÖHjeHa Tonjia MemsBHHa oxjiaAH na c o Ö H y T e M n e p a T y p y H y H>y NAACJBHBO cnna y 3 HenpecTaHO xJialjeifce 75 g jieaene Boue, H Ha Kpajy AOAa 100 g (JJHHO cnpauieHor icajiujyMôpoMuw. PeaKUHOHa CMeiiia ce AecTHJiyje 3arpeBajyhn Ha MajiOM neiuqaHOM KynaTHjiy Koje ce 3arpeBa jaKHM njiaMeHOM; AecTHJiaijuja He Tpeóa a s 6yAe cyBHuie JiaraHa. riouiTO eïïlujiôpoMUfl HM3 HHCKy Ta^Ky KjbyqaH>3, TO ce OBAe ynOTpeöJhyje IHTO je Moryhe AYATH K0HAeH33T0p ca HacTaBKOM (CJI. 45) H;IH 3MHjacTH KOHAeH33T0p, H nyiiiT3 6p3a CTpyja BOAe Aa Kpo3 A e r a npoJia3H. 5 o u a 33 xB3T3ft>e AecTHJiaTa HanyHH ce npe no^eTKa AecTHJiaiinje BOAOM H KOMaAHhHMa jieAa TOJIHKO, AA je Kpsj HacTaBks y p o a e H y BOAy. PesKunja je 1

IlpaKTHKâHT Tpeöa OÄ noqeTKa aa ce HaBHKHe aa BOÄH ÄHeBHHK y KojH he yHem CBe onHce orjieaa H CBa 3ana>KaH>a. KOÄ a a y i H o r p a a a H e o c . n a H . a j c e HHKaa Ha CBoje n a M h e H> e.

CyncTHTyuHja XNAPOKCH.UA H BOÄOHHK3 xaJioreHOM 3aBpmeHa

hhm

ÄHO.

6H ce AecHJio

AKO

BHiue He npe.na3e

ce Bpaha HaTpar y

K a n jb H u e,

yjbaHe

npn/iHKOM

79 Koje

na^ajy

Ha

AecTHJiauHje A a AecTHjiaT

no«me

Aa

KOH-

Ä e H 3 a T o p , OH^a ce y o ß o j H e 3 r o Ä H noMaaceMO TSKO, 3a xßaTait>e A e -

Aa 6ouy

CTHJIATA NOCTABHMO TAKO

HHCKO

A3

npaj

je

Ha-

CTaBKa caMO Ma^io y p o H>eH y

TeqHOCT, IIITO ce

TaKofje

MOHCE

OKPETAITEM

CTpaHy.

nocTHhn

HACTABKA HA

Kpajy

Ha

CA^PACHHA

ce

PEIIHNHJEHTA

emujiöpoMua, AOK>H o i o j , y emujieüiap KOJH j e T a K o l j e KOHij. cyMüopnoM mcenuHOM. n o i i i r o

c a n a y noroAaH JieBaK 3a onBajaft>e, wcnycTH

ml),

epJieHMajep ( 2 5 0

H H3ÄBOJ'H H3 e T H J i ö p o M H A a

H a c T a o n p H peaKUHjn p a c T B a p a j y h H r a c a ce n p a

oBowe

paBaae

cyncTaHije,

KHcejiHHa OÄBOJH

ocjioöaija

ce

TO c e x j i a A H y c M e i i i H

AOAaje

n a o AOH>H CJIOJ'.

CA^A

K o j a ¡ce

peuHnHjeHT

4)paKU.HOHHcaft.e

noTonw

BOAOM H 3 a r p e ß a

36or

c e IIOHOBO

OABOJN y

eranöpoMHA

3a

HHCKe T a n K e

KJbyqaiia Mopa

ce

3a

n p e n a p a r e

rioc^e

HJIH m o j b y

ORAEAA

3HA0Ba.

BAJIOH

KBaHTHTaTHBHO

BehnHe

3aK0Ha

&ajhe

npepa^e Beh

(ynop. 6OUH

y

g.

Kao H KOÄ CBHX

J E ^ A H MOJI

peaKixnja, o

ce

TeopHCKor npHHOca AOÖHO, n p n

(119) Y 3 E ™

naK opraHCKHx

Ha 0CH0By

35—40°

na3HTH, A a

3HA0BHMa,

H3paqyHaBa c e H OB^e,

HA J E ^ A H MOJI KA;IHJYM6POMHAA

KOÄ

3a

HanyaeHy

i e M y T p e ö a Aa c e na3H Ha c j i e a e h e . n p e M a xeMHcnoj jeAHaqHHH ycTBapH

OA-

KHce-

c y n y . XI,ajbe He

IlpHHOc: 7 0 — 8 0

HAyhnx n p e n a p a T a , KOJIHKH c e n p o u e H a T 6H

3A

n p e j i a 3 H H3MELJY

0TB0peH0M

c a TBHKHM

öa^OHy

Ae6ejiHx

3aBpmeTKa

JIEBKY

ca cyiunopHOM

n p n AoönjaHby

BpeiweHa HE n a j i a 3 u y

ce nyBa y

cyMnopHa

38—39°.

T p e ö a TOTOB n p e n a p a T , H a p o i H T O JICTH, AO iteroBe Ra

Hcna-

AOK ce He

XJI a ^ e i t e .

JiOH^e

nopuejiaHCico

a

AOTJIE

MAITEM

ocymeH

XAAAH C M e u i O M

ce y

KOA

HHKBA AY>Ke

eTH^6eH30Ji)

npoy3poKyje

xjia^eae,

MS-IHM N^AMEHOM. E T H ^ Ö P O M H Ä

H TO RJIABHA K o ^ I H ^ H H a

npenapaT

3a

Aa

H3 U,SBH 3a Kanait>e y 3 M y h n a i t e

Bajaft.e H Ha K p a j y A e c r a ; i H i i i e JIHHOM y

K o j a 6H M o i v i a

ToanoTa,

Koje

ÄejcTBy

Tpeöa^o

AJIKOXOAA

c e He

Maca

(46).

OAHrpaBajy

(II, 7), y3HMa

ce j e ^ n a OÄ KOMNONEHATA y BHiiiKy. npw qeniy c y NECTO Mepo^aBHa eKOHOMCKA

pa3MaTpafta. Ca

jeBTHHHjn

EKOHOMCKE

a ^ K o x o j i y BHiDKy,

ÄHFIBEITA n p e ß e j i o y ETHJIÖPOMHA.

Ta^KE

IVIEAHIIITA

Tpe6a.no

6H c e IIITO BHiue CKynjber

6H

y3era

6p0MH0r j e -

T o p e HABEAEHH KOJIH'JHHCKH OÄHOCH y 3 e r a

c y y car^acHOCTH ca OBHM pa3MaTpait>eM. H a 100 g K B r TeopHCKH H3paH y n a T O AO./ia3H 39 g T.j. A ß O C T P Y K O

a;IK0X0;ia,

AOK je

CTBapHO y 3 e T O

BHiue H e r o OA T e o p n c K o r .

npa

86 g

(90 g

H3paqyHaBaH>y

95-%),

TEOPHCKH

80

OPRAHCKO-npenapaTHBHH AEO

MORYHER

NPHHOCA

YNOTPEÖJBEHOR AJIKOXOJI KAKO

MOPA

CE J I P E M A

KAJIHJYMÖPOMHAA.

KOJ'H JE C K Y N O U E H H J N

Y3EJIH

KBR

Y

TOME

AKO

OBAE

Y3ETH

3A

CMO

XTCJIH

n,a N P E T B O P H M O

6H

OA K B R Y

ITEROB

OCHOBY

6POMHA(

KOJININHA

HekH

T A A A 6 H CMO

CBA-

BHIIIKY.

O ß A J HE CE N P E N A P A T A O U H H J E Y N O T P E Ö H T H 3A ETHJIMAJIOHCKH E C R A P ( V I , 7 ) . METHJIÔPOMHFL: AJIKMÓPOMK^A (Bygdén,

J.

RIPENAPATHBHO

NPOH3JIA3H

PR. 8 3 ,

421

NPEMA

[1911]).

AOÖHJAITE

JEAHOM

RIOIIITO

Y

OBOR

HAJJEAHOCTABHHJER HCTOM

NPHHIINNY

H>EROBA

TAINA

K O A 4,5°, TO JE T E N I K O MeïïiujiôpoMua

A O Ö H T H NAO N P E N A P A T

T3K3B,

3A

AJIH CE

BEOMA

NPENOPYQYJE

ANPEKTHY

NOCTYNKY

KJBYNAN>A

Kojn

YNOTPEÖY

P E A K I I H J Y H A M E C T O C K Y N J B E R JEAHTT>EKJA J O A A . R I P M U E H A AHAJIORA

JIOKH

BEH

CE M Y B A ^ A O rpuwapoßy

3A

ETHJIÖPOMHAY.

2. ETHJIJOFLHFL HB ETHJIAJIKOXOJIA 1 je^HOM ô a ^ O H q n h y , c a A P ® H H e

Y

t})OC(J)opa

CA 5 0 ml

MYHKAITE Y T o n y

n e T B p T c a T a 5 0 g e racoBHTOM pwfla.

BpoMOBOAOHHK

npn

leMy je y

MHornM

ita 6H ce peaKUHja ocTBa-

p e a r y j e Tente H OBAe j e MHoro n y i a n o i p e ö H O 3arpeBaH>e ajiKO-

xojia KOjH j e 3acHheH OBOM KHCCJIHHOM y 3aTon;beHoj ueBH. T o p e II3BEJIEHO A o f i n j a i t e e T H à6 p 0 MHÄ a

npn neMy c e H B r ocjioôatja H3 K B r AejcTBOM KOHU. cyMnopHe Ktice^HHe, npeT-

CTABJBA c a y q a j KOÄ Kora p e a K m i j a Teqe Bpjio jiaKO. XaopoBOÄOHHK MEIHJ6ojbe

H

p e a r y j e HajTeHte, H oBjie j e n o T p e ö H o nao Ha tip. npn Ao6njaK>y

eTHflXflopLüaa,

uHHKXJiopHA

HJIH,

na

Kao

ce

npHMeHu

KOÄ

HeKo cpeACTBo 3a 0Ay3HMaH>e Boae, Haj-

BHCOKOMOJIEKYJICKHX AJIKOXOJIA, ÄA ce 3arpeBa y

3a-

TBopeHOM c y Ä y nOÄ npHTHCKOM. ApoMaTCKH

ajiKoxoJiH, Ha np.

M o r y ce Ha OBaj Ha'iHH joui

6en3H jajiKo.xofl

jiaKiue Hero ajiHtfaTCKH Äa ecTepHíjMKyjy noMohy KOHU. xajioreHOBOAOHHqHHX KHcejwHa. HnaK

H Hj e

PeaKUHja IIRMA;

ce

y c n e j i o , Äa c e peaKUHja npeHece HA cjjeHOJie. MOJKe

H3BECTH TaKolje ca

ÄBO-

H

B H m e-B a j i e H T H H M

npH toiue saBHCH OÄ y c j i o B a paÄa, Kao UITO j e KOJiuqHHa

a n o x o -

xajioreHOBOAOHHKa, TeM-

n e p a T y p a HT.Ä., KOJIHKO h e ce XHAPOKCHJIHHX r p y n a 3 a M e m m i xajioreHOM; Ha np.: CH2 • OH I + CH2 • OH

HBr =

eTHJieHrjIHKOJI

HCl =

I CH2 • OH

y

He

p e a y K y j y h H .

I C H • CI

+ 2 H

2

0 .

ÄHXJlOpXHÄpHH

ÄejcTByje

Tano

0 ,

I C H 2 • CI

rjIHUepHH JOAOBOÄOHHK

2

CH2 • O H

I " CH • OH 4 - 2

H

+ H

eTHJieHÖpOMXHApHH

CH„ • OH

Beh

C H 2 • Br I CH2 • O H

Ha BHineBajieHTHe ajiKOXojie caMO ecTepHijMKyjyhH,

niHiiepHH

npejia3ii

npeKO 1, 2, 3-T p H j 0 A n p 0 n a H a

H30np0nHÄj0AHA. CH20H

CHOH • CH2OH +

CH2J • CHJ • CH2 • J + .

Cmwno

npejia3H

HJ =

2 HJ =

qeTBopoBaaeHTHH

Ma HHT

y

CH2J • C H J • C H 2 • J + CH3 • CHJ • CHs +

ajiKoxoji

e p HT p HT

BajieHTHH

ajiKoxoji

2 - x e K C H JI j o Ä H Ä.

HanncaTH

c e JI H H e

c y HapaBHO n p H C T y n a m e OBHM peaKunjaMa.

3

y

OBO

MOM H jOÄOM;

BHUie

nocTyna ce y

LUTO c e

MeuiaBHHa

y peaKUHjH, jieBKa

uiTa

THMe

3a paBajaH>e

AOAaje

Me^yTHM

2

0,

2-joAÖyTaH,

JEÄHAQHHE!

Ä p y r a peaKUHja Teqe KyAHKagio eueprHMHHje OÄ npBe, HàpoqHTo yje 6p'óMHOTHM cjiyqajèBHMa TaKo, Äa c e OBaj CTBapa Ten

a JI K o x o JI.A

H upBenor

(J)oc({>opa

HJIH H3

6poM y KanHMa, n a n Kao T o p e , AOAaje (JJHHO cnpameHH j o f l .

ripaKTHKyM opraHCKe x e M H j e

6

H

82

OpraHCKO-npenapaTHBHH .neo

I, 1 h 2

OBa peaKUHja Moate .na ce npHMeHH, nao h npBa, Ha bh uieBajieHTHe nao h Ha c y nC T H T y H c a H e aJiK0X0Jie, h to Mory c b e OH-rpyne aa ce 3aMeHe xaroreHOM, h xjiop o m TaKotje. Ha

Meero

CJiynajeBHMa

(JiociJjopTpHx^opH^a

qBpcTH

neHTaxjiopafl

p a T y p n h Kojn HMa eHeprHHHHje aíiKOxoJia

ce

ynoTpeójbaBa ncnapaBa

kojh

y

AejcTBO. O b a c je noTpeÓHO

MHT3B mojí P C 1 5 , nouiTo

peaKUHja

mhothm

Ha BHinoj TeMneHa 1 mojí

ao CTBapan>a mhoto

boah

HHepTHujer 4 ) o c < | ) o p o K C H X . 7 i o p H ^ a , Ha np.: CHS •C H HOBHje

y

OH +

2

BpeMe

PC15 =

C H 3 • CH2C1 +

ynoTpeójbaBa

ce

3a

POCl8 +

ncry

HC1.

peaKiinjy

thohhí-

x ji o p h a ; oh H M a t o n p e H M y h c T B O iiito cy K>eroBH n p o A y K T H

peanuaje

racoBHTH, n a He CMeTajy n p « n p e p a A H peaicunoHe CMeuue. C4H9 •C H

OH +

2

SOCl2 =

C4H9 • CH2C1 +

aMHJiajIKOXOJI EHeprnqHHje

AejcTBO

A a ce no3Ha, uito

eHe xajioreHHMa: C6Hs • O H +

PC16 =

(fceHOJi

(Br)

C 6 H 5 • C1 +

POCI3 +

(Br)

(Br)

HC1. (Br)

npnHOCH cy OB^e mhoto Maifee 3aAOBOJbaBajyhH, noniTO $oc(j)opoKCHx a o p H A ^ejcTByje 4>opHe

Ha jorn HepearoBaHH (})eHOJi CTBapajyhH

KHcejiHHe,

ecipe

(J)oc-

Ha np.:

POCl3 +

3 C6H5 •O H =

P O • (OC6H5)3 + 3 HC1.

MeTO.ua 3a Aofínjaite M e T H ^ j o A U A a

Koja je rope o n n c a H a ochhb3

ce Ha A Q O C T p y K o j h 3 m c h h n p e M a jeAHaqHHH: /OCH8 02S< + K J \ O C H s ^

/ O K -

MoHoajiKHJixajioreHHAH y BehHHH cJiyiajeBa h MeTHJiópoMHA racoBHTH,

Aajbe

t o cy

O

4

X

CnH2n

tchhocth;

+1

C1

(Br, J)

H3y3eTaK

n a o h eTHJixjiopHA, Kojn cy BHcoKOMOJieKyjicKH

+JCH

\OCHs

.

cy

iHHe

Ha

q^aHOBH

3

6e36ojHH

oÓHHHoj

Kao

Ha

h

MeTHJix./iopHA TeMnepaTypH

np.

ueTHJijoAHA

C 1 6 H 3 3 J Kojn npeTcraBjba nojiyiBpcTy Macy, cjiHHHy MacTHMa. Ohh ce

necTO

HenpaBHJiHO

jOAMeTHJI, ÓpOMeTHJI. jOAMeTaH. jioreH

joHoreHo

CBe nokpeTJbHBHjH.

xa^oreHajiKHjin H a np.

Ha CBOM M e C T y je H33HB

Be3aH

h

y

HH3y

e c t p h m a.

xjiopha-6pomha- j'oaha

oh

Xaje

K a o ecrpH. a^KHJixa^oreHHAH ce canoHH H2C =

OTuenjbHBaibe

KaflHjyMXHApOKCHAa

TepuHjapHe

6a3e,

nao

o^e(j)HHHMa.

CH2 +

HBr.

xaaoreHOBOAOHHKa 1

;

y

noMohy

ajiKO-

h c k h m cjiyqajeBHivia y 3 H M a j y

n h p h a h h,

xhhojihh

hjih

ce

ahmcthji-

a H H JI H H. Oa Beh

je

npeMa

peaKUHja noMeHyTa

H.

KHCCJiHiie

OBe

peaKUHja

nojia3ehH

Kolbe-y,

CHpheTHe peaKUHja

ajiKHJixajioreHHAa h>hxob3

BpcTe

oa

(ynop.

HaBeuiheMO

ce n p H M e i t y j y

Koje ca

MeTaHCKor npenapaTe Würtz-osy

3a

ch ht e3 e

KajiHjyMijHjaHHAOM peAa

nocpeAyje y

II, 5 h V I , 7 ) . O a c h h t e 3 y.

npocTnjnx

MeTa^HH

T p h j y m OAy3HMa x a j i o r e H h3 A s a MOJieKyjia, h o 6 a ce MeTHJiHa MeijycoÔHO

Beacy.

Ta«o

y HajnpocTHjeM

cjiy^ajy

HacTaje

h3

Koja,

chhtC3h Ha-

ocTaTKa

Memflôpo-

MHAa e T a H : H S C - Br Na 1

Br • C H 3 - * H 3 C • C H 3 +

2 NaBr

Na

Oßaj peaKTHB koj'h ce MHoro ynoipeöjbaBa

najöojbe ce npHnpaB.ta t3ko, aa ce y

100 ml MeuoinajiKoxoAci (eTHJiajiKoxojiHH pacTBop Ka jiHjyMxnnpoKcn.ua 6pao npe;ia3H cMOJiy) pacTBopn, 3arpeBaHieM hjih CTajafteM npeKo hoHh Ha xjiaano, 25 g Ka^HjyMXHflpoKCHaa y uiHnKaMa, oueiui oa KapôoHaTa H TmpauHjoM oape/w KOHueHipaunja K O H . 6*

y

OpraHCKo-npenapaTHBHH neo

84

ripenapaTHBHa X ^ o p M e T a H a,

7.

OBe

peaKUHje

Haj3a,A;

Ha;ia3H c e

ÖHTA r o B o p a

AOUHHJE

(B. I X ,

OBFLE

xa^oreHH^y

HCTOBPEMEHO

OÄy3HMa

Br +

CENG •

H JE^HOM

xaaoreH

H3B3H-

ea KU Hjy

o Kojoj

2

Wiirtz-OBE CHHTE3E no T O M e ,

APHJIXAJIOREHH/JY

H3TpnjyMOM

Br +

C2H5 •

AOÖHJIH

1).

Fittig- O B A C H H T e 3 a 1 p a 3 J i H K y j e ce O Ä IIITO c e

p

T p H (J) e H H .JI-

KO A

AJIKHJIXAJIOREHH^H

cy

3Ha»iaj nao NOJIA3HE c y n c r a H i j e 3a rpuwapoBy

peaaH be

nprnueHa

B. V I ,

Ha

Na

HJIKHJI-

H JE^HOM

np.:

C6H5 • C2H5 +

2

NaBr

ETH^6EH30JI Oßa Moaore

HMS o n m T H

PEAKUHJA

nao

6 P 0 M 6 E H 3 0 A A

A^KHJIÓPOMH^E. PEAKUHJE, MA AA

H

y

ÖPOMHÄA

ÄOÖHJA

TCPMHIKHM

TAKO

JE^HOCTABHO

(Aeree ,

Moryhe

ÄOJIA3H

ÄO

ÄEXHÄPHPAITEM

PAÄOBHIWA

y

PEAKUWJY

ueß).

Kao

UITO

Schiubach )

2

HATPHJYMOBO

HacTaje

OBO CAAA C T y n a

Y3

xo-

2 NaBr.

iteroBe nape KPO3 ycnjaHy RB03AEHY

HOBHJHM

4>A3H

H H K a. T e K

H HA

H CBE

APHJIÔPOMHAA

2 Na - * C6H5 • C6H6 +

peaKUHja HE TEQE

JEÄHAQHHE.

npBoj

A N 6 P 0 M 6 E H 3 0 ; I

MO^ENYJIA

npenaparaBHo

ce

(NP0B0ÄEHH

E

1. R • Br + 2 Na - > RNa -F- NaBr, 2. RNa + B r R ' -»• R — R' + NaBr. AJIH

KAKO

HATPNJYMOBA

roBe R —

CHHTE3E R

ôpœe

eTHJiöpoMHÄOM

PA^Y

Tpeöa

H;IH

Ilpn

3a Y B O ^ e a e )

Hero

ÄA

ce

H3pa^H KOJH j e

H Fttiig,

H3öeraBajy OBOR

Tollens

A m . Chem. Journ. 29, 588 (1903).

5

H8

a

H

o6a

cy KOÄ 0 U Í S U -

a a

Ha CJI.

46

anapaType

cnyacuMO H y

ce

KOMe

npeKO

n^yxe

ÖAJIOHOM® ce

3arpeBa

(ca ÄO

A . 131, 303 (1864); y n o p . 22 H3Ä. OBor aeaa, CTp. 111.

BHÄH TaKolje pan Schlenk-a, B. 50, 262 (1917). A. ch. [3] 45, 468 (1855); Beilstein H Gettner, A. 139, 332 (1866);

» B. 55, 2889 (1922); Schramm,

6p0MÔeH30Ji0M.;

npenapaTa

npuKa3aH

1

Cannizzaro,

ca

6 p o Mo M

2

1

TO

eTH^6eH30Jia.

c a x j i o p O M ,

KHcejiHHOM

ueBM

HATPHJYMOM,

R'Br,

Moryhe 3 p e a K i t n j e ca n p o a y K T H M a R — R ' ,

3. BEHSHJIXJIOPHFL

KaynyKa.

ca

RBr

p e a r y j e ' c a H S T p n j y M O M ö p a c e OÄ e m n ö p o M H Ä a ,

ca

jiaKO c T B a p a i t e

NPH

NPBO

R'.

Bp0MÖeH30^

npHMepy

pearyjy

Mory AA p e a r y j y ca

NPHHUHNHJAJRAO

H R' —

HaTpnjyM

RBr H R ' B r

H

JEÄHH>ETT>A

B . 18, 608 (1885). ripaKTHKaHT he ra ÄOÖBTH OÄ acHctcHTa.

CynciHTyuHja xHapoKCHJia h RonoiuiKa xajioreHOM

85

KynaTHJiy. l l p e Hero I U T O TepMOMeTap qnjH £ O H > h A E O noiHBa y jeAHoj cTaKJigHoj ueBqnuH I I Y J K H H E 3 A O 4 cm Koja je y cpe^HHH cyaceHa, H Koja c^y®H nao n o f l a o r a ,n;a TepMOMerap He cTojw AHpeKTHo Ha A H Y 6ajiOHa. KpajeBH oBe ueBHHije Tpeóa A A cy 3 A O 6 J B E H H &a He 6h 3 a n a p a ^ n A H O 6ajioHa. Kpo3 C R A K J I E H Y ueB Koja N P O A A 3 H Kpo3 dpyuieHH q e n yBOAH ce H3 qejiHHHe ó o u e jaica cüipyja xjiopa Koja npeTxoflHo MOpa Aa npoije n p o 3 Hcnnpa^HUY ca H 2 S 0 4 . X-rcop ce yBoan CBe aoivie A O K T e M n e p a T y p a y TENHOCT Koja » H B O K J B Y Q A H E A O C R A R H E 1 5 6 ° . T O P A N Kpaj ueBH K0HAeH3aT0pa Be3aHa je ca peuHnnjeHTOM y KOMe ce Ha;ia3H pacTBop HampujyMxufípoKcuna y KOMe ce a n c o p ó y j e BHiiiaK x a o p a . U,eB Koja O^BOAH xjiop H E T P E 6 A « A je Y P O H B E H A y p a c T B o p H A T P W J Y M XH^POKCHAA. H C K Y C T B O je N O K A 3 A . N O A A Tpaja&e YBOFJEIBE xjiopa 3 3 B H C H OA OCBETJBABAIBA;1 peaKijHja je npH jaKoj C Y H Q E B O J cBeiviocTH 3aB P M E H A 3A HCKOJIHKO QACOBA, A O K 3 A B P E M E M Y T H H X zana Tpaje H nojia AAHA. 3 6 o r Tora ce Tpeóa Y N P A B J B A T H , Y K 0 J I H K 0 je T O Moryhe, npeMa KJBYNAIBA

ce cnna

100

^

QHCTOR

TOJIYOJI,

CT3BH

iüojiyojia

ce y

HA B A 3 F L Y N I H O M

óanoH

K

pa

T

a

K

OCBET^>EFT>Y,

Ca^pacaj óajiona ce 3 3 T H M H E N O C P E ^ H O A E C T H J I H M E y BaKyyiny. riocjie npBor TOKa KojH ce cacrojH H3 HenpoMeibeHor Tojiyojia xBaTa ce rjiaBHa KOJiwqHHa y rpaHHuania OA 7 CTeneHH (Ha 12 mm OTnpn^HKe H3Meijy 63—70°). ÍLPHHOC

TAQKA

KJBYQAH>A

6 5 — 7 0 %

npenapaT H ayate

ce

KOJ'H

Apwn,

npHTHCKOM,

CKHM HNQHE

aejcTBy

y6p3aBa

jih

nOIIITO

AECTH;IOBATT>EM

npenapaT

npH

TOMe

Koja

AOJI33H

y

KOA

64°/12mm.

BANYYMY

^ecTHjiOBaH

je flO

KaTajiHTHWKH

xjiopMeTaH.

je

OTIienJbHBaifea

je

HHCTHJN

noA

aTMOC(J)epXflOpOBOflO-

HCTO

oHaa

Kao

na

5),

6

e

H 3 HJI I N A ^ o H C K H

H peaKUHjy

cacrojH

c e x a j i o r e n y o e n é Ha M e c i ó BOAOHHKS

3acwheHe

yr;b0B0.ii0HHKe.

cje.aHH>aBan>a

OBaj y r j b 0 B 0 f l 0 H H K n p e j i a 3 H

y

x;iopa

MOHO-,

OBy

peaKUHjy

CBeui0CT

c a BOAOHHKOM. AH-,

T p H-

AKO

ce

H T e T p a-

M BHLUH napai{)HHH M o r y T a K o i j e Ha O B a j HaqHH a a c e x j i o p y j y , ajiH n o c i y -

JIH»JHTH peaKUHOHH n p o a y K T H

yonurre Hajnpe

Y

(II,

P E A K U H J Y .

xaJioreHa

npenapaTHBHo He3roaan

ns xaop

H 3 H J M N J A H H A

HajjeflHocTaBHHja M e i o a a m

c;io6o.aHor

y 3 M e MeTan H x a o p ,

HHKy.

JIEACH

KHCE^HHE.

TeopncKH

naK

óeHaujixjiopuaa

je npeiHiuheH

Hero

Jlajba N P N M E H A 3 A 6 E e c T a p ( V I , 7 ) , rpuwapoBy ce y

QNC-ROR

TeopHCKor.

OA

napa(})HHCKOM

CTyna pe^y

H HMa

Ty j i o r n y

cipaHy

UITO c e

HCTOBpeMeHO C T B a p a j y

K o j n c e T e t u K o o M a j a j y jeAHH OA a p y r n x .

Ha

OHaj

a^KoxojiH

yrjbeHHKOB aTOM

KOjH

je

nocTojn

pa3-

npaBH^o

HajcHpoMauiHHjH y

BOAO-

KojH c y n p H C T y n a i H H j H y HHCTOM CTan>y o a

yrjbo-

BOjtoHHKa, MHHe HCKJbyHHBo nojia3HH MaTepiija«, npeMa npHMepy 1 H 2, 3aflo6njaH>exajioreHCKHX jeflHH>eH>a. MHoro ce nperjieiiHHje jiemaBa npouec cyncTHTyuHje x^opoM kor TÓJiyo^a H xoMo^ORHX MeTHfl6eH3o^a ( K c m i o j i a HT.j.)- OB^e HMaMo ABa ouiTpo o^BojeHa npoueca. 1. ys noMoh THnHqHHx npeHOCHoua xa^oreHa, nao IIITO cy onHjbUH r e o n t ^ a , j o a, cyncTHTyuHja ce Bpiun HCKJbyiHBo y je3rpy, H TO H3 ronyona HacTajy o- H /7-aepHBatH jeaaH nopen apyror. 1

B. 59,

G . Book 153

(1926).

H J.

Eggert,

Ztschr.

f. E l . 2 9 , 5 2 1 ( 1 9 2 3 ) ;

B . 5 9 , 1 1 9 2 ( 1 9 2 6 ) ; F.

Berget

86

OpraHCKO-npenapaTHBHH

2.

B e 3

Äeo

j e ü H o r OBaKBor npeHOCHOua, na i a K H Ha TeiunepaTypH K j b y q a a a , 6eH30Ji0B0

j e 3 r p o o c T a j e noTnyHo HeanpHyTO.

Bp3HHa c y n c T H T y i w j e MCTHJIHG r p y n e

( ö o i H o r HH3a) Ha

xjiaÄHO j e ôecKpajHo Majia, ana ce ca noBHiuèfteM TeMnepaxype noja^aBa y T o j Mepn, na j e 3a npenapaTHBHe

CBpxe

ÄOBOJBHa, j e p

CHCBHM

ce

npeMa

o n i i n e M 3aKOHy npn

T e M n e p a i y p e 3a 10° 6p3HHa peaKUHje noBehaBa 2 — 3 n y r a . Ha

cBeTJiocT

nao

cBe

H

peaKuwje

KOÄ

Kojnx

ce

O ß a peanuHja j e

BpuiH

noBHiuefty

oceTJbHBa

jiHpeKTHa 3AMEIIA BOÄOHHKA

x j i o p o M . n o r p e i i i H O j e c x B a T a a e , na 6H AOAABATBE (J)oc({)opneHTaxjiopHfla aejcTBOBajio yóp3aEajyhH. PeaKUHja H3Meljy T o j i y o j i a H x j i o p a n p y w a Bpjio Jien npHMep 3A cneuH o M

CKopo caB x a o p p e a r y j e ca npHcyTHHM TOJiyojiOM

na C T y n a a e

3Hawaja

6P3HHOM,

í p y r o r

aTOMa

Hero npBa 4>a3a p e a n u n j e .

Tano

npe H e r o UITO nan>e xjiopoBaH>e 6eH3HJi-

xflopHÄa Äolje BHÄHO ÄO H3paiKaja. CyceÄCTBo 6eH3o;ioBor je3rpa

j i a j e x j i o p y y 6OIHOM HH3y MaH>y i B p c T o h y

Be3HBaifaa,

T.j. Behy noKpewbHBOCT, Hero y c j i y q a j y MHCTHX napaHHa. T o ce o6jaiiiH>aBa THMe, na 6eH30JIOBO j e 3 r p o on MeTaHCKor yrjbeHHKa y3HMa 3a c e ö e BHiue e n e p r n j e Be3e, H e r o JIH aJiKHJi HJIH

BOÄOHHK,

pacnoÄefle Be3yjeMO

H

3öor Tora x j i o p y o c T a j e OÄ oBe B.e3e MSILC Ha p a c n o j i o ^ e a y

M

a^HHHTeia Hauie

OÄ

e Äa H3 KpaTKHX $ o p M y j i a n p o i H T a BHUIC, Hero

HITO My jeÄHOJiHMHO Be3HB3H>e nojeÄHHHX aTOMa MOHHM H30MepHH. MOÄCMO y o n u i T e Äa KaweMo, Äa c e npoMeHe Ha MeTHJiHOj r p y n n Tojiyona H aHajioro rpaljeHHX jeÄHH>eH>a ÄeuiaBajy y cyuiTHHH HCTO Kao H KOÄ MHCTO aJiHaTCKHX aJiKajiHHX r p y n a . NPH

npoÄy«y x j i o p o B a i t a Tojiyojia yjia3H y ÖOIHH HH3 Ä p y r n , H HanocJieTKy Tpehn

aTOM x j i o p a . B e E B a j i x j o p H i

C e H 5 • CHC12

je

6e36ojHa TCIHOCT,

Koja Kao H 6eH3HJixjiopHÄ,

H333HB3 c y 3 e H npeTCTaßjba TCXHHIKH nojia3HH MaTepwjaJi 3a ÄOÖHjafte

6eH3ayiÄexHÄa

Y n o p . npen. V , 3. BeH30TpHXJI0pHI yraipj

^eH30Ji0B0r

((JJEHHFLXÄOPO^OPM) C 6 H 5

je3rpa

Ha

OHHrjieÄaH.

J\OK j e x^opoijjopM npnjiHMHO pe3HCTeHT3H

TpHXjiopHÄ

H3BaHpeÄHo

KHcejiHHy.

riorpeuiHO

flaKO, 6H

OÄBajajyhw

6HÄO

CC13.

0ÄH0ce Be3HBaH>a cyceÄHHx yrjbeHHKa OBÄC j e BeoMa

BepoBa™

CBa

npeMa ajiKajmjHMa, ÄOTjie c e 6eH30-

3 aTOMa x ^ o p a ,

canoHH4)HKyje y

6eH3oeBy

Äa ce iipn TOMe caB x ^ o p HCTOBpeMeHO H3ÄBaja

npeMa jeÄHaiHHH: /CI NaOH /OH C6H5 • C T - C 1 N a O H - > C6H5 • C ( - O H + \C1 NaOH \ 0 H

/OH 3NaCi

C ß e c e xeMHCKe p e a K u p j e OÄHrpaBajy n o c i e n e H O ,

C 6 H- 5 • C L

+

H20 .

^O H TO Hajqeuihe H3Metjy 2 Mo^e-

Ky^a (peaKUHje Ä p y r o r peÄa H JIH ÄHMOJieKyjicKe peaKUHje). T a n o MOHCCMO H Harny peaKUHjy Äa pa3jio5KHMo y napunja^He n p o u e c e H Äa npeMa TOMe (JiopMyjiHuieMo: C6Hs

/CI Cc-Cl +NaOH \C1

/OH C6H5 • C ( - C l +NaCl (I)\CL + NaOH

+NaCI+H

2

0

+ NaOH

^ O C6H5 • C f (II) NCI

^ 0 > C6H5 • C ^ o H + N a C l .

87

CyncTHTyuHja XHÜPOKCHJIA H BOAOHHKS XFLJIOREHOM

Me^ynpojiyKTH (I) H (II) ITOJIJIOJKHH cy MHoro 6p«oj canoHH$HKaiiHjH ca ajiKajiHjaMa Hero nu 6EH30TPHXFL0PNA. Oiy.ua ce OHH H He nojaBJbyjy. 3a MeljynpoÄyKT

(I) Tpeôa

na c e n p a M e r a , na je,nHH>eH>a OBe BpcTe Koje Hoce

joui

XHAPOKCHJI H XHJioreH Ha HCTOM yrjbeHHKOBOM aTOMy He Mory «a nocToje, Beh OAMax n p e Tpne H3MeHy. \

/ O H

'

p C ^

- > ^ > C = 0 + HCI.

Cl OrJieji;: paciïiBopoM

HCKOJIHKO

Karm

KajiujyMXiiapoKCUM

KYNATH^Y

a3omnoM

cpeâpoHumpama.

AHajior 3aHor

c a ÛMCOXOJIHIIM BOA^HOM

pacw-Bopa

xaaoreHa) y

ce

Ha

HepacTBopeHH

(6e3

KyBajy

HEKOJIHKO MHHYTA. T S A S c e p a 3 6 j i a j K H BOÄOM, 33KHcejiH

KucejimoM,

AGO H 3 M y h K a y

eìiìpy

o r j i e A c a HHCTHM 6p0MÔen30Ji0M

ÓpOM-jOH.

K333TH

6en3ujixji0puaa

Pa3JIHKa

H3MEÍJY

enpyßeTH

H

AOAA

(HAYHN

3JIH(J)aTCKH

Kann

H6KO./IHKO

n p e n a p a T ) Hehe

no-

3pOM3TCKH

Be-

OApe^HBaibe

xa-

H

xajioreHa. A H a .A H 3 a

jioreHa y

c e n o Kapujycy uenaaeM

y

ca

0Apel)eH0r Tpeóa

KßaHTHTaTHBHo

6EH3HJIXÍOPHFLA,

c y n c T a H i j a M a K o j e campine a./iH(|)aTCK0 Be3aHH x a j i o r e H He H3BOAH 3aTonjbeHoj

u e B H ( y n o p . CTp. 58), B e h p a c T B o p o M

AJIKOXOJIHHM

THTpa.

ÍIOIUTO c e

ce HayqH

He caMO

OBa

MeTOAa

XHAPOJIHTH^KHM

KAJMJYMXH^POKCHJIA Bpjio

necTO

KaKO c e n p e n a p a T

Aoönja,

npHMen>yje,

TO

H Beh

ce

Rano

BpuUH KOHTpOJia. y

je^HOM q e i i i h e y n 0 T p e 6 j b 3 B 3 H 0 M

Ay>Ke B p e M e

yBoijeHa

6eu3ujixji0pufla

(OKO

1

ca

g)

(1

caT ca y c n p a B ^ e H H M

K0HAeH3aT0p0M,

BHtuaK

1/2

NPHÓJIHIKHO

HaïïipujyMxuapoKcuaa BOAe H T H T p n m e

MSJIOM ö a j i o H y , y K o j e M j e p a H a j e

BOAeHa n a p a , K y B a c e nyTa Beha

TaqHO N/1

H3MepeHa

KOflHHHHa

ÜJIKOXOJIHUM

pacwBopoM

Ko^HMHHa

OA H 3 p a q y H a T e )

pa36jiajKH AßOCTpyKOM

X H A p o K C H A a c a n¡2

jeA3H

3anpeMHH0M

COHOM mcenunoM

y3

A0AaT3K

4)eHOJi4>Ta^eHHa. Oßa ce MeToaa HapaBHo Mo>«e caMO OHaa na npHMeHH, ano He HacTajy HiinanBe apyre KHcejiHHe. y TOM cjiyiajy THTpniue ce xajioreH ca p o j a ' H H i o M 4. Ca

CPEAHHE BPATA

ueB Koja je n p e K o ropnbeM Kpajy C3CT3BiíHMa j e

Bpjio

OA 1/2 JIHTPA cacTaBKa y

óa^oHa yMBpinheH

CT3BK3, JieBaK 33 l o n a i t e

Be3H

6poM

6e3

napaa HBr, H p e r y j m m e ce A O B O A ôpoMa T A N O A a peaKUHja Tene > K H B O , ajiH Aa He nocTaHe óypHa. A K O peaKunja npeA Kpaj nocTaHe c n o p a , 3arpeBa ce joui KpaTKO B P E M E Ha B O A C H O M K Y N A R A ^ y A O K ce caB ô p ' o M He y t p o u i H .

Ca. 46

Ca. 47

T a ^ a ce peaKUHOHa cMerna AecTHJimue ca B O A C H O M napoM H 3 jeAHor Beher óajiOHa. M H M ce y K0HAeH3aT0py noiHy Aa H3Aßajajy KpHcra./IH p-xuôpoM6eH30Jia, H3MeHH ce peuHirojeHT, H cnopeAHH npOAyKT nomyHO npeAECTHJIHUIE.

Bp0Môen30Ji Kojn je Hajnpe npe^ecTH^Hcao, noiiiTo ce c á e m e , O A B O J ' h ce y jieBKy 3a OABajaite, cyuiH 1 caT ca KcuiifujyMXJiopuaoM H Ta^a AecTHa y j e . OpaKUHja Koja npe;ia3H H3Me^y 140—170° Aaje n p n noHOBJbeHoj AecTHJiaQHjH y r j i a ' B H O M ACcrajiaT KOJ'H npe^a3H H3Meljy 152—158° H npei - CTaBjba N P H J I H M H O I H C T 6p0M6eH30Ji; npHHOc 7 0 — 8 0 g. 3a AOiXHHjy npwMEHY K O A rpuwapoBe P E A K I J H J E (B. I X , 1) Mopa npenapaT joui J ' C A H O M A a ce (JjpaKUHOHHLue y yacHM rpaHHuaMa. H H C T O j e A M b e a e KJbyqa Ha 155°. p-J],u6p0M6eH30Ji. OcTâTaK, K O J H je 3aocTao y óaAOHy K O A npBe AeCTH^aiiHje, H3Jinje ce joui Bpyh y Majiy nopuejiaHCKy iuojby, H no o^BpuihaBaity 3ajeAHO ca npoAyKTOM H3 AecTHJiaunje c a boachom napoM O C J I O Ö O A H CMOJia, O A H O C H O ocyuiH Ha rjiHHeHOM Tan>Hpy. RIP« TOMe ce cyncTaHua He cine uinaiyjioM na yracKyje y rjniHy, Beh ce craBH H a a K o npHTHCHe — OBO BawH 3a cBe onepauwje Here Bp cíe — npn neiny ÄOJia3H ÄO nyHor H3pa»íaja ocoöHHa rjiHHe sa ycHcaBa Bjiary. JaKo CMOJiacTa cyncTaHua nocae BmiiewacoBHor CTajaiia no«HrHe ce mnaTyaoM H npeHece Ha Heno joui HeynoTpeôjbeHo Meció Taanpa.

riocjie cyuieaa npeKpHCTa^ume ce p-au6p0MÔeH30Ji H3 Majio amoxona H Ä o 6 n j y AHBHe 6e36ojHe npH3Me. TaHKa Too/beita 89°. B p O M O B O A O H H K n a o c n o p e A a H n p o j i y K T , IlpH peaKaujH HacTaje 80 g HBr 3a q n j y je a n c o p i m u j y N O T P E Ó H O O K O 200 ml B O A C CTora ce Mopa, aKo peu«nnjeHT HHje AOBOJbHe Be^iHHHHe, Aa oÖHaBjba

CyncTHTyuHja xtuipoKCHJia H BOAOHHKS xajioreHOM

caapjKaj

peuHnHjeHTa,

MHM n o ^ H e

npenmiihaBa

ce

mcejima Kojn

nojaBjbyje Marjia.

AecTHJiaunjoM

CT3BH KOHAeHsaTOp

ce

Aa c e

ca

89

H3 ó a j i O H a

19).

BOAOM (CJI.

3a

BpoMOBOaoHmna

(J)paKiíHOHHcaH>e

noqeTKy

y

Ha

AecTHAHiiie

BOAa, a 3aTHM c e Tanna KJbynaifca noAnrHe Ha 126°, H na TOJ' TeMnepaTypH npe^a3H 4 8 % - n a KHCCJIHHH Koja y JiaóopaTOpHjH CBar^a hms AOCTa Tano ce

MeHe.

Ha np. Moace

noTpeóaH 3a Ao6Hjaii>e npocTpaHOM cyAy MHHe

H3 H>e Aa Aofínje

ajiKHAÓpoMHAa

H3BpuiH

npn-

KojH je

KamjyMópOMua

y jeAHOM

.Ha T a j H3HHH, HITO c e

HeyTpajiHcaibe AOAaBaH>eM H3paqyHaTe

KOAH-

üowauie. JeflHO

npHCTynaqHe

KOPHCHO npaBH.no 3a THKBC onepauHje: MaTepnje

—

OflBcjHMo Ha CTpaHy

6p0M0B0A0HHiHy

OB«e

MajiH a e o Te>«e

K H c e j i H H y — aa

He 6H CMO

aoui^H y HenpHJiHKy y c;iyqajy aa npeKopaiHMO HeyTpajiHy Ta^Ky. Orjie^: H3ABaja

HHCT ópOMÓenaoji

npH

KyBafty

ca

He

KajiüjyMXUMpoKCUMOM

ópoM-joH.

Xa;ioreH

je

Ha 6eH30Ji0B0M

je3rpy

Bp^o MBpcTO Be3aH; a p o M a T C K H

H H a H He a a j y KapaKTepHCTH'ine peaKUHje aKHJixa;ioreHH.na.

xaiore-

CaMO KaTajiHTHqKH noóyf^eiiHM

HJIH nacueHTHHM BOJIOHHKOM cnawHor aejcTBa (HaTpHjyM y ajiKoxo;iy) M o x e xajioreH aa ce 3aMeHH, a

TaKofje

H ca

MarHe3HjyMOM

Mory

apHJixajioreHHan

a a c e a o B e a y a o peaKUHje

(npenapaT I X , 1); aajbe acwia3H a o oTuenjbHBaita xaJioreHa Koa HX H

ce

KOJH

oójacHH

je

ca

xaaoreHOM y

ce

o6a

Be3aH

h

OBe

BpcTe

Be30M,

HMajy

npHHUHiiHjejiHa

caApJKH TOK

Be3aHor

n a p a -

c y n c T H T y i j H j e Aa c e

Bpjio

pa3^HKa

H e

noBehaBa

ce

noiino

yrjbeHHK roBope

( B . III, 2 )

ca y

Ha HCTH

6HTH n p e A M e T

Hajnpe ce

ABocTpyKoj

aAHpa

Be3H

Be33Hn

xjiop.

x a j i o r e H O M

H KOA

ABOCTpyKOM

npHjior

y

6 e H-

3aMeHa

BOAO-

peaKUHje

KOA e m r c e H a

Pa3JiHiHTe

o - x j i o p -

H

BpuiH A w p e K T H a

6eH3HJix.nopHAa BepoBaTHa, 3a

xajioreHa

n o ; i o ) K a j y ;

npHJiHHHO J i a d a B O

cn0C06H0CT.

6poMy

c^yqaja

Ha a K T H B H o j

apoMaTCKH

npHHiíHiiHjejiHO

npeMa

Hh Ka KB a

npeTnocTaBKa,

peaniíHOHy

AOUHHje 6HTH p e q n noHaiuaite

Aa

o p i o -

Majio j e

Ha y r j b e H H K y c a A B O C T p y K O M

xa.aoreH6eH3o.fla.

CTBapatt>a

KOA

HapoqHTy

y

j e 3 r p y ?

MeTaHa H x j i o p a BOAOHHK

t3ko

KHCCÍHHU Aa

3OJIOBOM

xaJioreH

CH 2 ,

x a ^ 0 r e H 0 J i e 4 ) H H H

CIIOCO6HOCT

H H T p o - r p y n a M a 6 e H 3 o e B a

HMajy Aa

HC = Br

H

H3Meljy

He H a j i a 3 H M O A a Be30M

uatt>eHHue TOMe, Aa

o

hm3 HeKy KojHMa

6eH3oa

ha^hh K a o H e T H JI e H H H j e HAyher

he

npenapaTa.

6 p o M Ha A s o c T p y K y

0Ae B r C H

2

—CH

2

n

Br;

\

=

/ H

=

H

H

H ^ n \ HBr

n

SH /"• HBr

AAHUHOHH npo^yKT ETHJIEHA je 3acnheH, AOK je HanporaB AAHITFIOHH npoayKT 6eH3o^a jaqe H e 3 a c n h e H Hero caM 6eH30.fi, noiiiTO je nopeMeheHO CHMCTPHHHO H3jeAHa*ieH>e BajieHUH (Thiele), AaKJie noHHiirreHa je „apoMaTCKa" npHpoAa. Ra 6H ce OßA oneT ycnocTaBHJia noTpeÖHo je caMO AA ce H3ABOJH

ÖPOMOBUÄOHHK,

UITO

ce

AEINABA

CNOATAHO

y3

ocaoöaijaibe eHeprnje, H TO TAKO H3B3HPEAHO BCJIHKOM 6P3HHOM, Aa Apyra aKTHBHpaHa AßOCTpyKa Be3a HeMa BpeMeHa Aa aAHpa 6poM. H

H

H

H E N > A OÄBHJA.

JXa

KOA

„6eH3o.7IAH6POMHÄ"

H3MEIJY

6EH30JIA

cyncTHTyuHje

no3Haje ce no HHTCH3HBHOM B A A E 6eH30Jia ( B . I I I , 2 ) .

+

HBr.

B r ~ H

M O I V I O 6 H ce IIOMHCJIHTH H H A

npoÄyKT.

H

3 A N C T A Hacraje K a o MeljyCTBapaH>e j e A H o r MO-

npHMapHo

H 6pOMa

6eH30Aa

a A H np0Jia3H0M

npeKO

HacTajy

Kora

ce

3AHIJHOHH

PEAKHHJA NPOAYKTH

o6ojen>y Koje npara H H T p o-

H a AHpeKTHOj cyHqeßoj CBCTAOCTH aAnpajy ce xjiop H 6 p o M H TO no 3 MOJia Ha 3 AßocTpyKe Be3e 6eH30Jia H Aajy xeKcaxjiopiiHKJioxencaH H xeKcaöpoMUHKjioxeKcaH ( 6 E H 3 0 A X E K C A X A 0 P H A ) : H

He no3HaTa Ha npHMepy M A ^ E N U C K A KHceAHHa-H. H3paqyHaj kojihko je TeopnjcKH noTpeÖHo ajiK0X0.na 3a OHy kojihqnHy eTH^eHa Koja je noTpeÖHa Aa 6h ce 06e360jH0 ynoTpeöjbeHH 6poiw. Kojoj 3anpeMHHH y jihtphm3 OAroBapa OBa KOJiHHHHa eTHJieHa? A k o ce aHa^H3npa eiwieH AOönjeH noMohy cyMnopHe KHcejiHHe, (MeTOAa?), Haaa3H ce, Aa caApJKH Bpjio MHoro y r j b e H M O H O K C H A a . 3a AOÖHjafte iHCTor raca noroAHHja je MeTOAa ca 4)0c$0pH0M khccjihhom, ajiH Haj6ojbe je Aa ce H3 06pa30BaH0r eTHJieHÖpoMHAa 6poM noHOBO H3ABOjn noMohy ixHHKa y npaxy h raaiínja^He cnpheTHe KHcejiHHe Ha Taj H3MHH, Aa ce eTHJieHÖpoMHA AOAaje y KanHMa y cycneH3Hjy iiumca y üpaxy

OjietjwHH

93

y3eTor y BHiuKy (ajiH He cyBHiue MHoro) y ajiKOxoxy h rjiatfujamo} cuphewHoj mcejiuHu (2 1 / 2 MOJia), h Aa ce rae xBaTa y racoMeTpy HaA boaom. 6.

UHKJioxeKceH

H3

uHKJioxeKcaHO^a.

U,HKjioxeKcaAHeH

100 g i¡uK0xeiccaH0Jia 3 a r p e B a ce c a 80 g ûpuM. KajiujyMcyjiipauia Ha 120—130° (TeMnepaTypa y j b a H o r KynaTH^a). HmnoxeKcen npeAecTHJimue y Tony oa 1—IV2 caTa; oacjih ce o a HeuiTO boac Koja je 3ajeAHO c h>hm npeAecTHjmcajia, h n o c j i e cyiueita c a MJiifujyMxjiopuaoM joui jeAHOM peKTH(J)HKyje. T a n n a K^yiafea 84°. n p H H O c 80 n p o u . oä Teopnje. UHKJioxeKceH1.

UHKJioxeKcen-ÂHÔpoMHfl. 19 g limnoxencena pacTBopa ce y 30 ml xjiopocpopjua, h obom pacTBopy aoas, xjiaAehn ra npu tom jicaom, n a n no n a n 40 g ôpoMa pacTBopeHor y 100 ml x a o p o f J j o p M a . B o j a 6 p o M a Hcie3aBa TpeHyTHO, h Ten npn npajy peaKiinje M O » e as ce AOKaace eno6oahh 6poM ca joAKajiHjyM-cKpoÔHOM xapTHjoM. TaAa ce pacTBapaq npeACCTHJiHine y BanyyMy h AuôpoMua 4>paKUHOHHiue TaKolje noA CMaiteHHM npHTHCKOM. T a n n a K j b y q a i b a 9 6 — 9 8 ° Ha 11 a o UmcJioxeKcaAHeH2.

h 70 g

KynaTHJiy

g.

oa 35 g quicjioxeiccenm^poMum hjih AUMEWUJIANUNUHA 3arpeBa ce y

c a A y r a i K H M B p a T O M , caApjKHHe 2 0 0 ml y yjbaHOM

150—160°

Ha

ripuHoc 4 8 — 5 0

MeuiaBHHa

CBeace ACCTHJioBâHor XUHOJIUHÚ

ö a j i o H y 3a A e c T H a o B a i t e

12 mm.

(TeMnepaTypa

y

ôajioHy).

BajioH

ce

Beace

ca

jeAHHM K0HACH33T0p0M jaKor A e j c T B a Ha KojH c e npHKJbyMH p e u n n H j e H T kojh c e xJiaAH JieAOM. Tpeöa aKUHja

TaAa Beh

Peananja

noiHH>e y 3 n ô j a B y TaMHe 6 o j e .

n o A n h n Ha

JiaraHo npouuia,

joui

180° h ApacaTH j e ,

TeMnepaTypy

nouiTO j e niaBHa

10 MHHyTa Ha 188°. T a A a c e KyrjiHua

MeTpa

noAHrHe H3 t c i h o c t h y

AOTJie

AOK j o u i HeuiTO

napHy

$ a 3y

n p e j i a 3 H Ha T e M n e p a T y p a

pe-

TepMO-

h accthjihuic

A a j b e CBe

100°.

/JecmrcaT

ncnoA

p¿36n. cyMüopnoM mcejimoM, c y u i H c a KCuii}ujyMXJi0pufl0M h Haj3aA noHOBO naacjbHBO (JjpaKUHOHHiue h3H3a HeKOJiHKo KOMaAHha naUipujyMa. OpaKiiHja oa 80 ao 82° npeTCTaBjba A B O C T p y k o h e 3 a c h h e h h y r j b O B O A O H H K kojh caApncH joui 1 0 — 2 0 % U H K J i o x e K c e H a , c e H3Myhna c a

ripHHOC 7 — 8 g; aKo c e y n o T p e Ó H AHMem/iaHHJiHH npHHOc j e HeuiTO méHjH. HHTpaMOJieKjMicKo omenjbHBaH>e Boae H3 ajiKoxojia, HajyoôHiajeHHja MeToaa 3a äoôHjaite 0 n e ij) h h a, He Teie ca kohu. KHcejiHHaMa thko jeaHOCTaBHo Kao ihto n3pa>KaBa jeflHamma:

CH S — CH 2 OH

CH 2 = CH 2 +H 2 0.

Ajikoxóji ce Beh npw ôJiaroM 3arpeBaH>y ecTepH(}>HKyje kohu. cyMnopHOM khccjihhom y e T H J i c y M t i o p H y KucejiHHjr, h tck npHJiHKOM H>eHor pasjiaratfca ciBapa et e t h JI e h. CH3 • CH2OH 1

H 2 S0 4

L. Brunei, Bl. [3 33, « A. W. Crossley, Soc.

C H 3 . C H 2 • O — SO3H - > C H 2 =

270 (1905). 85, 1416 (1904).

CH2-HH2S04.

94

OpraHCKo-npepaTHBHH neo

MH ce cehaMO, AA ce Hajnpe CTBopeHa eTHJicyMnopHa KHcejiHHa 3arpeßaH.eM (130°) ca BeJiHKHM B H ui K o M ajiKoxojia pa3aa5Ke, H aa ce OBHM nyieM jtoönja e i a p . CH3 • C H 2 • O — S 0 3 H + H O • C H 2 • CH3

> CH3 • CH2 • O • CH2 • CHS +

H2S04.

TaKoije H npH ÄOÖHjaflby eTHJieHa Haciaje eTHJieiap Kao cnopejiaH npoayKT. E T H J I C H , „ r a c K O J ' H c T B a p a yjbe", ÄOÖHJIH cy Beh 1795 ROÄHHE neT xoJMHÄCKHX xeMHiapa Deiman, Troostwyk, Bondt, Lòuwerenburgh H Crells H3 ajiKoxojia H BHTpHOJia. TexHHMKH ce erajieH Äoönja H3 ajiKoxojia KaxajiHTHiKKM omenAHBaibeM BOÄB ca a JI yM H H H J Y M O K C H Ä O M (Senderens) KOJ'H ce 3arpeBa Ha 200 ÄO 300° H npeno H>era npeBOÄe ajiKoxo;me nape 1 . HCTO Kao H ajiyMHHHjyMOKCHA MOXTE H A J I Y M H H H J Y M ( } > o c c i J a T Äa ce ynoxpeóH 3a npenapaTHBHO H3BotjeH>e OBaKBHx peaKimja. yMecTo, Kao m T o je y HarneM npmuepy, TepMHMKor pa3JiaraH>a KHcejior eTHJiecrpa cyiunopHe KHceJiHHe, y3HMajy ce necTO ecipH Äpyrnx KHcejiHHa, Ha np. 6 e H 3 o e B e KIIc e n H H e, ia 6H ce H36er;io ynbeHHcaH>e Koje HacTaje aejcTBOM cyMnopHe KHceJiHHe. TaKotje ce Mory na ynoipeöe H n p H M. K a j i H j y M c y j i c J i a T H 6 e 3 B O Ä H a 6 o p H a HJIH O K C A J I H A K H c e j i H H a ( a K p o j i e « n H3 rviHuepHHa, l i H p o r p o H c i j a i i a K H c e j i H H a H3 BHHCKe K H c e J i H H e ) . O ß Ä e cnaaa H K c a H T o r e a a T H a M e i o i a no 4 y r a j e B y. XeMHCKa K a p a K T e p H C T H K a 0Jie CH2 • CH2 I I NO2 O • NO2

npeMa jeAHaqn'HH:

CH2 : CH2

C02

> CH2 — CH2 I I CI OH. TaKo c'e aoßnja e T H J i e H i a o p x H j p H B HCTOBpeMeHHM yBofjeH>eM y pacTBop xjiopnor Kpeia. 6.

A30TÄHOKCHÄ y JHHHTPOEIAHE: R — CH = CH — R V R • CH • CH — R I I NO2 NO2

Ca a 3 0 i i p u 0 K C H A 0 M HHTP03HTH.

7. O 3 o H (Harries,

Hacrajy

npHMaH>eM

N203

AHMOJieKyjicKH

/°\

HOC

CH2.

3roaaH nponnc 3a jiaöopaTopnjcKo ÄOÖHjaite Hajia3H ce KOÄ W. Kesting-a

38, 362 (1925).

nceyao-

Staudinger). CH2 : CH2 + 0 3

1

eTHJieHa H

Z. Ang.

95

OjietjlHHH

r i o u n o ce

O3OHHÄH

/ ° R • CH

npw 3arpeBaH>y ca BOÄOM pa3JiaHcy npeMa jeÄHaiHHH:

\ HC

R

- I ^ - > - R . CHO + R • CHO + HO • OH

I I o — o 0M0ryheHa je

THM

nyieM

cHHTC3a

AUEXEIA

(HJIH KeToaa).

XHapojiH3a

eiapcKOj BC3H h nao MeljynpoÄyKTH Hacrajy . n H O K C H a j i K H J i n e p o K C H Ä H

ce BpuiH

na

RH(OH)C • O —

O • C ( O H ) H R (BHÄH TAKOTJE V , 2) KOJH ce Äajbe pa3jiaHeroB TpH030HHÄ

(0306eH30Ji)

C'6H609

rJiHOKcaJia. Tene pa3JiaraH>e 030HHfla

xHApHpaneu

Koje

B O Ä H npeno jeanor HenocrojaHor OKCHaaKHJieTpa R • C — / H flo A U E X H I A

OÄH. K e T o H a.

\

O —

OH

C • R /

HO

\ H

Ynop. join Äo6Hjait>e

AIIIDIIHIHAFLIEXHIA

H3 UH-

ooxeKcaHa ( X I , 4). 8.

B o Ä o H H K.

peayKUHOHHX nyieiu,

OjiecjjeHH

He

Mpry

cpe/icTaBa ca HacueHTHHM

aa

ce

ca racoBHTHM BOÄOHHKOM y npncycTBy

(Sabotier),

naaanHjyM

(Pall,

xn.npnpajy

BOÄOHHKOM.

Skita),

TO ce

HHjeÄHHM

nocTHJKe

OÄ

CJ)HHO pacnojiejbeHor MeTa^a,

nJianiHa

(Fokin,

yoötmajeHHX

caMO KaiaJWTHMKHM Kao

Willstätier).

HHKa n

Ynop.

joiu

r i p i i TOMe HacTajy

a n-

npenapaTe X I , 1. 9.

BeH3onepKHCCJiHHa

(peaKUHja no ilpujiexajeBy).

KlIJieHOKCHJlH O • OH R • CH:CH•R

I + C0H5 • C : O

>- R

CH

\ ¡0.

XmpoKCHji.

TeMnepaTypH y H>nxoBe

rioMohy

• C H • R + CGH5 • C O O H .

/

0

iiepMaHranaia

npeBOÄe ce

ojiecfHHH

Ha

HHwoj

rjiHKOne:

R • CH : CH • R

>- R

CHOH • CHOH • R.

UejcTBO oßor OKCHaauwoHor cpejicTBa ÄOBOÄH jiaKo no nomyHor pacKH^afta ÄBoryße Be3e, np» neiuy ce ÄBoryöo Be3aHH yrjbeHHKOBH 3TOMH Äajbe OKcnnmuy. AKO cy jorn y HCTO BPEME Be3aHH H ca BOÄOHHKOM, HacTajy N H H e,

HHa'IE HacTajy

KapöoHCKe

«nee-

K e T O H H. /

/CH

^CH

3

R • C H : C

> R•COOH +

3

OC

\ch 3

\CH3

PeaKUHja ca nepMaHraHaTOM je nparoueHo H Miioro ynoipeöjbaBaHo cpeacTBO cno3Haßaibe H e 3 a c i i h c H e y XJIAÄHOM aJiKoxoAy, weHor pacmBopa ry6e

Be3e.

cupkemHoj npywa

aona

HCKOJIHKO KanH pacmBopa

uepMamauaiua. TaKoIje

KHCCJIHHH,

H y Möwe

co^e,

H iana

HCKOJIHKO Kann pa3öjia-

Bp3o necTajaibe upBeHe 6oje noKa3yje. npHcycTBo micToj, jia

ce

H

npeMa

nepMaHraHaxy

H3Bejie , E a j e p o B a

aajby M0ryhH0CT 3a pacno3HaBaH>e aBoryöHX

XJ10p0(J)0pM.

3a pa-

n p H p o Ä e HeKor opraHCKor jeÄHtt.eH>a. CyncraHua ce pacTBopw

npo6a".

Be3a.

nocTojaHoj 06e36ojaBaH>e

Kao pacTBapai

IBO-

zjiaifUjajiHoj 6 poMa

cayjKH OÖHHHO

96

OjieijìHHH

OaeíJJHHH ce a a o e noHauiajy y 33bhchocth o a npnpoAe MoJieKyjia qecTO pa3^HiHT0 y norjieAy Ha 6p3HHy KojoM CTynajy HaBefleHe peaKUHje aaHUHje. Ako y Henoj (Jjopinyjiii bhahmo ÄBOryöy Be3y, HHje raine 6e3 Aajber peqeHO, Aa MOHceMO ca h>om j a H3BeAeMO cae Moryhe peaKuwje. Tano Ha np. y o n u u e He noaa3H 3a pyKOM na ce 6poM ampa Ha l e i p a i f i e H H J i e T H J i e H (C 0 H 5 ) 2 C : C ( C 6 H 5 ) 2 . A ^ b b h t c t ABoryôe Be3e je pa3JiHqHT Aanae oa cjiyiaja a o caywaja. A k o Äße Aßoryöe Be3e CToje y cycencTBy, | t o oHe Mory npn peaKUHjaMa ajiwuHje aa pearyjy Kao 3 3 T B o p c H chctcm. TaKo 6 y i a « n e H ajinpa 6poM AeaHMHiHO y cMHCJiy cjieAehe jeAHaiHHe : 1

2

3

Br

4

C H 2 = C H • CH = C H 2

B r C H 2 • CH = CH

f b e r o B a niiKapôoHCKa micejiHHa, M y n o H C K a K i i c e J i i i H a , 3acHheHy A H X H A p o M y K O H C K y K H c e a H H y :

CH 2 Br. xiiApnpa ce y ß, y-He-

H O O C • CH = CH • CH = CH • C O O H ->• H O O C • C H 2 • CH = CH • C H 2 • COOH, y o6a cjiyqaja HecTaJy o6e npBoôHTHe Aßoryöe Be3e h H3Mel]y h>hx HacTaje jeAHa HOBa; aAHUHja je H3BpuieHa y nojiojKajy 1,4. HapoMHTO HHTepecaHTHy h npenapaTHBHO BaacHy npHMeHy Hauiao je npHHKHn 1,4n o OBoj chhtc3h aAwpa aAHitHje y „AHeHCKoj CHHTe3H" Kojy cy otkphjih Diets h Alder 1, ce ó y T a a H e H h MHoroópojHH s e p H s a i H ö y t a a H e H a (H3onpeH, UHKJionenTamieii) Ha nojeflHHaiHe ABoryöe Be3e H3Metjy yrjbeHHKOBHX aTOMa AajyhH AepHBaTe l e i p a x H Ä p o 6 e H 3 o a a . Tano HacTaje Ha np. H3 ôyTajweHa h aHXHApHAa MaaeHHCKe KHcejiHHe T e T p a X h ä p o (J) T a n h a K H c e j i H H a : CH2 y CH I CH

\c h

CO +

CH2

/ \ CH \ H L

\

\/

/

b

^

2

/ CH ,11 CH

\/

\ CH—C02H I CH—C02H

ch2

AflHUHjoM óyTaaneHa Ha x h h o h AOJia3H ce a o H a ^ T a j h h o b o t ^ HC

CH2

HC

\c h

CO / \ HC CH

HC

HC

HC

CH

\c / o

2

pea a :

CH2 CO / \ » / \ n ch2

.. ..c o

CH

ripHMeHa m i K J i o n e H T a i i i e H a Kao „AHeHa" boah chhtc3H e ii a o-u h k j i h w h h x n p c T e H a c T H X c h e t e m a Kao uito hx CTcapa ónjbHa heanja y Kaimjiopy h ApyrHM TepneHHMa, Ha np.: CH CH I CH V

CH

\

/

CHO

CH C H 2 + Il y/ CH2

CH

/ C\H — C H O

CH ~ Il CH.« I CH I CH

H3Bol)eHie P,u.nc-Ali Appone AiieiicKe ciiHTe3e (uHKjioxeKcaAHen h xhhom) onwcaHo je KOA npenapaTa VlII, 1. 1

A, 460, 98 (1928); bhäh TaKotje Z. Ang. Ch. 42, 911 (1929).

A.IKOXOJIH

H, 6

9 7

FlojaBa 1,4-aiumHje o6jauiH>aBa ce no Tuney Tano, na ce noM-cuna Koia ce Hajia3e pacnopetjeHa OKO Y R J B E H H K O B H X aTOMa Be3aHiix asoryóoM B E 3 0 M 36or npocTopue Ó J I H S H H C H3Me^y C H C AE^HMHiHO noTHpy, TaKO NA ce Ha C J H C Hajia3H BehH X ^ M H C K H noieHunjaji Hero Ha C H C ; TaMO cy npeMa TOMe tfiaB0pH30BaHa M E C Í A 3a aaHUHjy. 2

3

4

2

3

flpe.Ma 0B0j npeicTaBH npeHeioj Ha 6eH30Ji H M 3 M O y O B O M , ycaea yHyTpamH>er H 3 B A J I E H U H , MHoro jaqe 3acHheHy TBope&HHy Hero JIH I I I T O je T O Moryhe KOA BHiueBajieimiHX o.ieíjjHHa. Y 6eH30Jiy HeaocTajy TamKaj, a 3 a n i M noIKyT H noKa3yje BeJiHKy peanunony C\ H

H C H C

C H

/ \

\ C H H C

C H

/

W H

n

K

O apO

KoiijyroBaiiHM He3acHheHHM ciicreMHMa 6nhe AouHHje a a (V, 8).

BIIIUC

peiíi

Koa n o JI

H

e

11

a

T N H O H

6 . r ; i n K O J i (eTHJTeHrjiHKOJi) h s rJiHKOíiflHaueTaT.

y

6anon

eTHJieHópOMHfla 1

c a KpaTKHM BpaTOM, 3anpeMHHe

-jiHTpa, Kojn je cnojeH c a ycnpaBjbeHHM K0H,a;eH3aT0p0M

CT3BH

1/2

c e MemaBHHa

OA 63 g (1/3 Mo;ia) emujienópoMUfla, 20 g rjiai¡ujajine cupheüiHe mcenme H 60 g cbokc HCTorubeHor H ( } ) H H O c n p a m e H o r MJiujyMcmewawa ( y n o p . II, 2 )

H

3 a r p e B a A s a c a T a Ha neumaHOM KynaTHJiy

JIHKHM

ruiaMeHOM

j e ^ H e KO^eHacTe 1

Henry,

TaKO

AA

X H B O

K^>yqa.

ixeBH c a K0HAeH3aT0p0M

H^H

TAAA

Ha

M P O K H U H

c e SA^oH

noctaBJbeHHM

Beace

KOCO

Ha^; Benpeno

Ha AOJie

Bl. [3] 17, 207 (1897); C. 1907 I, 1314.

IlpaKTHKyM opraHCKe xeMHje

7

OpraHCKo-npenapaTHBHH fleo

98 PEAKUHOHH iuiaMeHOM

NPO/TYKT

3arpeBajyhn AUPEKTHO

AECTHJIYJE

Kojer CTSJIHO

noRpeheiwo.

BCJIHKHM MSIJSBHM.

N P E A «paj AecTHJisiuije

n;i3MeH c e

nojaqa AOAAB3H>eM B33AYX3. ^HCTHJiaTy ce A O A A AAJBNX 60 g ETHJIEHÓPOMHAA H 80 g KaJiHjy'MaijeTaTa, M e m a B H H a Kao H r o p e 33rpeBa Ha n e u m a H O M KyNATHJIY A B S A O T P N caTa AA )KHBO_ KJBYQA H N O H O B O Aecrajiyje. /LECMÍIARce

(JjpaKijHOHO

flecTH^Hiue

(cTp. 17)

CJIEAEHE (J)PAKUHJE: 1. O A N O N E T K A A

CTH^AUHJE A O 140°, 2. O A 1 4 0 — 1 7 5 , 3. O A 3 ce n o H O B O jorn j e A H O M 0AB0jeH0 auaifeüiani

cnnpajiy

BuaMepoBy

NPHMEITYJYHH

CKyiubsjy

n p n N E M Y ce OABOJEHO

AC-

175° A O npaja. paKUHje 2 H rjimon-

AecTUJimuy, n p w qeiuy IHCTH

NPE^IA3H H 3 M E ^ Y 1 8 0 — 1 9 0 ° (RJIABHA KOJIHHHHS K O A 186°). N P H H O C

OKPYRJIO 70 g. AKO xoheMo aa ce npHHoc noóojbiua, 3arpeBa ce OHajfleoflecToaTa,KOJ'H je npemaoHcnofl 180°, ca HCTOM KOJIH'IHHOM Kajiujyjiaqemawa UOHOBO 3 caía, a 33THM paaii nao UITOje rope onacaHO. npHHoc ce Ta.na noBehaBa 3a jorn aajbHX 15 g. TJIHKO^. ancojiyTHOM

ce

JXa 6h

„canoHHc|)HKyje"

H3 ecTpa

KyBaiteM

ca

MeTmia^Koxo^y.

npH qeiwy c e X J I A A H

A oA H pa

OA

IVIHKOJI, OBaj

ce

xjiopoBOAOHHKa

y

aioóoAaH racoBHTor

H C 1 y aücojiyülHu

YBOAEHH

iyBa

H

AO6HO

pacTBopoM

ca

Memujiamoxon

BaaroM,

AOÓHja c e

3 % - T H H pacTBop; n p n T O M e c e npnpaiiiTaj y T O K H H H y T B p A H Ha B a r « Koja H M a oceTJbHBocT 0,1 g H n p H e B e H T y a ^ H O M BHiiiKy H C 1 A O A a OAroBapajyha. KO^HQNHA

METH^AJIKOXOJIA.

49 g rjiuKonauai¡emaUia

(1/3 MOJia) H TIO mi Memunamoxona

3acuhenor

xjiopoBOflOHUKOM KyBajy c e 1/2 caTa y Ma^oiv óaaoHy (200 mi) JBEHHM K 0 H ^ E H 3 A T 0 P 0 M ;

Ha AOAe nocraBJbeH Koxom, rjimojia, MenoM, Majie

K0HAeH33T0p,

a OCTATAK c e

JXa 6 H c e

TAAA AECTHJIYJY

Majie

eKCTpaxyje

ce

KOJIHQHPE

HA O K O 50° A H P E K T H O HENPOMEIBEHOR

ocTaTaK y 6ajiOHy,

ca O K O 50 mi a n c o ^ y T H o r KOJIHHHHE

Memujiaifemalli h jeAaH Aeo

NPEAECTH^AME

3aocTajie

3AOCTA^OR

ca ycnpaBnpo3

y N O Q E T K Y NO^aKo,

Kojw j e

ecTpa

KOCO

Memujian-

y Banyyiviy^ OABOjHjie OA.

3anyiueH

ryMeHHM

y K O M E je T^HKOJI

HepacTBOpaH..

ETPA YKJIOHE c e HA KJBYQA;IOM

B O A C H O M Ky-

eüipa

NHTHJIY, a TJIHKOJI, KOJ'H ce npepyHH jorn Bpeo, AECTHJIHIUE ce H3 MAJIOR óaAOHa 3a (JjpaKUHOHHcaifce ca

Ba3AymHHM

K0HAeH3aT0p0M.

npejia3n K O A 195°. N P H H O C 1 7 — 1 8 g ( 8 0 — 9 0 %

F^iaBHH

Aeo>

O A Teopaje).

ErafleHópoMHfl Monee aa ce npeBeae y I-JIHKOJI H flupeKTHOM c a n o H H eroB ajiKoxojj — Hajnpe fleayjyhH ca KajmjyMaueTaTOM (qecTO H cpe6poaueiaioM) e c i a p c H p H e T II e KHCEJIBHEKOJ'H 6H ce Morao canoHHtJíHKOBaTH Ha onuiTH H HopinajiaH H3HHH ca BOfleHHM paciBopoM AJIKAJIHJA HAH MHHepaflHHx KHceflHHa. AJIH OBfle, KOA y BOAH pacTBopHor rjiHKOfla KaoKpajfter npoflyKTa, He Tpe6a fla ce Hanycra paa y opraHCKOM pacTBapaqy. 36or Tora cesofl ycJiOBHMa e c T e p H ( J ) H K a u H j e omen«.yje KHcejiHHCKa rpyna ecTpa H OBa y OKBHPJT paBHOTe>Ke pacnoflen>yje Ha o6a a^Koxo^a, rJiHKOí H MeTH^aaKoxoji. flouiTo ce OBaj no-

Ajikoxojih

99

CJieÄHjH Ha^a3H y bcjihkom BHuiKy TO ce ecTepHtJwKauHja Bpwii npBeHCTBeHO y H.eroBy KopHCT. Oßa BpcTa canoHHc^HKauHje 03HaiaBa ce nao j i B o r y ö a H 3 M e ï ï a e c r a p a , O 1 cTBapaiby h canoHHc¡)HKaunjH ecTapa BHAH ßjiiiiKe II, 7. O a peaKUHja HajnpocTnjnx ABOBajieHTHHx ajiKoxojia, 1,2-rjiHKOJia, HaBeuiheMO na npHMepy ocHoBHor jeauH>eH>a cjieaehe: rip« 3arpeBaH>y ca cyMnopHOM khccjihhom Haciaje y 3 H3ABajaH>e BOAe a u e T a njexHi. KOHU. coHa KHce^HHa aaje e T H J i e H X J i o p x H A p H H ; Apyra O H - r p y n e 3aMen>yje ce xjiopoM aajieico Tewe. HCl CH20H — CH2OH > C H 2 O H — CH 2 C1 + H 2 0 . OBO ce jeaHftcfte ao6nja TexHHqKH aAHUHjoM xnnoxjiopacTe KHccjiHHe Ha eTHJieH, npH >ieMy ce y pacTBop xjiopHor Kpeia HCTOBpeMeHo yBOAH C 0 2 h eTHJieH. ÄejcTBOM janor pacTBopa Ka^HjyMXHapoKCH^a Ha xjiopeTHJiajiKOxoji Aoöwja c e e i a j e a o K C H i y 3 h3ÄBajaH>e HCl: CHoOH . CHoCl

• C H 2 — Cha

Jipe cBera OBAe Tpeöa aa ce noMeHe m k npejia3 xjiopxiiApuna ca TpHMe-rmiaMHHOM y [jjH3H0JioiijKH BaiKaH x o j i i i i i , HHjfi xJiopHA Morne jiaKo Aa ce ÄOÖHje, ano o 6 e komiioh c h t c y eKBHMOJieKyjicKHM KOAHMHiiaMa (KOHueHTpoBaHH pacTBop 6a3e y ancojiyraoM anKOXOJiy) ÄCjcTByjy Heno BpeMe na Tonjio jeaHa Ha a p y r y . Ca o j o B O T e t p a - a u e i a T O M , P b ( O C O C H 3 ) 4 , AexHAporeHyjy ce rJiHKOJiH y3 pacKiwaifae C — C - Be3e. M3 eTHJieHrjiHKOJia HacTajy 2 MOJia (}) o p m a n a e x h a a. Ü B h a K o h ce pacnaaa Ha 2 MO.ua a u e t o h a 1 , no peaKUHjn Koja wae y cynpoTHOM cMHCJiy oa peaKUHje iteroBor CTBapaH>a: (H3C)X

C(CH 3 )„

"I

I

OH

~ 2 H - > - 2(H 3 C) 2 CO

OH

O npHMeHH oBe MeToae 3a cHHTe3y ajuexHAa bhah Ctir. Grundmann

Orjiefl ; PacTBopy oa 1 g ojiotiomempa-ai(ewawo? KucejiuHe ÄOÄa ce 3 nanu iJiiiKona; CTBa ca Ma^o cyMüopacme Kucejiune,

A. 524, 31 (1936).

y 40 ml eJiatfujmiHe cupfiemne

nocjie nojia caTa pa3opH ce BHiiiaK oKCHaauHOHor cpeAuejionynno ojiobo t3jio)kh ca pa3Ö.na>KeHOM cyMUopHOM

KUceniiHOM h y (JwjiTpaTy oa ojioBocyjie koa 65° 2 0 0 g MUHujyjaa h cóaKH nyT leica aok hg ncqe3iie upBeHa 6oja. ílpH x^aíjefty KpneraJiMiue mempa-ai{emam Kojn ce MOHte npeKpHCTajiHcaTH H3 TJiauHja^He CHpherae KHceJiKHe h KojH je, m a ce qyBa o a BAare, nocTojaH. (O. Diniroih h R. Schweizer, B. 58, 1375 [1923].) pacTBopa y n o p . R. Criegee, B. 64, 260 (1931). 8

O OApeljuBafty OAOBOTeTpa-aiwTaTHHx

G. Schroeter K W. Sondag, B. 41, 1924 (1908). 7*

OpraHCKo-npenapaTHBHH neo

100 ri0CTaBJbeH0M Meiap

OABOAHOM UCBH.

TeMnepaTypa

AecTHJiHuie,

ypoiteH

BpeMe, npe

y

nonHe

TCHHOCT, LUTO j e

Hero

Koja

ce. y

y 6a^0H

n p e A e c T H ^ H c a H H aMHJia;iKoxo.7i 3a

ce

OABojH 6ojbe hi

óajiOHa

ox;iaAH

noMohy ce

caTa

ca Ha

npHHOCOM

(J)HHO

cnpaiueHHM

yjbaHOM

KynaTH,ny

Ha

140°.

Bpaha

ce

Heno noHOBO

KajiuiyMKapóonaüinM.

(B. c T p . 1 7 ) .

ca

TaAa

boachom

noMohy

napoM,

KOJiOHe,

CupOBH aMHjieTap

3a

noTnyHO

nanipujyMaMuaoM ca

TCPMO-

n p e T X O A H O OABOJH C>A B o a e

100°, AecTHJiyje

OA 2 0 0 — 3 0 0 g.

iiOAaKO

noKa3yje

nacoBa

H c})paKLiHOHHiiie

BHAMepoBe cnnpa;ie ca

H nojy

8—-9

Kojn ce

Ha OKO

h aMH^a^Koxo^a

nocTHrHyTa,

BpeMe cyiiJH ca

H3 AECTHAATA y^>aHH c j i o j

168—172°

KyBa 2

0ABajau>e H KpaTKo

caap>KHHa

TOKy

OBa TeMnepaTypa

y

AeBKy

Boae Kjbyqa

MemaBHHa

MCmaBHHG

npejiasH

npe^HuihaBaite

(1, 5 g

ycnpaBJbeHHM

jom

Ha 1 0 0 g

eTpa)

K0HAeH3aT0p0M,

H TaAa

pa3ÓJi.

AECTHJIAUNJOM OABOJ'H OA HATPWJYMAMHAA. JL,ECTH^AT c e NPOMYHKA

ca

XJlOpOBO/ZOIlUIHOM KUCejlUHOM,

H Haj3aA

}kjbHBO A e c T H A y j e

npeno

KaJll}UjyMXJlOpiiaa

CyiIIH H3H3A

6pu-

HaülpujyMa.

8. XaopCHpheTHa KHcejiHHa hb cnpheTHe KHcejiHHe h xjiopa 1 y MemaBHHy OA 150 g rjiaiiujajine cupheüíHe tcucejiune h 1 2 g iipBenor e

Tonjbett>a

Aa

(JjpaKUHOHO

q e M y c e p a c T p e c H T H KPHCT3JIH

U,e!jett>e

H3Mel)y

BOAOM

Mopa

je

3a-

yBotjenbe

noceÓHO c e

BOAH T p j b a j y h n

HHaqe x j i o p c w p h e T H a

(III,

JieAeHOM

OA 1 5 0 — 2 0 0 °

cacTojn

Moryhe

PEAKUWJA j e

xjiopoBait>e

KOJH

3arpeBa

cBeTJiocTH,

ox^aAH

AaHa

npejia3H

h Ma;ioqac

HHTpoMeTaH

(VII, 2),

ce

IIITO j e

MOHoxjiopcuphewne mcejiune

JieAeHoj

HCTonnjia.

H üOHOBJbeHOM 186°,

KaA c e

3HMCKHX

KOJH c e

TyqKOM.

npeAa3n Kao

na

cy H ^ e B o j

(j)paKUHOHHcaibe noja

Ha H y q y ,

jep

h Koja

ce

J l e T H j e AOBOJ£>HO j e A H O A H e B H o

Ko.iHHHHa M 0 H 0 X J i 0 p c H p h e T H e

KOJIHMHHOM KJbyqa&a

Kojw

3a

xjiaAH y

HJIH

Tpaje,

HCTO

MyTHHX

Aeo

nocTeneHO Aeo

nocTyna

H Apyra

1

ce

ijunaTyjiOM

CMe A y r o MSMy

OBa

oqBpcHe

H3ABajaft>e

paKLiHja

h ombpc.ih

CTp. 8 8 ) , yBOAH

6HTHO 33BHCH OA OCBETJIEIBA.

npo6a

Sa^oHa

ueBH.

qauiy.

ujTariHheM caSwjy

H3

3a

(CJI. 4 6 , KJbyna,

A u p e K T H o j

uiTannheM.

BpeMe

h HAyhH a s h .

npoAy>KHOM

ce

Ma^a

JKHBO Ha

XJIOPOBAHIA

cTaKJieHHM

ce.AecTKJiyje y

Koje

Hajóojbe

MHM j e A H a

npoTpjba

K0HAeH33T0p0M

KynaTH^y

e c T a p

4).

R. Hoffmann, A. 102, 1 (1857); Rasanow, B. 25, Pe$. 334 (1892)

Taqna

80—125

(VI, 7),

g.

tjih-

101

CyncTHTyunja BoaoHHKa xajioreHOM

riouiTO MOHOxjiopcnpheTHa KHce^HHa, HapoiHTO TonJia, jano HarpH3a Kowy, Tpeöa ce lyßaTH aa ce c h>om He aolje y aoawp. XjiopMpan>e 3H3THO 6p>Ke Te4e, iaK h 6e3 c b c t j i o c t h , ano ce r o p i t o j kojihmhhh o a 150 g ejianujamie cupftemne KiicejiuHe zioja 1,5 g joß,a, 7 g PCl5 h.3 g i{pEeHOi cpoccpcpa'. Ilocjie 3aBpLueHe peaKUHje aeKaHTHpÄ ce oa ( f o c i o p 3 j 0 1 1 1 äok j e Bpejio, pa3ö/ia)KH ca 40 ml oauHja^He c n p h e r a e KHcejiHHe, ouean aoöpo Ha BanyyMy noc-ne xjiatjeH>a HCKpncTajiHcajia MOHoxjiopcuphemna Kucejiuha h nepe ca Ma.no rjiauHjajiHe cnpheTHe KHcejiHHe. Tano ce aoöHje c;ia6o upßeHKacT npenapai koj'h ce y eKCHKaiopy H3Haa KamijyjuxitAPOKcu/ a ocao6oah 3aocTajior joaa. CyncTHTyuHja 3acHheHor jiaHua xjiopoM jeaHa O = C rpyna. TaKO ce a a a e x H A H h h t o xajioreH c i y n a HCKJbyTOBo y a-no^oHKe aa ce y6p3a 0CBeTjbaBaH>eM h KaTa;iH3aTopHMa (npeHOCHouHMa). MecTo Ha Koje CTyna xajioren j e h OBae yBeK yrjbeHHK KojH ce Hajia3H y cyceacTBy ca Kap60KCH^0M, aaKJie a-nojiowaj. Kao npenocHJiau npH xjiopoBaH>y noroaaH je aKTHBHH x ji o p j o a, Ha np.: C H 3 • C O O H + C1J

j o a,

koj'h ce Bewe

ca xjiopoM y pe-

• CH 2 C1 • C O O H + H J .

riouiTo oßaKo HacTajiH joaoBoaoHHK aejcTBOM xaopa oaMax n0H0B0 a a j e j o a koj'h 33thm noHoßo cTBapa xjiopjoa, t o OBae HMaMo jacaH c j i y i a j K a i a m a e Koja ce xcmhckh MOHte JiaKO OÖjaCHHTH, y cyuiTHHH a p y K i n j e h MHoro KOMnjiHKoBaHHje a e j i y j e (J)oc• C H 3 • CO • O • C O • CH 3 + H C l . KHceJiHHa

h Meljy-

n p o a y K T Kojw TaKO HacTaje pa3jia>Ke ce H a j 3 a a x j i 0 p 0 B 0 a 0 H H K 0 M KojH npw peaKUHjw

HacTaje,

A H X B a p H a ce

caa

mhoto . jiaKiiic

cyncTHTyTHBHo

xjiopyje

Hero

Ha cJieAehH HaiHH: CH 2 C1 • C O ^ 6)

CH 2 CI • C O O H

> 0 + HCl H3C • C O / '

-> CH3 • COCI

Hohobo cTBopeHH a u e T H j i x j i o p H A M05Ke npeMa a) h3hobh aa erynn y peaKUHjy. Aok je y HauieM c^yqajy KO/inmiHa (|)oc(})opa orpaHHqeHa, ynoTpeÖJbaßajy ce, HapomiTO koa yBoljefba 6poMa, iecTO eKBHBajieHTHe kojihhhhc, HacTaje aaKae 6 p o m h ä k h c e i H a e h TeK Taaa ce cyncTHryHuie y a-noao)Kajy. Kao peaKuwoHH npoayKT jaßjba ce OBae ö p o M H a a - 6 p 0 M 0 B a H e k h c c j i h h c Kojn aejcTBOM Boae Mopa aa npelje y cjioßoaHy KHcejiHHy; TaKolje ce necTo aoöHBa aejcTBOM a^Koxo^a e c t a p (nocTynaK no Hetl-y, Volhard-y h Zelinskom. ct-xaJioreHKap6oHCKe

KHcejiHHe,

oa

Kojnx j e HajnpocTHja

xiiopcnpheraa

KHce^HHa, Hajia3e MHorocTpyKy npHMeHy 3a cHHTe3e. HoMeHHMO h>hxob npejia3 y o k c hK H c e ^ H H e (XHApoJiHTHHKHM oAßajafteM xajioreHa) H y a u H H O K « c e j i H i i e (npen. VII, 2): C1CH 2 • C O O H + H Ö H CICH 2 • C O O H + 2 N H 3

H O C H 2 • C O O H + HCl j- H 2 N • C H 2 • C O O H + NH 4 C1.

YßolieHie ce j o a a BpuiH no MeToan noMeHyToj Ha CTp. 81. ß-xa^oreHKap6oHCKe KHceflHHe aoÖHjajy ce aanuHjoM xaaoreHBoaoHHKa Ha a-ß-He3acHheHe KHce^Hne: HBr C H 2 = CH • C O O H • CH2Br • CH2 • COOH. aKpuana KHceaHHa 1

H. Brückner,

ß-6p0Mnp0nH0HCKa KHce^HHa

Ztsch. f. Angew. Chem. 40, 9 7 3 (1927); 41, 226 (1928;.

OpraHCKO-npenapaTHBHH aeo

1 0 2

„II. K a p ö o H C K e KHcejiHHe h

Ü H X O B H

npocTH

ßepHBaTH

1. XjIOpHßH KHCeJIHHE А)

A U E T H J I X ^ O P H A

1

H a 90 g (1,5 MOJia) 6e3B0AHe rjiaifujajine cuphemne mcejime Koja c e Ha^a3H y öajioHy 3a (jjpaKijHOHHcaibe ca K O C O Ha A o a e N O C T A B J T > £ H H M K O H ÄeH3aTopoM cwna ce, y3 X A A ^ E F B E B O A O M , H3 JieBKa 3 A n a n a i t e 72 g (poc(popiHpuxjiopiiaa. Taßa ce ypoHH A O K > H Aeo óajioHa y He cyBHiue Majiy nopuejiaHCKy m o j b y H a n y a e H y B O A O M 3arpejaHOM Ha 4 0 — 5 Q , ° H H A C T Ä B H 3arpeBan>e CBe Aoivie, A O K H E nonycTH pa3BHjaH>e X J I O P B O A O H H Q H E KHcejiHHe Koje j e y noneTKy ÖKJIO JKHBO, H ÄOK ce TeqHOCT Koja j e npe 3aRPEBAFTA ÖHJIA XOMOREHA HE pa3ABojH y A ß A c a o j a . I I O T O M ce aifeMujixjiopuA ÄecTHJiaiiHjoM Ha B O A E H O M Kynamrcy Koje J K H B O KJbyqa O A B O J ' H O A (pocípopacüle mcemne ( A O H > H cjioj). K a o peuHrwjeHT C / I Y I K H Majia 6 o u a 3a uet}EH>e Ha BaKyyM Koja je npeKo njiyTeHor 3 a n y m a q a Be3aHa ca Ä O H J K M KpajeM KONAEH3ATOPA. J L A 6 H 6nna 3 A M ™ H E H A OA BJI3}KHOCTH BA3AYXA HAßYQEHA j e noMohy KOMaA«ha ryMeHor upeßa je^Ha CaCl 2 -ueB. E I O H O B H O M j e c T H j i a u n j o M (ca TepM0MeTp0M!) npenapaT ce npemmihaßa. i p a K u w j a H3Mei]y 4 8 — 5 3 ° XBaTa ce noceÖHO (Taqka KJbyqaita M H C T O T aaeTHjixflopHAa 51°). ripHHOC 7 0 — 8 0 g . npHMeHa 3a A H X H S P H Ä c n p h e T H e K H C C J I H H C (II,

2)

H

A U E T O ( J ) E H O H

(IX,

3).

McnHTaj npenapaT Ha c a Ä p « a j $ o c i f o p a (PC13) Ha Taj Haiwi, UITO he ce HeKann aoaaTH y Majio Ton^e Boae, pacTBop y Ma^oj nopuejiancKOj wojbH ncnapnTH, 33THM. ÄBanyT ca JaKOM a30üiHOM KucemmoM IIJIH ÓPOMHOM BOAOM HcnapHTH RO cyBa H nanoKOH H3ßpuiHTH yoöimajeHe peanunje Ha (froapopny KüceAUHy. AKO ce e HC1, Koja c e Tana pa3Jia»a: C 6 H 5 • C O • Cl

TaqKa K j b y q a f t a 198°.

C6H3C0 • O H

„

250°.

XJIOPHAH KHcejiHHa H u a j y jaK ouiTap MHpnc H n y u i e c e Ha Ba3flyxy. BOÍIOM c e p a s n a w y CTBapajyhH pejiHo

flaKo,

KHcejiHHy nouiTo j e

H XJIOPOBOJIOHHK. 3TOM x j i o p a

MHoro

OBa

ce

peaKUHja

BpuiH

qecTo

jiaóaBHje BC3aH 3a ocTaTaK KHcejiHHe,

H3BaHHero 3a

^JIKHJIHH ocTaTaK. /1,OK j e 3a npeTBapaH>e xa^oreHa^KHJia y ajiKoxoJi BehiiHOM noTpeSno na

ce

K

a p-

104

OpraHCKO-npenapaTHBHH

aeo

OH ayn e, na 611 ce peaKmija npoH3Be^a. XjiopHiH cyj](J)OKHce^Hna cy nocTojaHH H3secHo BpeMe qaK h npeMa KJbyqa^oj B O A H ( B H A H 6eH3ocyji(j)oxjiopHA IV, 1). AjiKajmje, pa3yue ce, Aeayjy Ha xjiopiiAe KHce^HHa Aaíieno óypHHje Hero BOAa. Ca ajiKoxoJiHMa H (fieHOJiHMa pearyjy X J I O P H A H KHcejiHHa Aajyhu e c T p e. O R A E F L a : O K O 1 / 2 MI ai¡emiuixjiopuw yjiHje ce noereneHo y 2 MI BOAS KcTa ce Ha;ia3H y enpyueTH. AKO je BOAa BP^O x-íiaAHa Mory Aa ce npHMeTe KpaTKO BpeMe yjbaHe KanjbHue xjiopuAa noje TOHy y BOAy H ie, Mopa H3BecH0 BpeMe Aa ce KyBa. noc/ie xjialjefia HCKpHCTa,/iHiiie 6eH3oeBa nucejiuua. Ha H C T H H 3 H H H AejcTByj H A 6 E H 3 0 H ^ x v i 0 p H A c a 2N-pacülBopoM 6a3e. O r n e ^ B: Ha 1 mi amoxojia, Kojn ce Hajia3H y enpyBeTH ie cHpheTHOr ecTpa. Ha ajiKoxojia

Haqnii H3BeAH peaKunjy ca 6eH3oujixjiopuMOM ca HeuiTo y BnuiKy H HcnHTaj 6p3HHy AejcTBa no MHpncy.

HCTH

X J I O P H A H KHcéjiHHa ce HCKOpHiuhyjy, Aa 6H ce OAJiyqHJio, Aa JIH Heno joui Heno3HaTO jejiHibefte caap>KH IIJIH He caApwH ajinoxojiHy HJIH ijieHOJiHy x m p o n c m i a y r p y n y. A K O MarepHji pearyje ca X J I O P H A O M KHcejiHHe OHAa je T O AOKa3 npHcycTBa O B H X rpyna, n o u i i o cy cBa Apyra jeanfteH>a Hoja HMajy Be3aH K H C C O H H K y ApyroM oC.iHKy, Ha np. caApwe eiapcKO Be3ann K H C C O H H K , HHAHijíepeHTHa. JJoaaTKOM ajinajinja HJIH ajiKajuiHX Kap6oHara M O W E peaKUHja 3 H 3 T H O AA ce ojiaKuia. Haj3aa, aejcTBO xjiopH.na KHceJiHHa Ha ajiKoxoJie H ijieHOJie npHMeH>yje ce joiu H OH.ua, Kajia je noipeóHo Aa ce OHH H3ABoje H3 pacTBopa HJIH Aa ce oKapaKTepnuiy. 3a OBy CBpxy cJiywHMO ce Hajiemhe 6eH30HJixji0pHA0M. MeTHJiajiKOXoji Aaje Ha np. ca' p-H H I P O 6 E H 3 0 I U I X J I O P H I O M jien KpncTajiaH MeTHJiecTap, HITO J I O 3 B O J B A B A na ¿ce I * He3H3THe KOJlHIHHe H3AB0je H3 BOfleHOr pacTBopa. Ha COJIH K A P Ó O H C K H X KHCEJIHHA AE^yjy xjiopwaH K H C E ^ H H A najyhn a H x n a p H j e KHceJiHHa ( B H H H HFLYHW npenapaT). Mopa jorn na ce noMeHe aa ce auHflwpafte a^Koxojia, 4>eH0Jia H aMHHa ca XAopHflHMa-. KHceflHHa (H TaKolje aHXHApnaHMa) Meció no ciapoM IUomen-EayMCiHOBOM nociynKy — aejCTBo xjiopniia KHcejiHHa Ha aflKOXojiHo-BoaeHy cycneH3njy — .naHac MHoro nyia npeay3HMa y nHpHAHHCKOM pacTBopy. nnpHiiHH Taae Be3yje X A O P O B O A O H H K . M Ha a M o H H j a K Kao HHanpHinapHe H c e s y u i a p a e opraHCKe 6 a a e Aejiyjy X ^ O P H F L H KHceJiHHa ca B C J I H K O M ^ A K O H O M :

105

KapöoHCKe KiiceJitiHe H HJHXOBII npocTH aepHBaTH

C H 3 • C O • C1 + 2 N H 3 = C H 3 • C O • N H 2 +

NH 4 C1,

aueTaMHÄ C H 3 • C O • C1 + 2 C r> H, • N H 2 = C 6 H 3 • N H • C O • C H 3 + C 6 H 5 • N H 2 • H C l . aiinjinn aueTaHH^HÄ Or^efl,: npw

MCMy

CTaHe y3

a)

ce

MHM

oä

HCTO

6)

TO

HCTa

neTocrpyiKHa

AOAa

x^a^eite

oÖHJiaH

Je^HOM

nacTyna

rniaK ce

neniy

MOJKe

Tajior

ce

joui

ce

npe-

AOAaje H3Aßaja

Aa

noeeha

oueAH

H

npe-

6a3a

npe-

115°.

TONJB.

6eH30iuixji0puff,0M.

HCKopmuhyje 3a oKapaKTepncaBaibe

oprancKHX

BoljeffaCM y H>nxoBe BCHUHOM KpncTaJin30BaHe AcpHBaTe KHCE^HHA, H 3a pacno3naBaH>e Majinx Ko^immia,

npe c ß e r a

noTnyHQ

xeminx

6 a 3 a,

p e a r o ß a j i e — jep ce jeaaH

nyTeM

OÄpeljHsaHja

Tame AeJiOBe HenpoMeiteHor aijeTHJixJiopHAa

KJbyqaiba

npHMeHa

(V 8 ; ,

H

njiaiweHOM

HenpoMeiteHor

HHMSJIO

AecTHJiaanjoM

OÄBOJH

ca

BOAOM

pacïïiBopa

H

noorce

AOAATKA

Ha Taj HamiH,

PA36-AA>KeHe

HNOs

IIITO

c e jeAHa n p o ó a

AOA^

HCKO^HKO

Kann

cpeâpoHUwpaiïia.

Ha aHajior 6eH3oeBe

H3HHH

MO>Ke npenapaTHBHO

KHcejiHHe

M ô m e TaKotje Aa ce Aoônje

Kojn H

jieno

AA

ce

AOônje

KpHCTa^nuie

3 H X H A P « A

(T3mk3

Tonjb.

KaAa c e 6eH3oeB3 KncejiHH3 KyBa C3

42°).

BHUJKOM

aijxHApHAa cHpheTHe KHcejiHHe. JI, o 6 H j a H> e

6e3B0AH0r

HaTpnjyMaueTaTa:

Co

KpncTa^Hy BOAy (3 H 2 0 ) 3 a r p e B a ce y njiHTKoj 3Ae;iHUH

APMIH

HJiH HHKJia AnpeKTHO H3H3A njiaivieHHKa.

Koja

rBOHrìja

OA

ÍIouiTO je KpHCT3JiHa BOA3 ncna-

pHjia, p a c r o n oHBpcHe. CaAa c e 6e3BOAHa c o onpe3HHM 3arpeBaH>eM riocjie noHOBHor 33TBopeH cyA-

OMBpinhaBaita joui Tonaa c e

cnpauiH

H

OAMax

HCTOIIH.

CT3BH

H KynoBHH 6e3BOAHn aqeTaT Mopa c e TaKotje join

Ä e j c T B o a u e m a x f l o p H Ä a na HaTpnjyMaueTai jiemaBa ce n p e M a cjiejiehoj jeÄHaiHHH:

CHS . C = O ONa =

^ > 0 + NaCI.

CH3 • C = O 1 2

Baeyer H Villiger, B. 33, 1575 (1900). C. Gerhardt, A. ch. [3] 37, 313 (1853).

y

J'CAHOM

HCTOnHTH.

CHS CO • CI + CH3 • CO

ca-

II, 2

KapfioHCKe KHcemwe h ibnxoBH npocTH AepHBaTH

107

H MemoBHTH aHXHjipHflii Kojn caApwe ABa pa3JiHHHTa ociaTKa k h c c j i h h c n o r y Ha OBaj HaiHH Aa ce npunpeMe ano ce ynoTpe6e xjiopHA h co ABejy pa3AHiHTHX KuceJiHHa. f l o m T o ce, Kao u i t o je r o p e H3BeaeHO k o a aueTHAXAopHAa, H3 aflnaAHe c o a h KaKBe KHCeJIHHe H POCI3 MOIKe A06hTM XJIOpHA KHCejlHHe, TO 3a AOdHjaibe ^HXHApHAa HHje noTpe6Ho na ce xjiopha Hajnpe H30Jiyje, MO>Ke ce u n a BHiue oamsx AeaoBaTH Ha BHmaK coah, TaKo Aa ce m P O C l 3 h coah Mo>Ke AtipeKTHo Aa Ao6nje aHXHApHA (TexHHiKH n o c i y n a K ) . opMyjiHti]H OBy peaicuHjy! Hh>kh qjiaHOBii a n x H A p H A a K H c e j i H i i a cy 6e36ojHe TeiHOCTH, a bhuih MBpcTe «pncTa^iie MaTepHje. Ohh HMajy ouiTap mhphc, y boah cy HepacTBopHH, pacTBapajy ce MeljyTHM y HHflH^epeHTHHM oprancKHM pacTBapaqHMa. hbiixoBa cnemiifiHiHa TewHHa Beha je oa cneuHynaH>a jieiKH BHiue on TanKe KJbyqaiba OAi"OBapajyhe KHce^HHe: cupheTHa KHcejimia 118°, aHxnApiiA ciipheTHe KHceAHHe 138°. Taqna Torubefta jieiKH y o n u n e y3eBiiin HHHce. H h w h HAaHOBH Mory 6e3 pa3JiaraH>a M.a ce AecTHJiyjy noA o6imHHM npHTHCKOM; k o a bhuihx qjiaHOBa AecTHJiauHja Mopa Aa ce Bpiim y BaKyyMy. XeMHCKO n o H a u i a a e aHXHApmia npeMa boah, aAKOxoAHMa, (jjeHOAHMa Kao h 6a3aMa n o m y H o j e h c t o Kao h nonaujaH>e x n o p 11 a a, canio u i t o 3 h x h a p h a h p e a r y j y c n o p a j e oa xjiopiiAa. Oraeft: Ha OBaj noToue ce

3 ml

Ha a h o

n a K MSiiiaBHHa

pacTBapafte 6^a>KeHa

AOAa c e

h He p a c T B a p a

ce

qan

anxuapuw

CHpheme

pacTBapaibe

tcucejiune.

hh npn A y ^ e M MyhKaity.

aHXHApHAa h BOAe 3 a r p e B a

OHAa j e

cuphewne

Ako

Heno ce

BpeMe,

mccto

oHAa

BOAe

y3Me

KHceJiHHe ce bpao qecTO ynoTpe6jbaBa 3a yBoljeH>e

Kanw KOHiieinpoBaHe

cyMnopHe

O r J i e f l , : r i o M e m a j anxuapun

Boaenu.M

pa3uiBopoM

hojiom AOAaj jeAHy

pa3-

khccahhc

a n e i m n

6p3HHa peaKUHje ce H3B3H-

cuphemne icucejiuite p e A O M c a CIMOXOJIOM, anujiuHOM, (penojioM. MemaBHHH ca (j)e-

aMoiiujma, K a n kohii.

Ako

HacTaje

6p>Ke.

y aJiKoxoAini hah cj)eiio.iiHn x h a p o k c h a hah y hckh AepHBaT aMOHHjaKa

Hoahtkom jeAHe paAiio noBeha 1

tieiHe

1 / 2 ml

y 3 cjeAMbaBaH>e c b o a o m .

6asa,

Ahxhapha rpyne

Bo^e

H2SOi.

TepMHMKHM pa3AaraHjeM na y c n j a n o j ruiaTHHCKoj jkhuh npeBOAH ce 3 h x h a p h a cnpKHceAHHe y3 H3ABajaibe BOAe y MOHOMOAeKyACKH aHXHApHA CHpheTHe KHceJiHHe, y

JieTeH

(Wilsmore): H3C • CO > O -

H„0

>- 2 H 2 C = C

O.

H3C • CO npenapaTHBHO Ao6HjaH>e KeTeiia TepMHHKHM pa3AaraibeM aueTOHa C H 3 • CO • C H 3 3r0AH0 TeHCKOM

h ca Ao6p«M

JiaMnoM"

K a o cpeACTBO 3a

CHo : C O + C H 4 .

npHH0C0M

K o j y j e A a o E.

1

m o j k c Aa c e A o S n j e

Ott1.

KeTeH

aiy>KH y

KeTeH c a OTcycTBy

,,KeBOAe

aueTHJioBatt>e.

A H a j i o r H j a aHXHApHAa K n c e ^ H H a 3yMjbHBa aKo c e

(Schmldlin):

6^HHce pacMOTpn

c a x j i o p H A H M a KHcejiHHa n o c i a j e p a -

6^HCKa

cpoahoct

J. pr. Ch. 130, 177 (1931), — y n o p . TaKolje Berl

OBe A B e K ^ a c e

h Kullmann,

jeAH-

B. 65, 1114 (1932)

108

OprancKO-npenapaTHBHH .neo

K a o a O B A e , h tümo j e x h a p o k c h j i Kap6oieH aHjOHCKHM ^ e j i O M H e n e KHcejiHHe, koa x ; i o p H A 3 x ; i o p o M , koa aHxn.apn.zia aueTOKCHJiOM O • C O • C H 3 . Ahxhaphah o p r a H C K H x Knce^HHa M o r y A a c e 0 3 H a q e h K a o a h s u h j i o k c h a h ( a a H . i = pa,n,HKaji Kqce^HHe, Ha n p . C H g • C O = aueTH.rc), h A a ft.eH>a.

ce

(^opMaflHO

na^ajy

ynopeAe

ca

HajHHepTHHjHM

AOJia3n

BCJiHKa p e a K U H O H a

ApHAa?

C.na6o

MecTO

jiHajiKHjioKCHflHMa.

Ha n p . b o a s

uejie

cnocoÓHocT

HjHxobom

y

KHceoHHHHOM MOCTy, B e h a a h unja,

eTpHMa,

jeAHibefbHMa

opraHCKe

Ha

hcth

MO^eKy^y

Ha A B o r y 6 o j

Be3H ^

h aMOHHjaKa h

AP-:

npH-

OAaiuie

HamiH H 3 r p a i j e H H x

He T p e ó a >

Eipn

xeMHje.

C =

Aa

O.

Tpa>KHMO

OBAe

h9c-

>0 -

NH 2 ~

OH

H „ C — c_ =

Me})ynpoAyKTn

Kojn

_n

CToje

H8C — C ^ O H

; C3 N H 3

-O

H3C — c = o

Ha

Haciaje

Un

H3C — c = O

caA

anxH-

_ y

_HSC — C = O 3arpaAaMa

cy

napo'iHTo

_

jia6H^HH r

h H e r a t H B H a a q e T O K C H J i - r p y n a H3;i33e Ha hctom C - a T O M y ( y n o p . c T p . 87); ohh c e pa3Jia>Ky 3 Ó o r Tor Ha 2 MOJia n n c e ^ n n e hjih y c j i y M a j y aMOHHjaKa Ha c n p h e T H y , KHceflHHy h aueTaMHA- H a hcth HaMHii ( } ) o p M y j i H u i e c e h p e a K U H j a c a a j i K o x o j i H M a . Bhah c e , Aa n p n y B O t j e f t y j e A H e a u n ^ H e r p y n e n o M o h y aHXHApHAa KHcejiHHe ( y hckh a ^ K 0 X 0 J i , 3mhh h t. A-) y B e n jeAaH oa o 6 a o c T a T K a MOJieie He 6 y A e cnocoónocT

xJiopnAa

KHcejiHHa

hm3 hcth

HCKopnujheH. B e c u n a y3poK

nao

uito

je

peaKUHOHa

3a aHXHApHAe

oójauiHaeHo. 3. AijeTaMHfl 1 8 0 g aAWHujyMaiiemaüia

—

AoSnjeHor

H3 aM0HHjy¡nKap60HaTa

h

ivia-

Uwja^He CHpheTHe KHcejiHHe2 — h ' 60 mi rjiai¡ujajiHe cupheüiHe uucejiime 3 a r p e B a j y c e Ha Mpe)KHUH y msjiom 6 a ^ 0 H y c a Bmamcpobom ko.iohom, h OApacaBa 6 ^ a r o KJby^a 5 — 6 csth. r i a 3 H c e Ha to a a Ha TepMOMeTpy K o j H c e H3Jia3H y r o p a e M Ty6ycy KO^OHe T e M n e p a r y p a 6yAe 103° h A a n p e n o OBe He n p e í j e hhm3.to hjih caMO Ma.ao; r ^ a u n j a j i H a c w p h e T H a K H c e jihh3 h B O A a K o j a c e C T B a p a n p n p e s K U H j n OA^ia3e n o j i a K O H3 a n a p a T a h Mory ce

K0HAeH30B3TH n o M o h y

K p a j e M KOJiOHe h — npeuiflo 1

oko

8 0 mi

Majior K0HAeH33T0p3 c n o j e H o r e s

paAH KOHTpo^e — 33rpeB3 ce

jane

Aa ce XBaTájy y aok

TepMOMe'rap

ropH>HM

MeH3ypn.-K3Aa je He

noKajKe

140°,

y npHHUHny no Francois, C. 1906, J, 1089. Httsch h Gtlbert, ]. Am. Soc. 35, 1780 (1913); W. A. Noyes h Goebel, y hctom qacoriHcy 44, 2294 (1922). 2 Y 60 mi ejiaifujajwe cuphenme Kucemme Ha TeMnepaiypH 40—50° Aoaaje ce tojihko chtho cnpauieHor aMomijyMKapóoHama, aa Majia npo6a pasCjiawena ca boaom p e a r y j e a.iKaaHO. Tpefia HMaTH na yMy aa np» tom Ha 1 mo.i aMOHHjyMaueiaia Haciaje i i o i a H„0.

109

K a p 5 o n c K e K i i c e / m n e H ftHXOBH npocTH aepHBaTH

Ta^a

c e o c r a B H n a c e Ma;io o x j i a A H ,

H3;mje joiu T o n a o p a c T o n y

ó a ^ o H 3a (J)paKiíHOHHcaibe H r j i a B H a KOJiimHHa x B a T a , Ü,ecTHJiHiiie, Ha He o ^ B p c H e

oue^H ce

nopuejiany

AKO

195—220°.

npoaykT

A o 6 p o Te^HH

y encHKaTopy

KOJ'H

npn xjialjeiby

Aeo h o c i a T a K

K J b y n a Ha (II,

H

5)

Majia

223°.

Tonjb.

npo6a

ripHHoc

80°.

METHJIAMHH

(II,

MO»e

5 5 — 6 0

g.

Aa c e

Ha

n0p03H0M

(|)H./iTpaTa

H 3

A a c e AecTH.aauHjOM A o 6 n j e joixi j e ^ a H A e o ai¡eíüaMUAa. Taina

npe-

Tp;baH>y n o T n y H O

H

cymn

c e He CMe e B a i < y n c a T n .

oónqaH

noiiiTO HeuiTO

MOJKC

MHCTO jeAHu>eH>e

npeKpHCTajiHine

üpHMeHa n p e n a p a T a

3a

óemom.

H3

aaeTOHHTpH^

8).

H3 KHcejimie Mowe y o n m i e aa ce aofiHje a.MHa ano ce H>eHa a M O H H j y M O B a co noaBpnie cyBoj aecTHJiaiuijH, HJIH join 6OAC, aKO ce 3arpeBa aywe BpeMena Ha BHiuoj TeMnepaiypu. A U C T S M I I A aoóHja ce BehimoM 3arpeBaifaeM a M O na 200°. ripn TOMÜ peanmija He nae ao Kpaja, jep ae-iyje aejiiiMHiHo na auna KHcejiHHe; IICBH

CH3 • C — ONH4 — C H

jy M a u e T a T a y 3aTonjbeHoj o a a Koja npn peaKUHjH naciaje

H H

• C — NH„ + H„0.

3

II O

II O

FIOIUTO MH KOÍI naBeacHor nocxynKa a e c n u a u n j o i i HCTepyjeno CTBopeHy Boay H3 peaKUHOHe cneiue, cy36njaMO cynpoTHy peaKmijy H riOBehaBaMO npHHOc. McT0BpCMen0 BHiuaK r^auHja^He ciipheme Kiice.'iHHe aejcTByje cynp0TH0 aiicojinjamijn COJIH npeMa jeaHasHHH:

CH.. • C — ONH¿ II O

> CH3 • COOH + NH3.

y n o p . ys TO a.Hciyiiafta Jie«yiaH>a KHcejiHHa: cHpheTtia KHceJiHHa, TaMKa KJbyqaH>a 118°; nponHOHCKa KHcejiHHa, Taqna K^yqaaa 141°, aueiaMHa, „ „ 223 ü ; nponHOHaMHa, „ „ 231°. Ba3HH KapaKTep aMHHO-rpyne je CKopo noTnyHO Heciao 36or AUHJIHOR ocTaTKa KOJ'H je c H>OM Be3an. no3Haie cy ao ayrne COJIH aMiiaa ca jaKHM KHceJiHHaMa Koje ce MeljyTHM ca BoaoM oaMax noinyHo pa3jia>Ky Ha caciaBHe ae^oBe. CaMO K a p 6 a M H a, aHaMHa'yrjbeHe KHcejiHHe, rpaaH nocTojaHHje COJIH qwja je er3HcreHUHja o6e36et]EHA apyroM NH 2 -rpynoM

110

y

OpraHCKO-npenapaTHBHH

3a KojHMa

npn

a.MHÄe K H c e j i H H a je

Meiaji

peaKUHjH

—

KapaKTepncTHiHa

Ha

He

AMHAA c a

HaiHH

ÄHBHHHM

Kao

cy

OKCHAOM, Ha

—

ca ABOBa;ieHTHOM a 3 0 T . OHa

Be.3aH 3a

KHBOM Hacrajy

np.:

>• (CH3

CO

aqemaMUMa

O n i e f l : PacTBopn c e HeuiTO H

HBHXOBA jeAHH>EH>a

KOA COJIH, j o H o r e H o

2 CH 3 • CO • NH 2 + HgO

DKUBUHor OKCuaa

Aeo

3arpeBa. O ß a j npe./ia3H

y

NH) 2 Hg + H 2 0. BOAH,

npnTOM y

AOAA

otcyUior

Majio

pacTBop, n p a

qeiwy

ce cTBapa r o p e (JjopMy^Hcano j e A m f e e i t e . 0"peaKmijH H3ABajaH>a BOAG Koja BOAH AO H H T p H JI A H peanuHjn o AejcTBy xwnoxanoreHHTa Ha AMHAE KHcejiHHa roBoonhe ce KOA ÄOUHHJHX npenapaTa. ÜEJCTBOM XHAPOJIH3yjyhwx MaTepHja OTueujbyjy ce aMHHO-rpyne — ApyKmje Hero KOA aMHHa — jiaKiue HA» TeiKe CTBapajyhn n0H0B0 KHCejiHHe. O y3poKy oßor pa3JiHiHTor noHamatta ynopejiH IIITO je pe^eHo Ha cip. 108. O r n e f f : y enpyßeTH ce 3arpeBa HeuiTO aifemaMum ca 2 n paeülBOpoM HaUipujyMxußpoKCiiAa. Jaßjba ce jan M H P H C Ha aMOHHjaK, a y p a c r ß o p y Ha^a3H HaüipujyMaqewani, CnpheTHa KHcejiHHa ce AOKa3yje Tano, I I I T O 3aKHce./iH K O H I I . COHOM mcejiUHOM A O K O H T O p e a K i j H j e ; e n p y ß e T a c e I I O T O M 33TBOpH na^ueM Kjbyqaitel).

H

npoMyhna

H

Ta^a 3 a r p e j e

AO

JlaKMyc-xapTHja Koja j e CTaBjbeHa

enpyBeTe

OTBOP

ce

(KaMeHiHhH .3a

KJBYNAIBA

Ha

ce

noup-

BeHH. (OnniTH ÄOKa3 3a ncnapjbHBe KncejiHHe). PeaKUHja AMHAA ca PCI5 Koja BOAH npeno HeKa OBae 6yAe caMO KpaTKO noMeuyia.

A M H I S J I O P N N A

ÜO

H M H I X I O P U I A ,

4. K a p ö a H H j i , 11 c e M H K a p ö a s H ^ a)

K A J I N J Y M U H J A H A T

200 iuojbH

Ha rB03AeH0M jiHMy y enpyßeTH

n o r a y H O pacnaAnyTH. njbefteM

6

H

j e

H

3arpeBa

HCTH

ce

naiKJbHBO

y

2

nopuejiaHCKoj

n o m y H O He H3ry6n ßOAy; Maaa n p o ö a

ÄOK

He CMe a a ce o p o c n , Ha

TonaeibeM

O K C H Ä 3 H H O H H M

g icajiujyM(pepoiiujaHitfla

HJIH

3arpejaHa

A O

1

HamiH ce

KpHCTajiH

150

Mopajy

Aa

6yAy

g KajiujyMüupoxpoMama

CBana

3a c e cnpaiueHe, A o ö p o c e H3Meaiajy y aßaHy H TaAa y oöpouHMa

OA n o

4 — 5 g npeHecy KOJ'H

ce

jano,

BOAE.

OÖAABE

y rB03AeHy

CO./IH

rnojby

noTnyHO c y ß e ,

TO-

npeTXOAHO

OCJIOÖOAE

HJIH

Ha jeAan

ca CHajKHHM njiaMeHHKOM (TeKJiyoßOM

ajiH rniaK H e

AO

ycHjaita,

6 y A e TaKO B H c o K a , Aa ce y

CBSKOM

3arpeBajy.

cjiynajy

BejiHKH rB03AeHH

HJIH

BHAH

TpocTpyKoiw

TeiwnepaTypa JKHBO

JIHM

JiaMnoM) Tpeöa

Aa

CBeTJiyuaite; apHa

pacTpecHTa Maca Koja n p « TOMe H a c r a j e He CMe HH y KOM c / i y i a j y AA c e CTON«.

ca

CßaKH c e o ö p o K n o c j i e OKCHAaanje, K o j a c e 6p30 3aßpiiiH,

IUNPOKOM

METARAOM

MNATYJIOM

HA

CTpaHy

HJIH

CKHHC

ca

JIHMA.

CIWIOHH

HnTaßa

KOJiHiHHa MOJKe Aa ce 3a 1 — P / 2 ^aca n p e p a A » Ha OBaj HaquH. CjeAHiteHH o ö p o i u i c e 33THM y 6a;iOHy npe;iHjy ca 800

ml

Bpejior 8 0 % - H o r

amoxona

1 noujTO nodojH caMO j e j i H a uwjaHCKa KHcejiHHa, TO CMSTpaMO aa HHje TaiHO Aa ce H>oj He aa OBO HMe, H Aa ce OHa, Kao IUTO ce TO wecTO Aoraija, Ha3HBa H30unjaHCK0M

KHCe^HHOM. 2

mann,

C. A. Bell, Chem. News 32, 99 (1875); B. 26, 2442 (1893).

Gaüermann,

B. 23, 1223 (1890);

H. Erd-

II, 4 h

3

Kap6oncKe k h c c j i h h c h h>hxobh npocTH AepHBara

MHHyTa

OÄJinje

KyBajy

öhctph.

Ha

boachom

pacTBOp

oa

Kynarany

upHor

jkhbo

Koje

Tabora

y

111 KJbyna.

epjieHMajep

CT3BH y j i e A h MHja c e c a A p > K H H a u í t o j e M o r y h e ö p m e o x j i s a h rioc/ie ce

KpaTKor

e r a j a i t a (JwjiTpaT

y e p j i e H M a j e p h H3^yjKHBaft>e c e

CBa c o

He e K C T p a x y j e

xjiaijeiby). nyTa

(npoôa

C o c e 33thm a

ÛJIKOXOJIOM,

y

joui

Tpw

ca

80

40 g KajiujyMiiujaHama BOAe

h

OcTaTaK

KyBa

aok

y

npn

H3ABaja

ce npn

onepe aba

Haj3aA y

eKCHKaTopy

r.

ce

ao

ncnape

h

xjialjeiby

ocTaTaïc

nejmoBas>y

y

Jienniu

HepacTBopaH

Wöhlerona

pacTBopy1.

pacTBope

Ha b o a c h o m

ce

ce

pacTBopn

Mopa

ce

KapóaMHAa,

OßAe ce paflH o aamiHjH N H 3 Ha C = N C =

HcnapaBaaa

hckojihko

rpaMa

a30ïïiHa

mcejiuna,

koa

Ha y M y

a^KO-

KapóaMHAay npn

qeiuy

HHje y

boah

Hcnnpatba.

kojom ce npBH nyT a o ó h o BeuiTaiKHM nyieM npHMep

3a Muore peaKUHje

KHcejiHHy h H>cHe ecTpe

O =

pacTBop

KpHCTa^H3aiiHja.

K a p ô a M H A H H T p a T

hm3th

qeJiHja, a a j e ;ien

unjaHCKy

y 500

KynaTHJiy.

HHTpaT.

KpHCTaJiHMa.

c hh t e 3 a

HacTynn

132°. H 3 (JjH^iTpaTa n o c ^ e

Kao

iuto

(J)yHKUHje >khbhx

Ha peaKTHBHy

boachom

y

cyBa

He

ml B O A e h A O A a j e y K a n H M a KOHI¡.

H3ABaja

npoflynaT BpmM

Aa

aücojiyUiHOM ajitcoxojiy y ô a J i o H y h a j i K o x o j i H H

3a A O Ô H j a i t e h h t p a t a HeKOJiHKO

cacBHM

( 5 — 6 nyTa) a o k

K a p ô a M H A

mojbn

tcapóaMuna

Tonjbeaa H30^yje

co

h

40 g aMonujyMcyjKpama

h

nopuejiaHCKoj

y

ce

HcnapaBa

ce

eüipoM

nyTa

nepiwaHraHaTOM 6)

xoJia

AOTJie

MyhnatbeM.

i\ujaHawa B p a m

Ha (JjHJiTapcKoj njio^H A o ô p o oueAn,

33thm

UHjaHH^a

OKCHAauHja

TameH>e j e 6 e 3 3HaMaja. PeaKUHja ca aMHHHMa Äaje ôaMHfl V I I , 1), a ca XHÀpa3HHOM

PeaKUHje. canqHe r o p e

c y n c i n i y n c a H e

KapöaMHjie

(ynop.

MeTHJiKap-

ceMHKap6a3Hj:

onncaHHM, ca jeAHH>eibHMa

cpoAHHM itnjaHÇKoj KHcejiHHH p a -

3yMejy ce caïue no ceÖH.

Orne#:

Hckojihko

pa3ÔJiaMceHOM COHOM

MH^n^HTapa pacïïiBopa

nucemHOM.

c^oôoAHe tfujatiCKe mcejiime

ifujanama

HacTaje pa3BHjaH>e C 0

cacBHM omqaH Mnpncy

2

3aKHcejiH ce ca h

oiiiTap

MHpwc

S02.

1 J. Vol hard A. 259, 378 (1890); E. Ullmann h Uzbachian, B. 36, 1806 (1903); Marckwald, B . 56, 1325 ( 1 9 2 3 ) . HajôojbH riporrne n o m v e o a Gali-a h Lehmann-a, B . 61

675 (1928).

112

II, 4

OpraHCKO-npsnapaniBHH ACO

Pa3JiaraH,e CJioöoAne mijaHCKe KHCCJIHHC y BOACHOM pacTnopy CBOAH ce Ha ana/iory peaKUHjy. OHa aAHpa BOAy H Tano Hacrajia K a p ö a M H H C K a K n c e i H H a pa3Jia>Ke ce HA N H 3 H C 0 2 : H,O O — C = NH

O =

C
HKauHja, 3 a r p e B a H . e c a c j i a ô o pa36jiaHceHOM cyMnopHOM KHCCJIHHOM HJIH

ca

H H j a K,

jaKOM. 6a30M

pa3JiaHe OBe p e a K u n j e Ha cTp. 116. AKO c e

AfcjcTByje

HJIH H3 HaTpHjyMa aMHHH (peaKUHja n o

HacueHTHHM BOAOHHKOM

H ajiKoxoJia)

Ha HHTpHJie,

(Ha n p . H3 uHHKa H c y M n o p H e KHcejiHHe

TO c e aAHUHjOM 4-aTOMa

c T B a p a j y npHHapHH

Mendius-y):

. CH3 • CN + 4H Raibé, Maifae BaxiHe, JEAHAQHHAMA:

a JIH HnaK

onuiTe

CH3 . CN + H2S

>CH3 • CH2 • NH 2 . eTHJiaMHH

peaKUHje

HeKa

6yny

> CH, • CS • NH2, THoaueTaMHA

AaTe

caMO

cJieAehHM

116

OpraHCKO-npenapaTHßHH aeo

11,6

^N.OH CH3 • CN + NH2

OH

-> CH3 • \nh2 aueraMHÄOKCHa

CH3 • CN + HCl

-> CH3 •

CH3 • CN + C2H3OH + HC!

/NH

, \ci HMHÄXJIOpHÄ

/OC 2 H 3 ~ -> CH3 • C ¿ ^ N H HCl HMHHoeTapxjiopxHapaT

U i i j a H O B o j o H H i H a KHCCJiHua ce noHauia y mhohim cboj'hm peanuHjaMa Kao HHTpHJi MpaBJbe KHceflHiie H • CN . Hene qiifteHHiie, npe CBera H>eHa bcjihk3 xeMHCKa h (JjapMaKOJiouiKa cjihihoct ca h 3 0 h h t p h j i h m 3 > C = NR, roBope 3a je^Hy apyry KOHCTHTyuHjy, HaHMe 3a KOHCTHTyunjy

KapöHMHHa

> C

=

NH,

ca

jBOBajieHTHim

yrjbeHKKOM. r i o M e H y i e p e a K i w j e 3a HmpHJie itoje cy CBojcTBCHe h mijaHOBoaoHimHoj KHcejiHHH M o r y hcto TaKO Äo6po jxa ce n3Be^y h h3 OBe apyre CTpyKTypHe $op.My.ne. Koä HHTpHJiHor oßjiHKa ajiHUHja ce aeuiaßa Ha TpocTpyKoj Be3H n3Mefjy yrjbeHHKa h a30Ta, koä „MeTHfleHCKor oöjiHKa" aernaBa ce Ha Äße cjioöoaHe BajieHixe na ÄBOBajieHTHOM yrjbeHHK0B0M aTOMy, Ha np. :

,NHOH HC^N \ c = NH

/ +

H 2 NOH /

HC^

\

„ J ™ HOHN. \ c = NH h/

O ä npenapaTHBHor sna^aja je x j i o p x H Ä p a T

.NOH > /

HC/

/

XNH NHa

.OC2H5

(JjopMHMHHoeTpa

C H ^

HCl KojH HacTaje y nenuM 6e36ojHHM KpHCTaJiHMa npw yBoljeH>y cyßor xjiopoBoaoHHKa y pacTBop eKBHMOJieKyjicKHX KOJiHHHHa

6e3BOÄHe unjaHOBOÄOHHMHe KHcejiHHe h eTHJiajiKoxojia

jiy THOM e i p y . CTajaiteM Ha x m ä h o co c e jiejcTBOM aJiKoxojia jiaraHO pa3^a)Ke Ha

y

anco-

e c t a p-

opTOMpaBJbe

K H c e j H H e a aMOHHjySixJiopHÄ : /0C 2 H 5 zOC 2 H 5 HC¿ + 2HOCH 2 • CH3 = H C ( - O C 2 H 5 + NH4C1. ^ N H • HCl X>C 2 H 5

Oßa cHHTe3a ecTpa opTOMpaBJbe KHcejimie ejieraHTHHja je h jiaKuia Hero CHHTe3a h3 xiopoijiapMa h HaipHjyM-eiHJiaia. EcTap opTOMpaB^e KHceJiHHe HaJia3H npHMeHy npn a u e i B J O B a & y kctohckhx rpyna, Ha np. :

C00C 2 H 5 + HC(OC2H5)3 = CH3

C • CH2 . COOC2H5 + HC = O

aueTCHpheTHH eciap 6. CanoHHt})HKau,nja h h t p h j i e y K u c e j i i m y . O e H n n c H p f c e T H a KHcejiHHa 1 40 g (1/3 MOJia) iuaBHHOM 1

6eH3UJitfujaHUfla 3arpeBa ce

o ä 50 ml KOHI¡. cyMüopne

Stcedel, B. 19, 1951 (1886).

mcenune

Ha Baóo-^ieBKy ca Me-

h 30 ml BO^e y ßajiOHy o ä

II, 7

KAPßOHCKE KHCCJIHH6 H H>HXOBH NPOCTH AEPHBATH

\\J

1 / 2 JIHTPA ca YCNPAßJBEHHM BA3AYMHHM K 0 H A E H 3 A T 0 P 0 M , AOK He HacTaHe peaKUHja Koja ce no3Haje no CTBapaH>y MajiHx racHHx Mexypnha H Koja y c K o p o nocTaje B p^o óypHa, npn qeiviy HacTaje Ä H B O KJbyqaite H H3öauHBaifae 6ejinx napa. OCTBBH ce Aa ce oxjiaAH, AOAA AßOCTPYKA KOJIHqHHa BOAe H noc^ie H3BecHor CTajaita oijeAH HCKpncTajiHcaHa (penujicuphewHa icucemiHa. AKO ce Ma./ia npoöa He pacTBapa ö n c r p o y pacíüBopy cone ((JJEHH^aaeTaMHa), HUTaB ce npoAyKT pacTBopn y COAH, pacTBop n p o UeÄH H H3 ÖHCTpOr (JJH.lTpaTa (JieHHJICHpheTHa KHC6JIHH3 nOHOBO T3JI03KH cyMüopnoM KucejiuHOM. KHCEJIHHA MOJKE ATIPEKTHO AA ce npenpHCTa^Huie H3 npH^H^HO MHoro Bpejie BOAC, HJIH nocjie cyiueiba H3 neTpo-aeTpa. 3 6 o r CBoje HHCKe Taqne Tonjbeifcs (76°) y n o q e r a y H3rvieAa q e c r o y j t a c T a . 3 a npe^HinhaBaite MO>Ke TaKolje Aa ce npeAecTHJiHme y BaKyyMy H3 ca6jbacTor ßajiOHa 1 . ripHHOc H3HOCH 3 4 — 3 8 g, a;IH MO>Ke Äa ce HeuiTO noBeha eKCTpaKnpBor KHceJior (J)HJiTpaTa ca eTpoM. B y p H a peanuHja canoHHcJmKauHje, npn Kojoj yBeK cfeH3H.ttUHjaHHA HcnapaBa MOHte Aa ce H3ÖerHe, aiKe ii3BaHpeano .nano XHAPOJIHTHIKH na ce 3aMeHH ca O. ynop. npHMep VI, 7. 7. E c T p H a)

KucejiHHa

E T H J i e c T a p c n p h e T H e K H C S J I H H S H3 r j i a a H j a j i H e cnpheTHe KHcejiHHe H ajiKoxojia2

H a öajiOH OA 1 / 2 JiHTpa CT3BH ce n^iyTeHH 3 a n y m a q ca Aße p y n e ; Kpo3 jeAHy npojia3H ^eBaK 3a KanaH^e, a Kpo3 A p y r y OAßOAHa ueß, Koja je Ha ApyroM Kpajy Be3aHa ca AyrHM KOCO nocTaBJbeHHM K0HA6H33T0p0M. Y öajioH ce CT3BH CMeuia OA 5 0 ml ÜJIKOXOJIÜ H 50 ml KOHQEHÜIPOBAHE cyMüopne Kucemne, Koja ce 3arpeB3 H3 yjbSHOM KynaTH^y Ha 1 4 0 ° . HHM ce OBa TeMnepaTypa AocTnrne, nycTH ce, Aa H3 ^eBKa 3a Kanare.e nocTeneHo 1

Adams H Thal, Organic syntheses II, 1922, CTp. 64.

2

Bl. 33, 350 (1880)

118

OpraHCKO-npenapaTHBHH fleo

y 6aaoH CMeiiia o A 400 mi amoxona H 400 mi rjiat¡ujame cuphemw H TO y HCTOJ" M E P H , y Kojoj AecTHJiHiiie cTBopeHH cuphewHu ecülap. flecTHJiaT ce MyhKa y OTBOpeKOM óajioHy ca He cyBHiue pa36^a»eHHM pacvüBopoM coae Aa 6 H ce OTCTpaHH^ia CHpheTHa KHce^HHa, Koja je Tano^e npeiujia y AecTHJiaT, cBe AOK ropibH cjioj BHiiie He 6OJ'H njiaBy JiaKMycoBy xapTHjy y upBeHo. Ta^a ce y JieBKy 3a oABajafte oABoje o6a caoja H ropibH c^oj ce MyhKa ca pacTBopoM OA 100 gr ¡tanqujyMXJiopuM y 100 g Bo^e, « A 6 H ce y A a v b H o a a K O x o j i . Ta^a ce IIOHOBO OABOje o6a cjioja y JieBKy 3a OAsajaite, npn qeniy ce ropibH cyoiH ca 3pHaTHM KaauHjyMxaoo PHAOM H peKTH^HKyje Ha BOACHOM Kynara/iy. T. K . 78 . JlpHHOC 80—85% OA TeopHCKor. ÍIpoAyKT Moace Aa ce ynoTpeÓH 3a a a e r c H p h e T H H e c T a p h. a q e T H J i a i i e T O H (VI, 5 h 6). TEQE

¡túcenme

E T H J i e c T a p 6 e H 3 o e B e K H O C J I H H C aHajiorHo ce Ao6nja; y Ty CBpxy ce 4 naca KyBa 30 g óemoeBe mcenme y 100 mi aüconyüiHor amoxona ca 3 mi konif. cyMüopae ¡túcenme ca ycnpaBHHM K0HAeH3ap0M. IIOTOM ce iviaBHa KoaHHHHa aaKoxojia npeAecTHJiHiue, 3aTHM AOAa 300 mi BOÁe » eKCTpaxyje eTpoM. Ewapatu pacüiBop ce HeyTpajiHiue pacüiBopoM cone, npeno Hohn cyinn ca Na2S04, IIOTOM eTap ncnapH H ocraTaK npeAecTHjinrue. T. K. 212°. ripHHOC 30 g. CTBapaH>e ecTpa H3 KHcejiHHe H ajiKoxo¿ia oaroBapa ij)opMa;iHo cTBapaH>y KHCE^HHe H XH.apoKCH.ua MeTaJia:

COJIH H3

N0 3 • H + Na • OH = NOs • Na + H 2 0 CH3 • QOOH + C2H5OH = CHS • COOC2H5 + H 2 0 0 6 a npoueca TeKy cacBHM pa3jiH4HTo y norjieay 6 p 3 H H e peaKunje H c i e n e H a flo Kora je peanunja iioiiijia. JXOK KHcejiHHa ca eKBHBajieHTHOM KOAHIHHOM flOBOJbHO jane 6a3e npaKTHMHO o«Max H noTnyHO npejia3H y co (HeyTpaJiHiue ce) Ha qeiuy noqHBa ajiKa;iHMETPNJA H AUHJIHMETPHJA, jtoTJie H3 eKBHBajieHTHHx KOJiHMHHa KHcejiHHe H ajiKoxojia H e M o w e aa ce ao6Hje TeopHCKH H3paiyHaTa Kojiimmia e c i p a . IllTa BHiue cTBapa ce oapefjeHa MancHMajraa KonHíHHa e c i p a , Koja j e yBeK MaH>a OR Teopacne H HeMoryhe je, Ma KOAHKO aa ce TpajaH>e peaKunje npoayiKH aa ce eciepHfjjHKyje HepearoBaHa KHceJiHHa ca HenpoMeH>eHHM ajiKoxcuioM npeno Te rpaHHue. AKO ce Ha np. nycTH na eKBHMOJieKyjicKe KOJinqHHe cnpheTHe KHcejiHHe H aflKoxojia a e j c x B y j y jejuia Ha a p y r y y 3aTB0peH0M cHCTeMy, TO he caMO no ABe TpehHHe na crynH y peanuHjy H HeMoryhe je, a a ce H nocjie.iiH>a TpehHHa cnpheTHe KHceaHHe FLOBE^e JIO peaKunje ca ajiKoxoM. Crora MancHMajiHH npHHoc e c i p a H3HOCH caMo ABe TpehHHe, Tj. 6 6 , 7 % oa TeopncKor. P33JIHHHTH KBaHTHTaTHBaH TOK ropH>Hx peaKUHja noMHBa Ha TOMe, UITO j e cTBapaH>e ecTpa T3B. „ p e e e p a H B H a p e a K ii H j a " Tj. TaKBa, KOfl Koje peaKUHOHH npojiyKTH KojH ce Hajia3e HA aecHoj cTpaHH jenHanme (ecTap H Boaa) aejcTByjy n0H0B0 jejiaH Ha a p y r n H y ofipHyioM cMHcay:

CHa • COOC2H5 + H 2 0
hxobh n p o c T »

ripeMa TOMe

TeMnepaTypa

flepHBani

o A H o c e h t o , Kao

oApeljyje peasmioHe

119

luto j e no3HaTo y

tom CMHCJ1V, Aa yrviaBHOM h>cho noBHinefta n o T n o M a w e oHaj n p a s a u peaKUHje, k o a K o j e r c e e H e p r n j a a n c o p f i y j e (eHAOTepMHH), a o k H>eHo C H H w e f t e noTnoMaHfe

cynpoTHH npaBau

peaK-

UHje (er30TepMHH). Flocjie oBe KpaTKe KapaKTepHCTHKe pesepsHBHHX peaKUHja h3jio>khmo H.njnpe Ha n p n Mepy

ecTepHtj)HKauHje,

ykojihko peaKUHje

cTBapajy ajiKOxoa)

jiHHa +

KaKo HMa Aa c e o é j a c H H

KHcejiHHa h a^KoxoJi jejiHo c apyrHM

3auiTo

p e a K U H j a He HAe

ao

pearyjy, A a o e

yKo;iHKo c e Kao

npoAyKTH

e c i a p h BOAa, ymnHKo h cynpoTHa y3HMa cBe Beher

Haxa. H a j 3 a a ce

( e c T a p - [ - Bona =

peanunja

aocthjkc

Kpaja.

MOMeHai, y KOMe

ce

ocehcto

tojihko MOjieKyjia KHcejiHHe h a m o x o a a cjeAHHe y e c i a p , ko^hko c e MOfleKyjia e c i p a h BOAe pa3^03Ke y KHcejiHHy h a^KOXoa. O B e c e peaKUHje c a j a A p w e y paBHOTe>KH, h H3rjieAa, Kao Aa j e p e a r y j y h w chctcm A o r n a o y CTaite MupoBaiba. O b o MiipoBatte j e caMO npHBHAHo 3aTo, ujto y je^HHHUH

BpeMeHa hcto t o j i h k o MOJieKyjia

koahko h HiuiesaBa.

e c r p a HacTaje

no-

CTHTHyTO j e paBHOTeiKHO e a o K o r a c e , Ha ocHOBy r o p a e r pa3MaTpaH>a AOJia3H h o h m , Kaaa ce

n y c T H na peaKUHja o a noqeTKa Teqe c a c y n p o T H e

a o peaKUHje eKBHBajieHTHe KOJiHiHHe e c r p a h Boae.

cTpaHe, A a o e

K a « a ce AOBeAy

T a n a h e raKO^e na c e 3aycTaBH h pe-

aKUHja c a n o H H ( } ) H K a u H j e ó p w e hjih c n o p u j e , s e h npeMa ycjioBHMa y c j i e a ecTepn(|)HKauHje K o j a cynpoTHO TeMe, h t o OHAa, Kan 33 1/3% e c T p a 6 y a e canoHHíjHiKOBaHO. PaBHOTeiKa ce AaKJie ycnocTaBjba no;ia3ehH c o 6 e CTpaHe Ha hctom M e c t y — eKcnepHMeHTaflua K0HTp0Jia h koa MHornx A p y r H X

h na TOMe noiHBa

H>eHa npeuH3Ha

peaKiuija.

riouiTO j e 6p3HHa 6nMOJieKy;icKe p e a K m i j e , Kao hito j e paHHje noMeHyTo ( c t . 3), n p o nopuHOHa^Ha npon3Boay Maca K o j e p e a r y j y , i n j a ce KOHueiiTpamija H3paHcaBa y g-M0ji0BHMa, t o c e AOÓHjy obh npocTH oahoch:

v = Cs y Cs,

obhm

CA

k;

jeaHanHHaMa v j e 6p3HHa

V'=CE

Cw • K

ecTeptKjjHKauHje, a v'

peaKUHje

canoHH^HKauHje.

C a , C e , C i v c y KoueHTpaunje q e m p H M a r e p u j e K o j e y i e c T B y j y , khJc' c y KOHCTaHTe

6p3iiHa o 6 e peaKUHje. CTaH>e paBHOTOKe j e oKapaKTepncaHO THMe, na y o6a npaBua p e a r y j e hcth 6 p o j MO^eKy^a, T j . « a c y

o 6 e 6p3HHe jeaHaKe:

v — v' T a n a j e TaKotje

CS hjih

THMe

ce H3pa)KaBa,

•

Ca

• Ca

CE

• Cw

_

oóhhho ce o6ejie>KaBa ca

K

k

Aa c y y , p a B H O T e i K H

np0H3B0AH

KOHueHTpaitHja

k'

KOHCTaHTaua. Kojih>ihhk — ,

o ó p H y T o nponopuHOHa^HH pcaKunoHHU E o i e x e ,

k — CE • CW • k'

Cs

K

y

paBHOTewH

KOHCiaHta

p a b-

K.

A k o no3HajeMo BpeAHoer OBe BaHtne BejiHMHHe, y CTaH»y cmo na Ha npocT namm H3paiyHaMO. Kao uito h e AOUHHje 6 h t h H3BeACHO, ksko c e npaKTHHHo MeH.ajy kojihmhhc peaKUHOHHX n p o A y K a T a koa jeAHe

peBep3H6HJiHe peaKUHje,

aKO He y3MeMO

Kao ao caAa, kom-

noHeHTe peaKUHje y eKBHMOvieKyjicKHM KOJiH R • C O O C H S 4- C H 3 • S 0 4 N a

T e K Ha noBHiueHoj TeMnepaTypH MO«ce

na

ce

hckophcth

3a ecTepHe ecTapa H3 pnaa 3naiaj.

hjih

aHxuipiiiia

KucejiHHa

h

a n o x o j i a ,

Koje

HMa

h

xno-

npenapaTHsaH

II, 7

Kap6oHCKe KHcejiHHe H H>HXOBH npocTH AepHBaTH

AKO c e paAH o npeBotjeifey Hene TeuiKO n p H d y n a i H e k o p h c h o e^eraHTHa Hhhui

M e t o i a

qjianoBH

Ha Bohe, a bhluh

ca

iHaíoueTaHOM

e c T a p a

K h c e JI h H a

qjiaHOBH nao h e c i p n

KHcejiHHe y e c T a p ,

( V I I A , 1) Koja Bpjio

c y 6e36ojHe

apoMaTiiHHHX

TeiHOCTH,

nocjiywHhe rJiaTKO T e i e .

npHjaTHor

KHcejiHHa c y l e c r o

c y n c x a H u e . T a i n e KJbyqaiha ca HIDKHM aJiKHJiHHM ocTauHMa ( C H 3 , Hero k o a

121

MHpwca

KpHCTaJiH30BaHe

C 2 H 5 , C 3 H 7 ) J i e » e HHJKe

KHce^HHa: CH3

COOCH,

iaHia M e i H ] e c T a p a

na np.

j h e t h ji e c t a p

je

EcTpH c e q e c T o CTuapaiii,

Aa c y TaqKe

i B i i e i H « e c t a p

ecen mije

BHuie H e r o

k h c e ji h h e

tchhoct,

H3patjyjy, Aa 6H c e Kao TaKBH

m ii p ii c h,

BehHHOM OKcajiHe

ynoTpeSHJiH y H H A y d p H j y ,

3a BoliHe c o n o B e h t a .

Ajih n p e

Kao

CBera o h h

p a-

nrpajy

3Ha l iajHy y j i o r y y peaKmijaMa k o a Kojiix c e Meita KapóoKCHJiHa r p y n a . T a n o c e a a j y ajiKOK/ R ciiJi-rpyne3aMeHiiTii 0CTaT. n k a u h j y iiapcmiTO

6)

h3boah Mime-

aejiyje

noA

jecie

CpeiicTBo

Koje

a ji k o x o ji h h

a).

p a-

k a ji ii j y m x 11 a p o k c h a a.

H 3 0 - a M H ^ - H H T p H T

44 g

(H3oaMn;iecTap

khcc.IHHS)1

aMUJiaMoxojia

( 0 , 5 MO.ia)

ca pacTBopoM

3 7 g TexHHmKemiM

KiicejiHiiaMa

CTBOP

nnñiija

.

70

boas,

Ae6ejinx

oxjiaAe

3haob3

AeHaTypncaHe

ce

(cnojba

co;ih),

y3

3ajeAHO

HaWpuiyjiina

0o

JieA

h

MexaHHHKo

ineuiaibe. . y

nycm

CMeuiy, cé

Kanatbe, nepaTypa 1

Aa 4 4 MI He

K o j a ce HenpecraHo Mema,

noJiaKC) ICOHU.

Tpeóa

Kaiube

w¿

cone ímcemHe Aa

ce norme

Wiii, B. 19, 915 (1886).

jieBKa (en.

3a Te®.

H3HaA + 5 ° .

1,18)

(cji. 5 0 ) ,

EIotom

ce

npn

neiiy

H3MyhKa

TeM-

y JieBKy

1 2 2

3a

OpraHCKO-npenapaTHBHH

oflBajaH>e

ppcüiBopoM ÓHCTPH

ca

2 0 0

cone

ce

H

H

cyuiH

JiHiHHa

npejia3H

$HKauHje. npn

ce

OKO

o

30

npo^yKT

y 3

y

A o 6 p o

Kao

OBHX

npenapaTHBHe

ocoSiiHa

M

y

cy

OCJIO6O.hh a 3 0 T a c - T a K H c e j i H H a .

COJIH H e p a c T B o p H e

—

ce y

COJIH ( V I I B , 3 e ) ,

H 3 0 H H T p 0 3 0 K e T 0 H a .

ce

ieMy

auexcHpheTHor

ecTpa, ca

HacTaje HaTpHjyiuoBa c o

RO -

HCTOM

CMHCJIY

npHMepn:

3JIKHJIHHTPHTOM

N =

KO-

OA

TeopHCKor.

O

anmn¡a

KHcejiHHe

N

2

0

—

y

Ha

HCTH

y

KojHMa

Ha ojie(J)HHe.

3

Ha KeTOHe y 3

2

cTBapaite

HaiHH,

Kao H npH

NONa

I

+ 2 R O H

R — C = cHHTe3a

a30TacTe

o63Hp

H36erHe.

H HaTpHjyMaJiK0X0JiaT0M,

R — C =

RONa

h canoHH-

8):

>

eJieraHTHa

mm

DiaBHa

pacTBapaiHMa

H3BOJH TaKOlje

+

Teie

6 0

UITO c e y 3 H M a y

COJIH

jiejcTBo H N 0

VI,

Majio

AO

KHcejiHHe M o p a a a c e

yMecTO

H3OHHTpo30KeT0Ha ( y n o p .

| R — C O y

OBa CHHTe3a

KeTOHHMa,

R — CH2

7 5 %

pa3JiaHcy,

opraHCKHM

jio6HjaH>e q B p c T H x HHa30HHjyMcKHX MeCTO

CJIOJEBA, ca

5 0

peumiHeHTa.

BHrnaK c o H e

c e ajiKHjmuTpHTH

nojHMa c e m e a n

KOA

npHHOc

7

pa36jia>KeHHM

ep^eHMajepy

BaKyyMy

yjbe.

ca

oABajaita

CBO]'OM BejiHKOM 6p3HHOM c T B a p a i b a

MeTojie. CpaKH

ynoTpeOjbaBajy

NOCJIE

MaaoM y

•CBHM OHHM c j i y i a j e B H M a ,

CHHTe3a

cjioj, n e p e

xjia^eifce

« y - r o

oajiHKyjy

II,

BOAOM.

AecTHflHiue

21)

KHcejiHHe c e

BOACHH

NYTA

M H H e p a f l H H M K H c e ^ H H a M a c e TOTOBO T p e H y m o

nponHCHBaity

36or

cTp.

Ha

a30TacTe

oTiiycra

HCKOJIHKO

ÍIOTOM

(ynopeflH

EcTpn

BOAC,

peaKUHOHH

JCCUIIIUJYM-XJIOPUAA. npHTHCKa

mi joui

.neo

0

H a T p B j y M a 3 H j i a

ca

xH.npa3HHOM

H

(Siollé):

AFLKHAHHTPHTOM

N \ H2N — NH

2

+

RO — N =

O +

RONa

-> ||

>N

• Na +

2 ROH +

H

2

0

N / Bpjio

wecTO c e

.aMHJiajiKOXOJia, MaH>a

npeTnocraBJba

E T H J I H H T P H T : Koja

Aa y 3

MyhKaibe

ce

K0HAeH3aT0p0M u e ^ e & e

Aa

ce

3Óor i t e r ó s e

jep

je

BHCOKC

yKJiaitaibe Ta'ine

KJhy-

npeAecTHJiHiue BOAOM

c y m e i t a

IIITO j e

Jiano

O n i e f l :

o ó o j e i t e .

HCKOJIHKO

HeKO.iHKO

TPEHYTAKA,

KanU

nann

mi KOHíf. a30WHe

Kojoj 1

ca ce

TyóycoM, Hajia3H

3 0

Koja je

cine

cone

HHHH

y

je

cyA n o c a e

HHCT H

3Óor

ynoTpeÓHTH.

Myhna

HacrynH

mcemne

noToriH

OAMax

ce

AOAaBaite

ü p e n a p a T

je

« a

n o c a e

AOBOJbHO

eüiujiHuinpuína

H e

ce

ca

HHK3KBO Aa ce

3a

pa3MPNO HCKO-

joa.

Teac.

ox^aijeHjy ca

g KapóaMuaHumpaüia

Lossen, A. Suppl. 6, 220 (1868).

ra

n p e n o p y q y j e

óajiOH

40 ).

Haj6ojbe

(en.

Be3aHa

ce

cjiynajeBa

E T H J I H H T p a T

l i o

B O A a.

o

IIOTOM

HJIH

u3XBaja

mcemne

g KapóaMUA-Huiüpawa.

30

peTopTy

a

pa36jia»eHe

HHTCHSHBHO

xjiai)eH>e.

IIOIIITO

BehHHy

ÜMUJI-

3a

JI e A C H a

KajiujyMjomaa.

B) 250

(6oua

CMeuiH

(T. K. 1 7 o )

HCnapjbHB

ce

peunnHeHT

y

25°, 3a

ÜJI-

nycTH

n a KOJH j e n p H K J b y n e H

emumuMpuia,

noneTKy

mi

6 0

Be3aH

croj«

üowamoM

pacüiBopoM

ójiaaceHHM

JIHKO

(y ca

H

óajiOHy,

BaJiOH je

nponyurra ce

(})paKiiHOHOM

mi KOHIÍ. cone mcejiune.

42

AejcTBa

KO]H

HampujyMHiimpuma

xjia^eHOM

Kanjbe

K0H^eH3aT0p

Ton^OM

Tora

JieAOM

A o S p o r

Ha B a K y y i n ) ,

Kpo3

KpaTKor

H y

H3oaMHJiHHTpHTy,

OTOKÍIHO,

pacwBppa

CMerny

y

nocTeneHO

3a

KncejiHHe

y

Ha.na3H

ca

ca

KaTKa.ua

(136°).

jcoxojia,

ca

e T H JI.H H T p H T

KOJ'H H3 OBOr H a c T a j e

1

'

1,4)

cana

nycTH ce

150

Aa

nojiOBHHa

K0HAeH33T0p0M H

ce,

npoKjbyqa pacTBopa

cpeAH>e

mi amoxojia.

y

BejiHHHHe

PeTopTa

ce

Kap6oHCKe

KHCCJIHHC H H>HXOBH n p o e r H

123

aepHBatH

nawjfaHBo 3arpeBa Ha nemqaHOM KynaTHJiy. FIOIIITO OTnpHJiHKe jeAHa TpehHHa c a A p « a j a npeAecTHAHine, noMeiua ce A p y r a nojioBHHa npoKyBaHe a30THe KHcejiHHe ca 100 mi amoxojia KOJH

c e cTaBH y ryóyc

H OBa CMeuia AOAaje nojiaico H3 jieBKa 3a K a n a a e ,

p e T o p i e . O n e p a a w j a T p e ó a Aa c e

6e3 .npe-

H3BEAE

KH^aita, j e p MemaBHHa ajiKoxcuia h a30THe KHcejiHHe He CMe Aa c e .Aa CTOJ'H nyxíe AIECTHJIHCAJIA

TOJIHKO,

.Aa 6H c e yKJi0HH0

cyuiH

cone

H3H3A

H

OBOM

OCTA^O

nyTa

ABA

joiu

ca ca

JEAHOM

KcuiiiujyMXJiopuaa

JíecTHJiauHjoM Ha y

je

AA

mi,

5 0 — 1 0 0

J.

BOAOM,

BOAOM

H

je

3AMTHTHE

OA

BOAE!),

peKTHy, Ha np. y njiaMeHy, pacna.ua e K c r u i o 3 H B H o ; OH enana y HCTy KJiacy MaTepnja nao HHTporjinuepHH H 3 a f o n a 3 H ! ETH.1ajiKoxo.11 ce -He OKCHflHIUe 1 H C T O M 330THOM KHCejIHHOM nOfl OriHCaHHM yCJIOBHMa, Beh ce CaMO •ecTepwíjjHKyje. /I,0B0JbH0 je MetjyTHM na cy npncyTHH cano TparoBH a30TacTe KHcejiHHe, na Jia HacTynn OKCHjiaiiHja. ASOTMOHOKCHA, Kojn Tajia Hactaje H3 a30Tacie KHcejiHHe, oiiMax ce nouoBo oKcanmiie y NO z , oKcnjiauHja oa M3JIHX noieiaKa mwpH ce cyKixecHBHo aaae, .noínja CBe BHwe y 6p3HHH ycjieji peanunoHe TonJioTe Koja OB,ne HacTaje, H npeTBapa ce Haj3a.a y fiypaH eKcnjio3HBHH npouec. PeaKUHje oBe Bpcie, KOA Kojnx MeljynpoiiyKTH noBehaBajy .nporpecHBHO 6p3HHy, 03Ha>iaBajy ce nao „ a y t O K a T a J i H 3 e " . FlpBH ripoayKT O K C H a a u H j e ajwoxojia je a u e T a j j e x a i , a Bastan KpajfbH mpoflyKT je (pyjiMUHCKa K H c e j i H H a , naja ce Mowe H30Ji0BaiH caMO y npncycTBy c p e ó p o B H X H JI H J K H B H H H X j o n a . C OBHMa oHa CTBápa tjjyjiMHHaie nodojaHe •npeMa a30TH0j KHCCJIHHH KOH. KOJHX Tpeóa aa ce npemocTaBH, CJIHHHO Kao KOH MepKyuwjaOHHjia, xoMeonojiapHa — a He joHCKa — Be3a. CTBapaite (JtyjiMHHCKe KHcejiHue je npoy3poK0BaH0 peaKTHBHoiuhy MeTHJiHe rpyne, Koja je aKTHBHpaHa cyceAHHM KapóoHHJioM aJiaexH.ua fH Koja npywa a30TacT0j KHCCJIHHH Meció 3a Hanan. I~Ioje.nnHH cxa^HjyMH oABHjajy ce npeMa (OBHM (JiopMyjiaMa: HC • CHO H

3

C

• C H O

HC

|| N O H O

2

N

COOH

02N • C

||

>

COOH

||

N O H

N O H

X

->

/ C =

N O H

+

C0

->C =

2

N 0 H

+

H N 0

2

H /

A30TacTa KHcejiHHa aejiyje oBae Ha a^Koxo^ Ha cjinqaH HamiH, Kao noreHH npn cTBapaH>y x^opoiJiopMa, joaoijjopMa. r) 300

CanoHH(J)HKaixHja

g 6mio

Koje

MACTH

ca 300 mi OKO 5 n-pacTBopa 50 mi pacülBopa noc^e .AOAAJE

JEAHOR

ce n o

caTa 100

M

HJIH

ac

T H

yjba

ÓHjbHor

H ^ H

(OKO

MOJia)

L/3

mi

aejiyjy xa-

Y J B A

ce

canoHH(J)HKyje

HaTpujyM-xHApoKCHAa:

H 50 mi H 2 0 ce 3arpeBajy, AOAA

UITO

joiu

pacülBopa

75

mi H

pactüBopa.

BOAE.

Mopa

n0T0M ce

riocjie NECTO

enna Macül

jota J E A H O R A A ce Mema H

a

CATA CME

OpraHCKO-npenapaTHBHH aeo

124

Aa ce 3arpeBa caMO AO c^aöor K J B Y Q A I B A . n o c j i e A A J B H X 4 caTa A O A A ce OCT3T3K pacTBopa, ano je noTpeÖHo npeTxoAHO ce Aoanje HcnapeHa BOAa. OneT nocjie jeAHor caTa AOAa ce 1 / 4 jiHTpa BpAe H KyBa ce Aajbe, cBe AOK He HacTaHe rycTa xoMoreHa ¡naca (OKO 2 — 3 caTa). T A A A ce, 6pH>KJBHBO MíiuajyhH, AOAa 2 — 2 1 / ¡ ¡ jnrrpa Bpyfre BOAe, npa qerviy Hacraje rycTa npoBHflHa ace^ATHH03HA Maca. H A J 3 A A ce HCOJIH ca 100 jg' Kyxuwcue cojiu, A O K joui KJbyqa H ocTaBH ce Aa CTOJ'H npeno Hohn. OnepauHjy je norpeÔKO H 3 3 0 A h t h y B C J I H K O M eMajjincaHOM cyAy 3Ôor jaKor neHyiuaita. nocjie oxjia^eita, HAyher jyTpa meajin ce oxJiaijeHH KOJiaq canyHa H onepe OA JiyjKHue. KOJIAQ ce T3HKOM JKHIJOM Hceqe Ha Majie KOMa^e KojH ce ocTaBe Aa ce BHiueHeAejbHHM cTajatteM npocyme. HaTpHjyMOBe COJIH BHUIHX ivíacHHx KHce^HHa cy y xjiaAHoj BOAH TeiiiKo,. a y Tonjioj BOAH JIAKO pacTBopjbHBe. A K O Mana KOMA^AH canyHa pacTBOpnMO y noTpeÓHoj KOJIHHHHH Kjbyqajie B O A E y Ma^iOM nexapy H nycTHMO Aa ce oxjiaÄH, AOÔHhe ce nnxrajacTa Maca. PAß« BOAH,

HA

npeiHiiihaBaita M O » E Bpejio HCOJIH H NOHOBO

MA^A KOJIHQHHA AJIKA^HJA,

AA

ce 20—30 g

OCTABH

pacTBop« y K,FT>yqa.Jioj

AA OMBPCHE;

Koja j e 3 a o e r a ; i a

y

THME

ce

YAA^YJE

CNPOBOM N P O A Y K T Y .

PeaK-

ocraje ajiKa;IHA HA jiaKMyc H K Y P N Y M A xapTHjy. M E I J Y T H M X H A P O ^ H 3 A CACBHM iHCTor canyHa HHje TOAHKO jana AA ce AOCTHTHC KOHUCHTpaunja O H - j o H a , AA 6H ce oöojwo (J)EHO^(J)TAJIEHH. UHJA

H a n n H A O Ô H j a i b a C J I O Ô O J H H X M a C H H X K » C E A N H A : OKO 150 g CHpoBor BJiajKHor cauyita 3arpeBa ce y jiHTpy BOAe cKopo AO Kjbyqaiba; raAa ce AOAa y 3 Aoöpo Meniate 2 n-cy.\iûopna mcemna, CBe AOK pacTBop HE pearyje jacHO KHCEJIO Ha KOHPO xapTHjy H AOK ce CMeuca MacHux KUcejiuHa HE H 3 A B O J H Ha noBpiiiHHH nao yjbacTa Maca. EIOLUTO Majio nocTojn HA x ^ A A H O , OBA oqßpcHe, ano ce noui^o OA HBPCTHX Mac™. Kojiaq ce noAHrHe, HCTOÌIH ce join JEAHOM Ha BOACHOM KynaTHJiy y M3JIOM nexapy ca HeuiTO BOAe H noHOBO ouBpcjie KHcejiHHe AecTHJinmy ce y BaKyyMy. T . K. 220—225° Ha 1 2 mm. AKO ce canoHHcjjHKyje yjbe, OHAa je canyH Man.fi' qBpcT H KHce/iHHe caMO Ae^iHMHHHO KpHCTajiHuiy (3aniTO?). Y TOM cjiyqajy eKCTpaxyje ce eïïipoM H AaJbe ce paAH Ha yoÖHiajeHH HanHH. T j i H u e p H j i : DiHiiepHH ce Hajia3H y MpKoj OUCAHHH, Koja ce Hajnpe T3MHO HeyTpajiHiue COHOM KHCCJIKHOM («HAHKaTop KOHro-xapTHja) MyhKa ca JKHBOTKH>CKHM yivbeM 1 , Aa ce y A a ^ e H3ABojeHe MacHe KHcejiHHe, npoaeuH Kpo3 HaôpaHO ueAH^o H TaAa KOHueHTpHine HcnapaBaibeM y BaKyyMy noMohy anapaTa onncaHor Ha CTp. 27. KaAa ce nocjie n3BecHor BpeMeHa H3ABOJH Kyxuwata co, KanHJiapa I O T K B A npecraje Aa AejcTByje H TaAa ce HacTaBJba HcnapaBaite Ha BOACHOM KynaTH^y. JaKO KOHueTpoBaH pacTBop ce OCJIOÔOAH KyxHHjCKe COAH ae^efceM HA BaKyyMy; co ce Hcnepe ca MaJio') MHiuhefte ca jkhbothhjCKHM yr^eM je weeTO H3flHiiiHo.

KapöoHCKe KHCEJIHHE H H>HXOBH npocTH AEPHBATH

1!, 8

ajiicoxojia BOÄe.

(JwjiTpaT ce (oneT y BaKyyM-öajiOHy)

H

IIOHOBO

OcTaTaK c e anreprniie ca 150 ml ajiKoxoJia

125

cacBHM

npoue^H

H

O O I O Ö O Ä H

Kpo3

MSJIH

Hyq, a noTOM Hcnepe ca 5 0 ml a.iKOxoJia. npoueljeHH aJiKoxoJiHH pacTBop ce

j e Moryhe

LUTO

c e npeöauH JiHiiie

H3

BHiue

cnnpaiteM

Hajnpe

OBOR

KOHueHTpmiie

ca

Ha

KynaTHJiy,

B O Ä C H O M

a^iKOxo^a y Ciaisen-OB

M3JIO

a;IK0X0./I

BO,a.a

H

H

ôajioH

r^aBHa (JjpaKUHja ce xBaTa H3Meijy 1 8 0 H 195° Ha 13 mm. Ha

6H

ce a o ö h o n o m y H a

Jiaunja ^a c e

MacTH.

KßaHTHTaTHBaH

MacTH min y j b y a a j e

„jojiHH

rpaMHMa, KOjy XGMHJ'CKH B e 3 y j y ryönx

OpHHOC OKO 3 5 g.

6e3BO£HH iviHuepHH,

H

Mopa ÄecTH-

IIOHOBH.

AHaji¡i3a HeKoj

HHCT

ÄecrH-

y BaKyyiuy.

rjiui}epuH

HAJ3AÄ

ocTaTaK H

H3pa3 3 a 6 p o j yrjbeHHKOBHX A B o r y 6 n x B e 3 a noA THM n o j j p a 3 y M e ß a M o

6poj";

100 g

neKe MacTH. y

B e 3 a y opraHCKiiM jeAHH>eibHMa

0ÖHqH0

HOBHje

noMohy

KOJiHiHHy

joAa

y y

BpeMe OApeljyje c e 6 p o j ABO-

6 e H 3 0 - n e p K H c e J i H H e

(ynop.

CT. 9 5 ) . j o Ah o r

OjipefjHBa ite

MepKypuxjiopuAa Mcuiajy.

noceöno y no 5 0

rioc^e

12-'iacoBHor

ópoja,

ml

PacTBopn

micTor

ce

2,5

mmnaRKoxona

cTajan>a c e y jeAHoj

n p o 6 n cm 1 0 ml

JORO,

mirror

g

h 6HCTPII

ce

h

3

pacTBopn

OApeAii

THTap

g no-

jo.ua

ca

n 10 pacniBopoM rauocyjitpama, AOAaBiim 1 0 mi lff':0-no¿ pacawopa K], 0 , 5 — 0 , 7 g Macinìi Koja c e HcnHTyje pacTBop« c e y 1 5 ml XJiopotpopMd y cyBOM e p a e H M a j e p y O A 5 0 0 ml; TOMC c e AOAa 2 5 ml THTpiicaHor pacawopa joua, A K O nocjie K p a b e r B p e n e H a 6 o j a pacTBopa npelje y C B C T J I O Mpny, OHAa j e noxpeöHO j o u i 1 0 ml p a c T B o p a joaa. riocjie 4 c a i a r p e ô a 6 o j a join yncK ;ui ocTaHC T 3 M H O Mpna. Caaa ce / l o a a 2 0 ml 1(P!0-HO¿ pacaißopa KJ n T i n p i i m e joui upiicyTHn joA Kao U I T O j e HanpeA pe>ieHO. M3paqyHaBaH>e c e BpuiH Ha ocHOBy aeiJjHHimiije „joAHor 6 p o j a " . H c n i i T a j c B H H> c K y M a c T, h ™ M a c u l i n o B o y jb e, muí n a H e n o y jb e. üa

c a n o h il c|) il K a u H o H h

c e ojpejiH

G p O j1

n e n e MBCTH KyBa c e 0 , 5 — 1

cyn-

g

ml n/2 a.'iKoxoimoi pacntBopa KOH 1 / 2 caTa c a ycripaBjbeiniM KoiijicHsaiopoM TiiTpHuiy HeBe3aHe aji«ajnije c a n¡2 HCl ynoTpeôHBuiii çeHOflcJjTa^enH.

cxaiinc ca 1 0 H

noTOM

iMeioaa je n

H

a BC33HUX

onuuer

Kiicejiiiua

ËKBHBajieiiTHa

3i¡aiaja, y

jep

Te>KHHa

a •

ecTpa =

y T p o u i e H o r HopMajiHor pacTflopa

b — ml

A03i30JbaBa

A3 c e OApeAH

e KB HB a n e h T h a

ie-

ecTpuMa. 1000 ^

npu

qeMy j e a

H3MepeHa

uojinquua

y

g,

ajiKajinja.

J l a n e H o yjbe je HajBaîKimje Met)

T 3 B . „ c y U I H B H M yjbHMa". IIOA T U M c e

yjba, Koja c a A p a i e jaiy Aa AiipeKTHO aAHpajy ibHXOBe n p o a y K i e TpaHc^opMauHje. M a c i n n o B o ce H c e 3 a M 0 B 0

y ."b e n a n p . „He c y i u e " . / I a u e i i o y^>e c e y n o T p e f í ^ a B a

Kao Be3HBHO c p e a c T B o y c m i K a p c T B y

Ba3flyuiHH

K H

cernii y

C]7H31

KHceoHHK cTBapajyhH

iBpcTe

n Koja c y c T o r a ' y

nepoKcme

H

yjbaHHM ôojaMa H 3a H3paAy 4>npHnca.

8. Aerpa^ai;nja KapôoHCKHX KiiceJiHHa flo npBor H^ylter Hn'wer aMHHa a) X 0 ( J ) M a H 0 B a y 80 g =

ôajioH

OÍ;

p e a K u h j a. M e T H J i a M H H H3

1 / 2 JiHTpa

2 6 ml ôpoMa

5 0 g icajiujyMxuapoKCUAa

CT3BH

H TOMe ce

1

floA THM c e NOAPA3YMEBAJY mg B . 15, 7 6 2

(1882);

30

g (0,5 MO^a)

ao^aje y3 ^o6po

y 3 5 0 ml

2

ce

B0JI,e,

KOH,

B. 17, 1406 N 1920

(1884).

MacTH

ai¡ewaMUMa

x^a^e»>e

CBe ÄOTJie,

Koje 1 g

ai;eTaMH^;a2

Ä O K

y no^eTKy

yTpouiH.

ca

pacTBop OÄ M P K O

OpraHCKO-npenapaTHBHH «eo

126

upBeHa 6 o j a He npeije y CBCTJIO ynyry, cnpeMjbeHe

Aeo

KaaHjyMOBe

3auiTo h e 6HTH noTpeÓHo HajB&hH

.nyjKHHe.

Ta^a ce

OBaj

pacTBop

nycTH Aa

HCTeqe H3 aeBKa 3a n a n a i t e 3a HCKOJIHKO MHHyTa y HenpéKHAHOM

MJiasy

y pacTBop OA 80 g KaaHjyMXHApoKCHAa y 150 mi BOAE, KOJ'H c e

Ha;ia3H

y óajiOHy OA 1 JiHTpa H KOJ'H j e 3arpejaH Ha 70—75°. H a OBOJ'

TeMnepa-

TypH c e apacH

CBe Aoivie,

6e3ÓojHa

(1/4—1/2 q a c a )

H TA.UA

K0HAeH3aT0p

je

AOK peaKUHOHa

c e MewiviaMUH

cnojeH

ca

peannHeHTy 1 cm Ayóoko

jiyjiOM,

CMerna

He nocTaHe

npeAecTH;iHiiie ca BOACHOM napoM;

HHJH j e

Kpaj

ypofteH y TeraocT y

( y peiiHnneHTy c e Hajia3H 100 mi OKO 5

Kucemne).1

MHM k o h a c h 3 3 T y K0HAeH3aT0py

HcnapH c e

ca^p^aj

peuHnneHTa

He p e a r y j e

AO cyBa y nopuejiaHCKoj

n-cone

ajiKajiHO,

BHuie

3Ae./IH Ha BO-

AeHOM KynaTH^y, OCTBBH n p e n o HohH A a CTOJ'H y eBaKyacaHOM eKCHKaTopy, Aa 6H c e yAajbHflH ca aucojiywmM

nocjieAifcH

oeraim

BOAe,

H cacBHM cyBa c o

npoKyBa

OJIKOXOJIOM; npH TOMe aMOHujyMXJiopua o c T a j e HepacTBopeH.

FIOUITO c e npoue^H, ó n c T a p y ca Maao mmpuuia y jeABa KHcejiOM BOAeHOM pacTBopy. 6) C u r t i u s - O B a BeH3xnApa3HA : 2

pea

K

i; H j a.

24 g éwunecwpa

EHH/MHJAHAT

6eH3oeBe

(CT. 118) 3arpeBa c e ca 9 g xunpa3UHxnp,pama ca M3JIHM ycnpaBJbeHHM KOHAeH3aTOpOM.

THJiy

Kojn c e CTBopno Moryhe

6ojbe

Mewujiamoxojia.

mcenune

6 cara

— 3/20 MOJia

Ha BOACHOM

iiphjihkom oxjialjeii>a, nocjie Henor BpeiaeHa c e

oueAH

Ha BanyyMy H n c n e p e ca Majio vicaom

AKO je n p n H o c

Kyna-

HBpCTH KpHCTajIHH K O J i a i , IUTO

je

oxjiaijeHor

c a a 6 H M n a ) K J B H B O

eKcmioayje

pyKyje.

AO K p a j a A e c T H j i a i i H j e XlecTH^aiinja

npH

6p30M

KOHitcmpoBaHOM

Kpajaer

YnoTpeÓH

Tp e 6a

Aa

saniTHTHe Haonapn

ce CB e

4>eHHJiiiHaHaTal npoAyKTa

ce

BpniH

y

HCTOM

CJiyjKH 3a pa3JiaraH>e, no MoryhcTBy y Claisen-OBOM Ha KOJ'H ce H a ï u e c ™

3arpeBaH>y,.

H2S04,

Kanajiapa H TepMOMeTap,

ôajiOHy,

KOJ'H

ôajiOHy OA 7 5 — 1 0 0 ml,.

j o i n npe Hero HITO ce H3-

BeAe pa3JiaraH>e. Cße Mopa Aa 6 y A e AOÔpo cyBO. y

6anony,

Koco N0CT3BJBEH0M

HaBy^eH

KOHAeH33TOp —

MSJM

Aa 6H cnpeiHJia 6 0 — 7 0 ° 12 T0n/I0M

yjia3aK

BJiare

g 6eH3CL3üw

BOÄOM

ca 40

HanyHi'eHoj

npeKO HHje j e iieBH 3a K0HAeH3aiiHjy

Ha r o p a e M K p a j y ce HaJia3H ueB ca Ç a C l 2 H3 Ba3Ayxa —

ml óensom

3AejiH,

T3KO

Aa óaaoH

AHO 3Aejie, NPH l e i u y noHHH>e Aa ce JKHBO nonycTH,

IIOBHCH

oxjiaAH,

npeyAecH

ce

TeMnepaTypa

anapaTypa

Hajnpe 6eH3o;i noA

AO

3a

OÔHHHHM

3arpeBa

(cyuieHor

ce

OKO 80°,

npHTHCKOM

33THM

KAAA pa3BHjaft>e ce

n y c r a Aa

NOA npHTHCKOM OA 2 0 — 2 5

RecTHJiaT

Mopa

Aa

ôyAe

mm.

Ha KJbyqajioM BOACHOM K y -

T . K. 60° Ha 20

Kao BOAa

ce

y B3KyyMy H AecTHJiHiue

NATHJIY, a OAMAX 33THM, OXJISAHBIIIH NPETXOAHO KYNATHJIO AECTHJIHIUE

ílujaHaíñ

HA

He CMe Aa A O A n p y j e

pasBuja a30M.

Aecra^aiiHjy

JiaraHO

H3H3A HaTpHjyMa) y

mm.

(penujig,

llpHHOC j e 7 — 8

ÔHCTap H T p e ô a

OAMax Aa

ce

CT3BH y 6 o u y h A o ö p o 3aTBOpn (Haj6oA.e 3aTonH). ripe CTaHiia

Tors

Koja c e

cnna c e HCKO^HKO

Kann

y Ma;io

BOAe.

CTBapa j e A m j j e H H j i K a p ó a M H A -

i>eHHJiypeTaH.

Äpyra

jeAHa

npoôa

KpHCTajiHa

KaKO

cana ce

y

OBaj

cyn-

HacTaje? h

ÙJIKOXOJI

pa-

CTBapaq Hcnapn. HenpoMeiteHH a3ua

(OKO 2 g)

KyBa ce

y

5 ml

amoxojia

ancojiyraor

V a caTa ca ycnpaBjbeHHM K0HAeH3aT0p0M2. Floche KOHueHTpHcaita HcnapaBAH>EM HCKPHCTAJIHIUE TAKOÎJE Pacna^aae BehHHOM ca

YPEIAHA

y 3aTon^>eHoj iieBH

iwaHjHM

{pemuiypewaH.

npHHocoM,

HA

T . T. 52°.

a M H H, C 0 2

H ajiKoxoji

ca COHOM KHCCJIHHOM.

pa3Jiaratt>e

noMohy

h3boah

n o r o A H H j e je,

AecTH^aunje

ca

ce

MaAa

KajiiiHjyM-

XHAPOKCHAOM. riOMeuia ce jiHqHHOM

AOÓHJ'CHH

rauienor tcpeta

(peHUJiypewaH

KOJ'H npejia3H, MO)Ke, ca Maao 1 1

ca T p o c T p y n o M TCHCHHCKOM KO-

H X e c m n H i u e najKJbHBo H3 Ma^e p e T o p T e . yiaeiuHocra

G. Schroeter, B. 42, 2339, 1909. Th. Curtius, B. 27, 779 (1894).

AHUJIUH

AA c e peKTHtJïHKyje, H3 M a j i o r

128

OpraHCKO-npenapaTHBHH

•öajiOHHHha, noMohy

ajin

y

peaKuwje

CBanoM ca

ripH p e m a B a i t y

c-ziynajy

Tpeôa

neo

ra

ÄOK333TH

nao

aifeuiaHUJiuM

nwiatba c T p y K T y p e n e c i o HacTaje noTpeôa, na ce ynajbH KapöoKCHjma

r p y n a Koja j e Ha np. H a c í a l a nejcTBOM o K c n n a m i j e H na c e Ha Taj HamiH MojieKyji „ o n r p a n H " . HajjenHocTaBHHjn n p o u e c oBe BpcTe, «OJ'H

ce

nocTHwe

H

K p C M o M,

x j i o p H H M

necTHJiaunjoM

nene

ejiHMHHHcafte

COJIH ca

noHeoe

yrjbennHOKCHna,

H A T P N J Y M X H A P O N C H J O M

(y

oöjiHKy

iCOiiHcaHor Kpeqa) : R

COONa + NaOH

eehiiHOM He Teqe rjiaTKO H noBonw no

RH +

Na2C03

HeKor yrjboBonoHHKa,

ca KojHM TeuiKO M o r y

na ce

jiajbe peaKUHje H3Beny. Hoffmann-oßa,

C Tora c y o 6 e cponHe peaKUHje onrpaljHBafoa KHcejiHtia, on

a M H ,U a

KHcejinna

Curttus-oBa

H

on

xnnpa3Hna,

on

Koja noJia3ii

BejiHKor

npenapaniBHor

3Haiaja. 06e cone

Ka

O M o r y h a a a j y , na

HCTOM UHJby

HejcTBo

ce

npeno

XHnoöpoMHTa

NH 2 -rpynH 6p0M0M.

noôiije

HCTOr

IlpBH

npHMapHH

3MHH

MçfjynponyKia,

Ha —

CONH2-rpyny

Hnyher

HHHHXOBH

HnTpojeamfceH>a

III.

129

pejiyKUHOHH npcwyKTH

'HHTPOJE,HHH>EH>A H H,HXOBH

pe^yKi^HOHH

npoflyKTH

1. HHTPOMETAH 1 2 0 0 ml BOAÊ H e y T p a j i H i u y NINPOKOM n e x a p y ; K TOME c e SOJA p a c T B o p OA 7 5 g HawpujyMHuüipuma y 1 2 0 ml BOAC. OKO 1 0 0 ml OBE C M e r n e n p e H e c y c e y ô a j i O H OA 7 5 0 ml HA KOJH c e CT3BH ; i e B 3 K 3 a KANAKE H KOJH c e OCHM T o r a BONE c a K0HAEH33T0P0M NOCT3BJBEHHM KOCO H A A O ; i e . I l p n 94

g

TÄHHO

ce

CHajKHOM B3TH)

xjiopcuphemne

3arpeBaii.y

noHHfte,

H3ABajan>e neHHM

C0

,

AOTHuaaeM cyBHiiie

ce

peuHriHjeHTy

y

yjbaHe Koja ce

HHTpoMeTaH, npeuiao.

100

no

35

g)

BOAe,

AOÖpO

npHHOC

TCJKH ce

3a

HHM H

(nocTeneHO

óypHa

OApJKaBa

Kanaibe,

a^H

ce

BOACHOM A6CTHJI3TOM

npejia3H

cjioj.

Kjbyqa,

pacTBopa

ca

ca

peuHnnjeHT

pacTBopeHor

H joui

3arpe-

peaKiiHja, y

TOKy

He

AonyuiTa

H

napoM Burne

He

y3

nocTe&&

H3Aßaja

OCyiIlH

AecTHJiHiue.

HHTpOMeT3H3

XßATA

100

join

noejia3e mi

c e OKO

Ce

AOA3 H

OHOM

T3A3

1/4

ijeJiOKynHe

ACCTHJI3T.

ÓHCTap

KaJlliUjyMXJlOpUffOM

KOjH j e

p3HHje T . K.

ACCTHJIHllie.

AO101°.

TeopHCKor).

AJIHTJIATHHHO HHTpoje,HHH>eH>e; KOÄ BHIUHX MATTE rJiaTKO. MexaHH3aM peaKUHje j e jacaH:

je Haj;iaKiiie npncTynaqHO

AO6HJAH>A

Merana

HHTpocHphcTHa

oneT

H3HJI33H

20—24 g (33—39% OA Kolbe-ovz

npeAecTHJiHiiie

HHTpOMeTaHa.

jeAHOM

Tora

AeCTHJI3T

HHTPOMETAH xoMo^ora

H3 .neBKa

nocjie

H3AB0jeHH ÓHjeH,

pacTBopa

HuMpoMeniaH

MpejKHiiH

BOAC, O A n p B o r AECMNATA OABOJ'H a n p e o c T a ^ H b o a c h h CJIOJ CJ'CAHHH c a A^CTIWIATOM K o j n j e O ß a j p a c T B o p c e 33CHTH K y x H i t c K O M COJIH, ( H a CBSKHX

joui

noc^e mi

KJbyqaite

Kao

Ha

pacTBop

y3

npoMeijH

caApJKH

y

wiu

LUTO

Hero

ce

6ypHa.

Kann,

KOJiHHHHe

npe

Koja

óy^e

( 5 3 g)

coaoM

Ha Ba6o-Ji&BKy

Beh 2

pacTBOpeHe y

mcenune

6E3BO^HOM

ca

Teie

Koja ce Hajnpe CTBapa, pa3Jia)«e ca Ha C H 3 N 0 2 H CO¡¡

KHceJiHiia

H3 CJIHIHHX PASTORA, KOJ'H o6jamit>aBajy pa3JiaraH>e MajioncKe KHCEAHHE. OCTAJIH H H T p on a p a (JJ H H H ce BEHWHOM A o ô n j a j y npeMa n o c T y n K y Kojw j e OTKPHO V. Meyer — peaKuwjoM AJIKHJIJOJUUA ca cpeöpoHHTpmoM. TaKoije METOAA KoHOBaJiOBa — 3arpeßaH>e ca BEOMA pa3ÔJiaiKeHOM 330TH0M KHCejIHHOM HA 120 — 130° — ÄOBOÄH HeCTO KOÄ 3aCHheHHX yrjbOBOÄOHHKa, HapoMHTo OHHX xiijipoapoMaTHiHor pe^a, ao UHJBA. O (PEAHIBHIPOMCIAHY roBopnhe ce y OAEJBKY V I , 8 FloTceTH ce Ha H30MepHjy HHTpoje,nHH>eH>a ca aJiKHJiHHTpHTHMa! KAKBA PA3FLHKA nocTojH y peaKUHjaMa? RIPHMAPHH H CEKYHIIAPHH HHTponapaijJHHH cy HeyTpajiHe cyncraHue, AJIH «ejCTBOM (Hanizsch): AJIKAMIJA npejia3e n p e r p a l j H B a f t e M y COJIH H30MEPH0R aci-o 6 n 11 K a R

\

R

>CHN02

>

R / OBO je onujHpHHje OrJiefl: pacTBopa

Ha

H

Aa

nycTH

TpajHor 1

OAEJBKY 1

ml

xapTHjy.

oôojeita

0

A H

o i a y i o M e p n j H

T3Aa n/10

ce

yTpouiH

ce

( V I , 8).

BOAH H

y AOAa

pacïïiBOp

J. pr. Ch. 5, 429 (1872); Steinkopf,

ripaKTHKyM opraHCKe xeMHje

N =

/

HumpOMemana

K3NJBE H3 ÓHPETE

upBeHKacTor

H. Kolbe,

y

ce

jiaKMycoBy

>C =

R

MTO

PacTBopH

\

yTBpA«

HeiiiTO

peaKUHja

(peHOJitpwajiema flö

HawpajyM-xuapoKCiißa.

OBor

OKO

2

ml,

B. 42, 3438 (1909).

IIITO

je

3H3K

130

OpraHCKO-npenapaTHBHH

jieo

Aa j e H3 H E Y T P A J I H O R H H T P O M E T A H A HacTajia je^Ha K H C C J I H H 3 , aci-HulüpoMeUlaH H 2 C : N O O H . Je^Ha Majia npo6a Tora pacTBopa Aaje KAO KpB U p B e H O o ö o j e i t e ca (pepuxjiopuMOM, IIITO je KapaKTepHCTimHO 3a ßc/'-jeÄHibeiba. CO^H ac/-jeAHH>eH>a ce jaKo X H A P O J I H T H I J K H pa3MHeM n/10 pacüiBopa xuapoKcuaa paCTBop ce 6ojn HHTeH3HBH0 upßeHo. AKO ce nooie Äo^aBaita 10 ml paCTBopa XHÄpOKCHÄa CT3BH caAa 5 ml n/10 com mceuune, pacTBop he ce o6e36ojHra, jep 0CJi060^eH0 ac/'-jeAHibeite noTHCKyje xHÄpoji«3y CBoje COJIH. TpaHC(J)opMaaHja H 2 C : N 0 2 H y H 3 C • N 0 2 AemaBa ce TaKo 6p3o, Aa ce 3a HCKOJIMKO TpeHyTana n0H0B0 Bpaha. EHeprHqHOM pe,nyKUHjoM HHTponapaKHO HCTa KOJIHMHH3 aMOHujyMxjiopuaa. 3aTHM ce AOAaje Ma^o no Majio y3 xjialjeifce (TeMnepaTypa OKO 10°) H CTajiHO MyhKaite TpocTpyKa KOJinmiHa ifunm y üpaxy. ripoue^eHH pacrßop peAyKyje ÜMOHiijaiHU paciüBOp cpeöpa a a

a j w c TOM rpaayaJiHOM

öpoMHHipojeAHneite,

L

IV

Br ONa J

Br

rpa^H

c e K y H i a p H H M

ca

npxtiapHHM

T3B.

Ha n p . :

+ Na Br

Br

HHTponapacjjHHHMa

nceyioHHipoJie,

KOJ'H

cy

H H i p o j n e Kao

HHTpo30-

JEÄHH>eH>a o6ojeHH 3ejieHo HJIH iuiaßo.

a)

H 2C = N = O H„C | + "ONO OH

6e3

CTBapa

MHOFO Beha KOÄ HHTpoje.nHH>eHia.

b

ONa

H ceKyHÄapHHX

TO h e pehw ÄeinaBajy c e n o a ycjioBHMa n o a K O j H M a c e

->

TH22C — N = O 1 rH | | \ L NO OH OHJ

-»>

HC - N0 2 + H 2 0 II NOH

III, 1

HNTPOJE,NHHJEH>A H H>HXOBH PEAYKUHOHH npoayKTH

131

CHg • C • CHg 6)

CHo • C • CH, '3 II

-»

0 = N—OH

Or;iefl:

MeTHJiHHTpoflHS

CTBopH ce y 30 ml 2 n-pacwBopa H noMeiiia c e

CH3 • C • CH, 3

NiO /OH 0=N/ \0H

+ H20

|\NO NO 2

KHCCJIHH3.

3,2 g HumpoMemana

naïïipujyMxuapoKcuaa

y 3 x^aJjeite

ca KOHU. pacTBopoM 3,5 g HawpujyMHuUipuwa.

HapaHijacTO

acyr,

a

JieAOM

Ta^a ce,

xjia^ehH AAJBE, nycTH AA Teqe K TOME 4 N-cyMüopna mcejima K a n a k e AO T p e H y r a a na^a npBOÓHTHO

paHe

H3 JieBKa 3a

T3MHO

UPBÉHH

p a c T B o p ' nocTaHe

KajmjyMjoAHA—cKpoóna

xapTHja

join

He normaBH.

OX;I3AH noHOBO BOACHH pacTBop,

T a ^ A ce e K C T p a x y j e AßA nyTa ca empoM,

AOAaje My c e noHOBO Kan no Kan cyMnopHe KHcejiHHe CBe-Aoivie, AOK ce jacHO He nojaBH a3omacma

mcemna

H T3Aa 3aa./iK3JiHme noHOBO

ca 5 n-

pacTBopoM xH^poKCH^a AO jaKO HapaHijacTor o 6 o j e i t 3 . T a ^ a ce oneT AOAA ce j o m Mome AOK333TH

A3je TOJIHKO KHcejiHHe,

a30TacTa KHcejiHHa H

joui c e ÄBa nyTa e K C T p a x y j e eTpoM. CjeAHiteHH eTapcKH ekCTpaKTH c y m e ce 2 ca-ra KajmujyMXJiopuaoM,

x^a^ehn cnojb3 a c a o m .

T a ^ a ce y

óaAOHy

ca KanHJiapoM oTCTpaHH e i a p y BaKyyjviy Ha BOACHOM KYNSTHJIY OA 15—20° H A o ô w j e ce Kao ocTaTaK OKO 1 g Jieno KpHCTaJiH30B3He, CASÖO >KyTo 060jeHe MewujiHuwpojiHe

icucejiune.

ü p e n a p s r MOJKE AA ce OAP>KH C3MO HCKO-

JIHKO C3TH Ä3 ce He pscnsAHe. HCNNTSJ H>eroBo noH3m3ii>e npeM3 3JiKaJiHjaMa. C p e 6 p.o (J) y JI M H H a T 1 . mcejiuHe

pacTBopH ce

aaoniHe icucemne MHHOM BOAE)

y 4 ml

0,5 g

cBejKe - cnpaBJbeHe

BOAe H 3 a r p e j e

MewujiHuwpojiHe

AO K J b y ^ i f e s ca 1 ml 5 n-

(KOHU. KHcejiHHa en. T. 1,4 pa3Ô^aKH c e ca HCTOM 3anpe-

H 4 ml 1 0 % - H o r

pacîûBopa

cpeôpcmiiwpaïïLa,

HA CAOÔOAHOM

njiaMeHy y m n p o K o j e n p y B e ™ . n o c j i e KpaTKor BpeMeHa HacTaje p e a K i m j a y 3 CH35KHO pa3BHj3ifce r s c a (NO), cpeôpocpyjiMUnam.

a HCTOBpeMeHo ce H 3 ^ y q y j e KPHCTSJIHH

K y B 3 ce AaJbe j o m h c k o ^ h k o MHHyTa CTaAHo MyhaKajyhH,

nycTH Aa ce OXJISAH,

npoAyKT o u e ^ H

n p o ô a OA OKO 10 mg cyrnn ce,

3 a a

Ha BaKyyM H o n e p e BOAOM. ce

HE

Tpjba,

Majia

Ha KOMaAHhy

no-

po3Hor nopue^3H3 H ncnHTyje 6pn33HTHOCT y n^3MeHy H y A s p o M ueKnhs. ynoTpeÔH

33uiTHTHe

r^3BHa c e

KOJIHHHHA

CT3ft>y TpeÔ3 H3ÔehH

Haoqapnl jom

BJia>KH3 CT3BH

y e n p y B e T y — H y OBOM

CB3K0 npHTHCKHB3H>e MeTaJIHOM UinaTy^OM HJIH M3-

K3KBHM TBpAHM npeAMeTOM — H n p e j i n j e ca 2 ml KOHI\. cone meemne. TOME MOME Aa c e o c e m

MHPHC CJIOÔOAHE

tpyjiMUHCKe Kucejime,

Ilpn

KOJ'H j e

cacBHM c^nqaH MHpncy u,HjaHOBOAOHHqHe KHcejiHHe. r i o c j i e no^a caT3 33r p e B 3 ce

CAAP»HH3 e n p y B e T e

j o m KpaTKO BpeMe

HA BOACHOM KYNATH^Y

Koje K^YHA, AOAA j o m 4 ml BOAE, OABOJ'H UEIJEIBEM cpeôpoxjiopuff Tp3T HCNSPN AO cyB3 330CT3JIH

CTaKJieHoj 3AeAn

H3 BOACHOM

XUapOKCUMMOHUjyMXJlOpUa MOHCE Ce AOK333TH

UHOHOM AejcTBy 1

y Ma^oj

H3 oMOHiíjoHHU pacUlBop

cpeôpa

H 4>HJIKYNSRA^y.

NO CBOM PEAYK-

H H3 a

nocjie COHOM

ÄA

ce

Mopa

y H H m T H,

c BaKo M

y

OÄMax

c ^ y n a j y

HajjeAHocTaBHHje

KOHU.

ca

KHCejIHHOM.

H H i p o j H e K H c e j i H H e cy 6e36ojHe, ajm ce pacTBapajy y ajiKajmjaMa ca 3aracmo upßeHOM 6O]OH, npn i e M y ce nopea HHTp030 rpyne, Koja aaje 6ojy CTBapa 11 aciHHTpo rpyna. IipBeHHM cojiHMa ce npmiHcyje OBa c})opMyjia, Ha np.: HC — N = O N O ONa ripn

3arpeBaH>y

y

pacTBopy

HHTpojiHa KHcejiHHa Ha a 3 0 T a c T y y

npHcycTBy

cpeöpoHHTpaTa

3aKHUie^>eHOM

Kao

\>C = N O H o2N/ T a j HaMHH, n p e n o

KHcejiHHOM

pa3Jia>Ke c e

OBa c e MÖWE

K H c e j i n n y ;

MeTHJi-

H3ÄBO]HTH

cpe6poc{)y;iMHHaT.

H

Ha

a30TH0M

u ipyjiMiiHcsy

-> N 0 2 H + C =

MeTHJiHHTpoJiHe KHcejiHHe,

N0H.

CTBapajy ce

j M H H a T H

O TOMe j e öiino roßopa Ha CTp. 122. Co ÄBOBa^eHTHe Ä H B e HHTpoMeiaHa pa3Jiana ca aflÄexHÄHMa y3 H3ÄBajaH>e Bojie. OBHM n y i e M JMKO ce aoöHja ( P E H H J H H T P O E I H J I E H . '

CGH5 — C H O - f H 3 C • N 0 2

i e H H J i H H T p o e r H ^ e H .

pacTBopn

ce y

ml

20

1

anxoxojia

3,2 h

KCUMO

xunpoKcuna, y

npoöa

ml

5

HacTaae

n0TnyH0

He

jie,n,OM oxjial^eHe Ha

y

je

ml

y

nuwpoMeMaHa ce,

Äe B o ^ e

ce

h

pacTBopn

emujiamoxojia aKUHOHH

KOJ'H

boäc

g

TOMC

./ie^a H COJIU, y 3 CHaiKHO M y h n a i t e pacüiBop

> C 6 H 5 — CH = CH • N 0 2

o^BpcHe

nopue^aHy

g

H

60

ml

oijeÄH

npeicpH-

(peHtuiHumpoeiliiuieHa, Tauna

Ton^>ett>a

58°.

4. Cßa npHMapHa HHTpojeÄHH>eH>a Kynayjy ce ca ÄHa306eH30Ji0M; MecTO o'ieKHBaHHX a3ojenHH>eH>a Haciajy npeMeuiTaH>eM $ e H H J i x H j p a 3 0 H H a-HHTpoaJiiexma: R .C= N = 0 H I + H O — N == N • C 6 H 5 ONa

->

HO

/ \N =

H 1

Thiele

H Haeckel,

A. 325, 7 (1902); Bouveault

ONa

\ / R . C —N =

H Wahl,

0

N • C6H5

Compt. rend. 135, 41 (1902).

HHTpojeflHH>eiba

•

H H>HXOBH PEAYKUHOHH NPOIIYKTH

133

R . C — N0 2 || + NaOH N — NH C6H5

HHTpoMeTana no,n flejjaKiix aJiKannja. 2 ce MOJieKyjia KOHaeH3yjy y3 H3.nBajaH>e Bone y T3B. Meia30HCKy KHccjiHHy, Koja HMa KOHCTHiyuHjy HHipoauciiuinoKCHMa (I) (Meister)1. 2H„C=N = 0 H n HC C= N = O HC — CH,NO„ " ! ^ Il H I ; I II ONa NONa ONa NOH 5. H a B e m h e M O OBjie jorn j e a i i y Bpjio H H T e p e c a H T H y p e a K U H j y

CTBOM

H3 OBe je Sieinkopf ao6no ca THOHHJIXJIOPHAOM ayro TpaiKeHH HHTpoaueTOH H T p H Jl2 CH2 • N0 2 • CN, a H3 OBOr CanOHH(J)HKailHjOM HHTpOCHpheiHy KBC e .1 H H y.s 2. HHTpoBaH>e apoMaTHHHor yr;i>0B0fl0HHKa HlITp0CeH30JI H flHHHTp06eH80JI a)

HHTpo6eH30Ji

y 125 mi — 2 3 0 g KOHifeHuipoaaHe cyMUopne mcemne, Koja ce Ha;ia3H y 6ajioHy 0 4 OKO 1 / 2 ^HTpa, ernia ce nocTeneHO y3 MyhKaite 100 mi — 140 g KOHifeumpoBaue a30uiHe icucejiune (cn. T O K . 1,4). RIOUITO ce jorn Tomia cinema, noTanaiteM y x^a^Hy BOAy, oxjia^H Ha coÓHy TeMnepaTypy, AOAaje ce y3 ^ecTO MyhKaite nocieneHO 90 mi = 78 g (1 MOJI) 6en30Jia. A K O ce npn TOMe nonHe TeMnepaTypa H3HaA 50—60°, noTana ce cyA KpaTKo BpeMe y JieAeHy Boay, npe Hero IUTO ce Aajbe AOAaje 6eH30Ji. ripa CB3KOM AOAaBaiby 6eH30Jia onajKa ce hhtchshbho mpko o6ojeibe, Koje 6p30 Hiime3aBa. IIOTOM ce Ha óaaoH cTaun B33jj,yuiHH K0HAeH3aT0p H jorn y 2 caTa rpeje Ha BOAeHOM KynaTHJiy qnja je TeMnepaTypa 6 0 ° ; AOH>H c./ioj, KOJ'H ce cacTojH OA cyMnopHe h a30THe KHCCJIHHG, OABOJH ce y JieBKy 3a OABajaite OA ropfber, KOJ'H ca^pMiH muipo6eH30Ji4. OBaj noaieAH>H ce npoMyhna ca BOAOM y jieBKy 3a 0ABajaH>e, n0T0M ca pa30;ia>KeHHM pacTBopoM HampujyMXUAPOKCUNA, Haj3aA jom je^HOM BOAOM, npn neMy Tpe6a HMUTH Ha yMy Aa HHTpo6eH30Ji caaa oópa3yje AottH cjioj. floiiiTO ce ncnepe H OCTHBH Heno BpeMe Aa CJierHe, HcnycTH ce HHTpo6eH30^ y cyB SaJioH H 3arpeBa AOT./ie Ha BOAeHOM KynaTHJiy (Ba3AyiunH K0HAeH33T0p) ca KajiiiujyMXJiopujjOM, a o k y noqeTKy MJieqHa Te^HOCT He nocTaHe SncTpa. HHTpo6eH3o;i ce Ha Kpajy npeuHmhaBa AecTH^auHjoM H3 6a;iOHa 3a (^paKUHOHHcaibe ca Ba3AyuiHHM K0HAeH3aT0p0M, npn-qeMy ce He AecTHJiniiie CSCBHM AO Kpaja. T. K. 206—207°. npHHOc 1 0 0 — 1 0 5 g. 6)

flHHHTp06eH30J]

y CMemy OA 14 mi = 25 g icoHiienuipoBaHe cyMttopne tcucemne H 10 mi = 1 5 g UyuiJbUBe a3omne mcejiune yHece ce nocTeneno 10 g nuuipoO MexaHH3My OBe peaKii.nje bmh A. 444, 15 (1925). B. 41, 1048 (1908). 8 B. 42, 3925 (1909). 4 Ha HCTOM ce npnniiHny peKynepmua cMeuia 3a HUTpoBaite yHHflycTpHjw; 3a peaKUHjy ce OBfle y3HMa 1 \/ 2 MOJI HN0 3 . 1

2

134

OpraHCKo-npenapaTHBHH neo

6eH30Jia

(pa,nn

3arpeBa

ce

CMerna

noA

no^a

ce

y3

HuMpoâeji30Ji

BOACHOM

Ha

Memaite oiieī,

H

nopuejiaHa

H y3

Kane;iOMl)

caTa

H3flHje

y

qeiuhe

xjiaAHy

BOAOM,

Hcnepe

MyhKas>e

Kynamny.

Boay,

OTBOpeHOM

oxJia^eHa

noTOM

npHTHCHe

H 3 amoxona.

npeKpHcraJiHiue

y

Ma.no

Ha

Tanna

ce

TaaHpy

öajioHy

peaKUHOHa

o^BpcjiH OÄ

nopo3Hor

90°.

TonA>eH>a

RU-

npHHOC

10—12 g. OcoÔHHa, « a npH aeJcTBy a30THe KHcejiHHe Ä a j y HHTpoaepHBaTe,

KapaKTepHCTHKa j e

j e Ä H i t e i t a . B e h npeMa ycjiOBHMa noÄ KojuMa c e HHTpoB3H>e H3B0ÄH, Mo>Ke

apoMHTCKHX

Äa c e y B e ^ e jeÄHa HJIH BHiiie HHTpo r p y n a . 4>opMyjincaTH p e a K U H j y ! A K O apoMaTCKa noÄ

ropitHM

jeÄHitetba HMaJy

ycjiOBHMa,

yrjbeHHKOBH

yBeK

3TOMH 6eH30Jia

caMO

3acHheHe ajincfiaTCKe 6 o i H e

6eH30Ji0B0

Be3aHH caMO ca jeÄHHM

HH30Be HHTpoBahe ce,

a He 6OHHH HH3. n o u i T o

je3rpo, aTOMOM

BOÄOHHKa,

TO c y

cy

ÄOÖHjeHH

HHTpo ÄEPHBATH TepunjapHH ¡ npeMa TOMe HHcy y CTaH>y, Kao npHMapHa H cenyHÄapHa

HH-

T P O - j e n H f t e f t a Ra r p a j i e COJIH HHTpoaHe KHcejiHHe HAH n c e y a o - H H T p o j i e . HHTpo r p y n e

Mory

TaKoije

AA c e y B e a y y

6OHHH

H H 31.

AKO ce Ha np.

Tojiyoji

HJIH eTHJi6eH30Ji 3arpeBa ca cjiaöoM 330th0M KHCCJIHHOM (cn. T e w . 1,076) y 3aT0njbeH0j ueBH Ha HEMTO n p e n o 100°, ÄOÖHhe c e HHTPOETAH

4 '

e H H J 1 H H T

P

Q H C • C H 2 • N 0 2 HJIH ( J I E H H J I -

0 M e T a H

C6H5 • C H ( N C y • CHS.

HHTpoBaTH c e M o r y He caMO ocHOBHa apoMaTCKa jeÄHH>en>a yrjbOBOÄOHHKa, Beh H CBH HTÄ. H n a n HHTpoBaae n e n a e

H.HXOBH aepHBaTH, Kao cJieHOJiH, 3MHHH, aajiexHÄH, KHcejiHHe CBy.ua ca HCTOM jiaKOhoM,

e r a r a c e M o p a j y 3a CBaKH c j i y i a j H3HahH

HajnoBOAHHjH ycjioBH

3a peaKUHjy. AKO c e HeKa MaTepnja Bpjio JiaKO H H T p y j e TO c e M o w e HJIH Äa H3Beae HHTpoBaH>e 330TH0M KHcejiHHOM, Koja c e npeMa noTpeöH pa3ÖJia>KH BOÄOM, HJIH ce cyncTaHua Tpeöa Äa H H T p y j e

pacTBopn y HCKOM

pacTBapa^y,

Ha Kojn

a30THa

KHcejiHHa

He

Koja

Äejiyje,

3auiTa c e necTO y3HMa rJiauHjajma cnpheTHa KHcejiHHa H OBOM c e ÄOÄaje a30THa KHcejiHHa. A K O c e HeKa cyncTaHua T e « e

HHTpyje, TO c e OBa yHOCH y KOHueHTpoBaHy

HAH n y m j b H B y

a30THy KHcejiHHy. AKO c e m i T p o B a i t e BpuiH TeuiKO, TO c e H3ÄßajaH>e BOÄe ojiaKUiaBa ÄOÄaBaiteM KOHueHTpoBaHe c y M n o p H e KHcejiHHe oöHMHOj HJIH rryuiJbHBoj a30TH0j KHcejiHHH. Flpn p a a y ca pacTBopoM

3aKHcejbeHHM

cyMnopHOM

KHcejiHHOM

a30THe KHcejiHHe KajiHjyMHHTpaT hah HaTpnjyMHHTpaT. MOÄH^HKOBaTH

joui Ha ÄBa HaHHHa,

a30THe KHcejiHHe.

ynoTpefjjbaBa ce

KaTKaÄ

MecTo

OnHcaHH Ha^HH HHTpoBafta Ä a j e c e

npH neMy c e Bapnpa

1.

H 2. KOJiHiHHa

TeMnepaTypa

TaKO c e MOHCE HHTpoBaTH y 3 xjial)eH>e CMernoM 3a xjial]eH>e, HJIH jieaoM,

HJIH BOÄOM, HJIH y 3 ô j i a r o 3 a r p e B a f t e H Haj3aÄ npn KjbyqaH>y. flajbe MOMCE « a c e y3Me BHUiaK a30THe KHcejiHHe HJIH TeopncKH H3paiyHaTa

KOJIH^HHB. K o j a OÄ OBHX MHoroöpojHHX MOÄH-

(jjHKauHja .naje HajöoJbe p e 3 y j i T a T e , Mopa c e npeTXOÄHO yTBpÄHTH orjieÄHMa y MajioM. n o u i T o c y HHTpojeÄHH>eH.a

sehHHOM y BOÄH HepacTBopHa

HJIH TeuiKO pacTBopHa,

TO ce oHa M o r y

H3ÄBojHTH H3 CMerna 3a HHTpoBahe pa36jiajKHBafteM ca BOÄOM. y j i a 3 a K HHTpo r p y n e y OCHOBH He Metta xeMHCKH KapaKTep cyncTaHue. TaKO c y HHTpo ÄepHBaTH ca HHTpo r p y n o M y j e 3 r p y HeyTpajiHa jeÄHH>eH>a Kao H caMH yrjbOBOÄOHHUH. M e IjyTHM aKo j e HHTpo r p y n a cTynnjia y. HeKo jeflHH>eH>e Ha np. KHcejior KapaKTepa, TO h e c e OBaj

THMe

na n o j a i a ;

HHTpocjieHOJiH

c y Ha np. j a ^ E

KHcejiH

BejiHKH 3Hatiaj

HHTpo jeÄHH.EH>a nÒHHBa Ha H.HXOBOM

MeMy h e 6HTH roBopa KOÄ H Ä y h e r n p H ÄBOCTpyKOM 6 e H 3 0Ji,

MaTCKa jeÄHH>eH.a c y y npBOj BAH>e H 3 . cyji(j)OHOBaH>e. jeÄaH jeÄHHH 1

Konowalow,

6eH30Jia

noHauiafty

CTBapa c e CKOpO

HaBeÄeHHM

onuiTHM

ce

n p y peÄyKUHjn, o

6eH30jia

HHTpo- HJIH CYJNJJO-ÄepHBaT.

B. 27, Pei}). 194 H 468 (1894).

HCKJbyiHBO

3aK0HHMa

JIHHHJH THnnqHe Tpn p e a K i i n j e :

A K O noijeMo OÄ caMora

MOHOxajioreH,

CJIHHHO

npenapaTa.

HHTpOBaH>y

uiTO j e y Be3H ca HHwe

OÄ $eHOJia.

c y MaH>e 6a3HH OÄ aHHJiHHa.

ÄernaBa npn HHTpOBaay 6a3HHX cyncTaHun; H H T p a H H J i H H H

m-R H H H T p o -

cyncTHTyunje. 3a

apo-

1. x a j i o r e H O B a a e , 2. HHTpo-

TO j e , pa3yMe

c e Moryh

A K O c e naK n o l j e OÄ

caMO

MOHO-cyn-

Ill, 3

HHTpojeOTfteHja H H>HXOBH peayKUHOHH npoayKTH

135

CTHTyncaHor 6eH3o.na, TO xajioreH, HHTpo- HJIH cyjiijjo- r p y n a Mowe a a c i y n H y 0-,

m-

HJIH

p - n o j i o w a j . MHH>eHHue c y MeljyTHM noKa3aJie, aa ce n p n TOMe aemaBajy flBa THna peatcunja, n p n neMy ce y jeflHOM cjiyqajy CTBapa npeTewHO 0- H paepHBaia, AOK ce y a p y r o M

cjiyqajy npeie>KHO CTBapa

6H,nepHBaT, n o p e « caMo Majio

m-

m-aepHBaT, n o p e a caMo Majio o- h

P-AEPHBAIA.

C y n c T H t y e H T H KOJH FLHPHLRYJY yjia3aK xajioreHa, HHTpo, cyjiijjo H a p y r n x r p y n a y 0- H p-

nojiowaj

30By ce cyncTHTyeHTH n p B o r

peia.

CyncTHTyeHTH KOJH c y n c T H T y u H j y

p H r y j y y m - n o J i O H c a j 30By ce cyncTHTyeHTH j i p y r o r cy:

xajioreHH,

rpyne n m

ajiKHJiHe r p y n e , XHjipoKCHJiHe r p y n e n o p e a o-aJiKHJi H o-auHJi rpyna, aMHHO

CyncTHTyeHTH

j p y r o r pe«a c y : HHTpo r p y n a ,

cyjicJjo r p y n a , aji.aexH.HHa r p y n a ,

Kap6oKCHjina r p y n a , nopea COO-ajiKHJi, C O • N H 2 H CO-ajiKHJi (y KeTOHHMa), 0 = N H3 0 B 0 r yBeK

Hafipajafta

CTHTyeHaTa I I pe.ua

H3Jia3H Kao KapaKTepncTHiHO,

3acHheHH

IJIOPMAJHO

06paTH0.

H He c a n p i K e

flajte

Tpe6a

ce noBehaBajy

6eH30Jia. CHMETPHHHH HHTpo

HOBHX

Be3y,

tpHHHTpo6eH30J a30TH0M

H p-cyncTHTyunja

rpyna.

BCJIHKOM

cnoco6Homhy

nejioM

3a

6H ce yBejia

J\a

TCIHOCTH,

KpncTaJiH3aunjy

apyra

HHTpoBaity

HacTaje TeK npn BHiuejiHeBHOM K y B a f t y AH-

KHCCJIHHOM H oneT

Beh MeTHjiHe r p y n e y Tojiyojiy. T p H H H T p 0 T 0 J i y 0 J i cy

CKopo

m-nojiowaj.

caMo

ca

ynope.nn ca OBHM 0JiaKiiiaBaH>e c y n c T H T y u n j e y n p n c y c T B y O H HiiTpojeaHH>EHJA

I pe.ua

AOK ] e KOA c y n -

noTpe6Ha c y Beh jiajieKO jaMa cpejicTBa Hero n p n

JENNFTEH>a ca nymjbHBOM

H apyre.

CBH cyncTHTyeHTH

cy

HanoMeHyTH a a c e 0-

TeuiKohe 3a yBoljeiteM

HHTpo r p y n a y HHTpo6eH30Ji

na

HHJEFLHY M o r y f i y

yBeK BpuiH jiaKiue, Tj. ca BehoM 6p3HHOM Hero CTynafte y OB^e

m-

p e a a. CyncTHTyeHTH n p B o r p e . u a

a

AEJIOM

npHH0C0M.

CJI36HM

H N H 2 r p y n e , Kao H

Kao eKcn,no3HB.

iBpcTe

Koje

MaTepnje

H Koje y KOJIHKO

iiecTHJiHmy

HMajy MHoro BHiuy T a i K y KJbyqaita on. YRJBOBOAOHHKA 'IHJH c y

ce

6e3

OAJiHKyjy

pa3JiaraH>a,

AEPHBATH.

ce e T H JI e H noABprae aejcTBy KuceJiHHe 3a HHTpoBaite TO HacTaje Kao U I T O je Beh noMeHyTo H H T p o e T H J H H T p a i C H 2 N 0 2 • C H 2 • 0 N 0 2 . HHTpoeTHjiajiK 0 x o JI KOJH npBO HacTaje annuHjoM a30THe KHcejiHHe CTa6HJiH3yje ce ECTEPNCJJHKAUHJOM JIOK BepoBHTHH npHMapHH annuHOHH nponyKT H N O S Ha ABory6y Be3y 6eH30Jia, ycjiea Beh BHrne n y i a noMenyTHX pa3Jiora, H3HBaja Boay. O A H O C H cy aHaJiorHH Kao KOA peaKUHje erajieHa H CeH30Jia ca 6 P O M O M (CTp. 8 9 ) . AKO

3.

PeAyKUHja a)

A H H J H H

HHTpo-je,piH>eft>a H 3

y

aMHH

H H T P O 6 E H 3 0 J I A '

y SajioH ( O A 2 JiHTpa) C T S B H ce 120 g C H T H O rpaHyjioBaHor tcajiaja2 H 61,5 g (1/2 MOJia) HuUip06eH30Jia H TOME ce AOAaje nocTeneHO 270 ml = 220 g KOHqeHuipoBaHe cone mcejiune Ha OBaj H 3 H H H : yHece ce Hajnpe caMo O K O AeceTH ^ E O coHe Knce^HHe, TaAa ce OAMax daaoH B E ® e ca Ba3AymHHM K0HAeH3aT0p0M, He cyBHiue y3aHHM, H MyhKa. FlocJie KpaTKor BpeMeHa CMema ce caMa O A cede 3arpeje H Haj3aA NO^He H C H B O K^.yqa. XjiaAH ce T O J I H K O xaaAHOM B O A O M , as peaKunja He npecraHe cacBHM H TaAa ce AOAaje MaJio no Ma^o y3 erajiHo Myhnaibe ocTayiH Aeo coHe KHceaHHe npn qeMy peaKunja CTa^HO Tpe6a M C H B O Aa Tene. Ha Kpa]y ce 3arpeBa H 1 caT Ha BOAeHOM KynaTHJiy, pa36^a>KH Tonao pacTBop ca 100 ml B O A C 1.

1

A.

2

AKO ce HeMa RPAHYJIOBAHOR Ka^aja, TO ce OH Mowe «O6HTH Ha Taj HaiHH, a a ce y

44,

283,

(1842).

miaMeny ayBajbKe HCTonH KOMnaKTHH

KOMaa Kajiaja KojH ce npeTxojiHo

KarnHKy

oH^A

y

cya

ca NPUIKOM

HanyaeH

H H3AHBOM,

BOAOM.

na

ce

H3^Hje

K a n a j y h n

ca

CTaBH y

BHCHHC

OA

TB03fleHy 1/2—1

m

OpraHCKO-npenapaTHBHH j i e o

136 ÄOfla 200

nocTeneHO BOÄe,

ml

K0HAeH3aT0p0M y

Bpejiy

BOAa, 25

jimue.

cnpaoieHe

TexHHHKor

g

peaKijHje1.

KOCO

jom

Kyxuwcice FIOTOM

ce

OKO Ha

com

oä

l c a n a i t e OÄ 2 0 0 ml.

100

^o^a

a

Kao

ce

TCIHOCTH

ml

napa

ÖKerap h

no eKC-

ca

HCKOJIHKO

SHHJIHH

npe,a,ecTii-

TCXHHIKOM

Kpo3

n o c T y n K y

cpeÄH>n j e n p o ß y i e H a

3

:

MemajiHua

K0HÄeH3aT0p, a c a a p y r e jießaK 3a

M ö w e Äa c e 3 a r p e B a Ha yjbaHOM

KynaTHJiy.

3 0 0 m l BOÄe H 3 0 ml KotmennipoEane

¿eoxfa*,

BO^eHa

Beh

ocyiim

Hcnapw,

^yraqKHM

TeopncKor.

OÄ 2 j i m p a ca Tpn r p j i n h a ;

BajioH

nmenoz

ca

TCHHOCTH,

ml

pacTBop

c a 3anTHBaieM, c a j e ^ H e CTpaHe cTaßn c e ycnpaßjbeHH 2 0 0 g upaxa

yBOÄH

M;ieqaH,

HaBe,a,eHH n p o n w c j e n p H J i a r o ^ e H

Y3Me c e öajioH

OÄMax

CB3KHX

eTap

90—100%

Beate

300

eTapcKH

KajiujyMxuapoKCuna,

FlpHHOC

h

ce

BHiue

HHje

y

HaffipujyMXuapoKcuAa

Bauern

H a Rone

j,ecTHJiaT

eüipOM2.

184°.

Ha)Ke

150

npeÄeerHJiHiiie

MBpcTor

TK. 2.

^a

ÜHUJIUH

KOMaAHha

oä

aaKajiHe

nocTaßjbCHHM

ce

CHTHO

Tpaxyje

jaKO

T G H H O C T . , MHM

nycTH

g

pacTBop

ao

y

6a;ioH c e y H e c e H KyBa

coHe Kucenme

10 MHHyTa y 3 C H 3 J K H O MemaH»e. TaÄa c e nycTH Äa Kanjbe 1 2 3 £ Hum.po6eH3ona

y TOKy 3 / 4

c a i a , npH neMy c e 3arpeßaH>e MOiKe Äa y M e p n . H a K p a j y c e KyBa j o m l o w e , ÄOK TeiHOCT K o j a c e B p a h a H3 K0HÄeH33T0pa He nocTaHe 6 e 3 6 o j H a (OKO 1 caT), TaÄa c e n o c j i e ÄOÄaßaita 15 g npe,aecTHJinuie anunun

HampujyMKapöonama,

BOÄCHOM

napoM. FlpHHOC

9 0 ° / o OÄ T e o p n c K o r .

OcoöHHa j e HHTpojeÄHH>eH>a ajiHtjjaTCKor Kao H apoMaTCKor peÄa, Äa eHeprniHOM p e ÄyKUHjoM

npejia3e y

npHMapHe

a M h H e.

3 a peÄyKUHjy

CBaKe HH'rpo

rpyne

noTpeöiio

j e 6 aTOMa BOÄOHHKa. y

TexHHUH 3a peÄyKUHjy He cjiyiKH CKynn Kajiaj, Beh c e paÄH j o u i ÄaHac n o CTapoM

nocTynKy

ca

Beehamp-a

r B 0 3 i e H p

onHJbiiHua

HJIH

r b o } k 1}em

y

npaxy.

Ko-

jiH^HHa coHe KHcejiHHe K o j a 0 Ä r 0 B a p a jeÄHaqHHH: CGH5 • N 0 2 +

3Fe +

6HCl =

C,;H 5 • N H „ + 3

Fe C l 2 - f 2 H 2 0

(A)

y HHÄycxpHjH c e HH H3Äa.neKa He Tpornn; H3Jia3H c e c a 3HaTHO MaH>OM KOJIH'JHHOM Ha iepnxaopHÄa H3Äßaja c e (jjepnxHÄpoKCHÄ H yßeK noHOßO coHa KHce;iHHa

CTojw Ha p a c n o j i o w e i b y 3 a HOße k o j i h h h h g rßOJKlja. O K C H Ä H rßoiKlja Kojn ce Ä o 6 n j y Ha K p a j y n p e B O Ä e c e n 0 H 0 B 0 y rB03ÄeHH

npoueca, y

HOBHje

KäiaJiHTHMKH

je

BpeMe 3a Äo6HjaH>e

nöcTynaK

3 a peÄyKUHjy

XHÄporeHOBafta

H3

BOÄOHHK3

n p n upBeHOM

HHTpo6eH30Jia

yrnao

y

ycnjafty.

HHÄycTpnjy

H T O c a 6aKpoM Kao KOHT3KTHHM M e i a ^ o M .

HHTpo jeÄHH>eH>a y J i a ö o p a i o p H j n

HJIH CTaHoxJiopiiÄ H KOHU. coHa u n j a HÄe i e c T O

npax noMohy aHHJiHHa

HajnOÄecHHjH

Kaaaj

KHcejiHHa. C a HBpcTHM cyncTaHuaMa 6 e 3 p a c T B a p a i a

peaK-

TeuiKO H 3 a x T e B a ÄOÄaiaK

y3HMa c e Kao

a ^ K o x o a a HÄH r j i a u n j a ^ H e

cnpheTHe

KHcejiHHe.

K p a j p e a K u n j e n o 3 H a j e c e n o TOMe UITO peaKUHOHa CMema n o ÄOÄaTKy BOÄe o c T a j e ö n c T p a . B a 3 a c e OBÄe

Haaa3H Kao

xaopHÄ

(xÄopxHÄpaT), a x^opHÄH c y TOTOBO

6e3

H3y3eTKa p a -

CTBopjfaHBH y BOÄH. T p e 6 a HM«e pacTBopJbHBe ÄBojHe c o ^ h ca CTaHOXJiopHÄOM aJiH c e OBe BehHHOM p a c T B a p a j y y KJbyHa^oj BOÄH. 1

O E J I E K T P O J I H T H M K O M H3ÄBajaH>y KaJiaja B H Ä H VIII, 3.

2

y

HHÄycTpnjH c e HcojbaBaHje He BpuiH, Beh c e aHHJiHH OÄßaja, a „aHHJiHHCKa BOÄa"

ynoTpe6Ä>aßa 3 a HÄyhy ÄecTHjiauHjy c a BOÄeHOM napoM. 3

y n o p . H. E. Fierz-David,

i

OcTaan

^a6opaTopHCKH

j a n o o6ojeHe npoÄyKTe.

Operationen der F a r b e n c h e m i e , n p e n a p a T H ca rBOÄ^eM

Man>e c y

IV H3Ä-,

1938, e r p . 3 5 .

noroÄHH H O 6 H H H O Ä a j y

HHTpojeambeiba

H H>HXOBH

pejiyKUHOHH npoayKTH

137

Ako ÄBOjHa co HCKpHCTa^Huie y Behoj kojihihhh, ohm ce oBa H3ÄBojH ueljeiteM Ha

BanyyMy. Pa3JiaraH>eM noMohy ajiKaJinja, hjih joui 6on>e ca cyMnopBoaoHHKOM, aoônja ce 6a3a JiaKO y ihctom CTaH>y. npHMapHii Moiio-aMHHH cy aejioM 6e36ojHe tcihocth, Kao Ha np. aHHJiHH, oTOJiyHAHH, KCHJIHAHH, HJIH 6e3ÔOjHe HBpCTe MaTepuje, Kao p-TOJiyHÄHHi nCeyÄOKyMHÄHH, HaijlTHJiaMHHH h apyrii. Ohh ce aajy aecTHJioBaTH 6e3 pa3Jiaran>a h HcnapjbHBH cy ca BoaeHO^ napOM. y BOaH cy npHJlIHHO TP.LUKO paCTBOpjbHBH. aHHJIHH Ä0 3°/0. IJ H a M H H H H nOJIHa m h h h cy BehimoM iBpcTH, ca BOÄeHOM napoM HHcy HcnapjbHBH, a y boäh ce MHoro jiaKwe pacTBapajy Hero jih moho-3mhhh. Amhhh HMaJy 6a3HH KapaKTep; 6a3HiHOCT je nnaK ycjiea HeraTHBue nptipoae (jjeHHJi rpyne 3HaTH0 cjiaönja, Hero koä aJiH^aTCKHX aMHHa. Clora boAeHH pacTBopn HeyTpaJiHHX (cTexHOMeipncKH) hhhjihhckhx cojih ycjiea XHapojiH3e pearyjy KHcejio na jiaitMyc xapmjy. M3 hctot pa3Jiora Monte aa ce H3 Boaenor pacTBopa aHHjiHHCKe cojih H3ÄB0JH Majia KOJiHHHHa cJioöoÄHe 6a3e eKCTpaxoBaaeM ca eipoM. (ÄOKa3 ca eiapcKHM pacTBopoM cone KHcejiHHe hjih nocjie HcnapHBaita eipa noMohy peaKunje ca XJiopHHM KpewM).

OrJießH: 1. Pa3ÖJia>KH ce 10 ml aHUJiuHcice Boae (AOÓHjene MyhnaiteM 3 Kann 3HHJIHH3 ca 10 ml BOAe y enpyßeTH) ca 100 ml BOAe h AOAa ce Majio npoaeljeHor BOAeHor pacüiBopa xjiopiwr apena. Haeraje j b y Ö H H a d o oóojeite {Runge-OBa peaKunja). Oßy ßpjio oceTj£>Hßy peaKunjy Aaje caMO boachh pacTBop oioöoAHor aHHJiHHa, a o k H>eroBe cojih He Aajy; CTora ce 6 a 3 a Mopa Hajnpe Aa o c j i o ö o a h h3 co;ih. Oßa ce peaKUHja Moate TaKolje hckophcthth Aa ce AOKa>Ky Majie KOiHHiHHe 6en30Jia hjih Humpo6eH30Jia, ano ce HSßeAy y MaJiOM (y enpyßeTH) peaKUHj'e Koje cmo MaJio npe yno3Ha./iH. PeaKUHja ca XJiopHHM upeioM je cneuHa3a p e a n u n j e

c a c i o ] « y aAHUHjn BOAe Ha o 6 e cjiofioAHe yrjbeHH-

KOBe BaaeHue. n p e M a TOMe HMaMo &a c})0pMy;iHiiieM0 0BaK0: OH C6H5 • N =

c S = C = N • CgH5 + H 2 N • C6H5

C6H5

(})eHHJiceH(j)HO yjbe riopen Tora ce H3ÄBaja a Majia KOjiH^HHa aKTHBHo j e Ä H f t e i t e

Kap6oAH^enHJiHMHA

Kojii j e npHcyTaH y pacTBopy aajyhH

cyMnopBOÄOHHua H Haerajio HCOÖHHHO pe("HiJieHHjiuHjaHaMHA)

Beate c e ca araaHHOM,

TPHTJJEHHJIRBAHHIIHH, HCTO Kao IIITO ce H3 caMor

UHjaHaMH.ua H aMOHHjana CTBapa npocT rßaHHjHH. H ; N • 'QHS

s = :C

H

5

C

6

.N=C =

N -C6H5 +

H j N • QHS H2N C 6 H TpHtJteHHJirBaHHÄHH

H2S

OpraHCKO-npenapaTHBHH .neo

140

CeHtJiHa y j b a noKa3yjy npHHumiHjaJiHo n c i e peaKUHje aiwunje Kao H H>HM3 H30JIOI-HH ecTpn unjaHCKe KHcejiHHe (B. CTp. 126), Ha np. 0 = C = N • C 6 H 5 . HnaK oßa p e a r y j y Miioro cnopnje, UITO Beh npoH3Jia3H H3 Haqmia ÄOÖHjaiia $eHHJiceH(})Hor y ^ a (({jeHH^unjaHaT ce OÄMax pa3JiaHy CTaKJieHHM n i T a n H h e M HCKpHCTajiHiue MuompßaHUJiUA, K O J H ce n p e ^ H i u h a B a H3 amoxona paAH OÄpeljHBaiia Tanne Tonjbeiba. n p n 3arpeBaH.y ca ÄyTHM HCHBHHOM OKCHÄOM, cyMnop ce 3aMeH>yje KHceoHHKOM H Äo6nja ce e c T a p u w j a H C K e K H c e j i H H e Kojw MOHte aa ce no3Ha no CBOMe Heo6HqHO OUITpOM MHpney: C 6 H 5 • NCS + H g O = C 6 H 5 • ftCO + H g S (JjeHH^uHjaHaT

ÖrJiefl:

5,5

ml (pemvicetupHor yjba n o M e i u a c e y e n p y ß e T H ca

npeMHHOM 3/cyBor yjba.

ce

>KyTH

0Kcu.ua

OKCHA

pa3BHja

BeoMa

HCTOM

3a-

o/cuae u 3 a r p e B a h c k o B p e M e ÄO KJbyqaK>a c e H f J m o r

npeJia3H

ouiTap

npHTOM

y

IIPHH

JKHBHH

cyatjjHÄ;

(peHUJiifujaHaiüa, i H j e

MHPHC

HCTOBPEMEHO

nape

HaÄpajKyjy

O^H ÄO cy3a. 6)

y

RPEBAIBEM

6p30 H

m-H

öajiOHy

H T p S H H J I H H

ce

amoxony

y

FFL-Ä

(Ha

1

g

Ta^a

c e ÄOÄa K0HueHTp0BaH

6eH30Jia 0 , 8 g a M O H H j a K a ) .

TO

ÄHHHTPO6EH3O;IA

aMonujaic ( c n .

BpeMe

ce

He y B O Ä H

Äa^e

H

AAKOXOJIA),

S

—

K0HÄeH3aT0p0M. CBe Ä O T a e , ÄOK

noHaBJba

AHHHTpo6eH30Jia

He n o ß e h a

ljeH>a He H a c T y n H ce

onepe

yBOÄH y

ce

0,913)

pacTBOp

A K O

ynoTpe6n

OÄ

^ÄHHHTPO-

noßehaibe

3arpeBa

BOÄ6HOM

— Ky-

y B o i j e t t > e H . . S Ha XJIAAHO H n 0 T 0 M ce

3a CB3KH r p a M

ynoTpeöjbeHor

A K O y c j i e a HeÄOBOJbHor x ^ a -

TejKHHe,

oH^a 6 e 3 o ö 3 H p a

Ha TO,

T p « n y T a . T a ^ a c e p a 3 6 a a ) K H BOÄOM, o u e ^ H ,

Ta^or

pa36^aMceHOM COHOM

KHcejiHX ^ H J i T p a T a o c ; i o 6 a l j a c e HUMpaHUJiUH. H e y T p a j i H c a i t e M

H3

aMOHujanoM,

7 0 — 8 0 %

1

H Taaa

BOÄOM H e K C T p a x y j e BHiue n y T a , y 3 3 a r p e B a n b e ,

mcejiuHOM.

(Ha

c a T a Ha

nojia

OKO

TOKHHS 3A 0 , 6 g.

noTpeÖHO CBeMy

Te>K.

cyMüopBOAOHUKOM 2

3arpeBaft>e

ca

ml

5

A

pacTBopa 3 a -

RIOUITO c e 6a;IOH 3 a j e Ä H O c a c a Ä P > « a j e M T a p a p a ,

Ha o Ö H i H o j T e M n e p a T y p w

naTHJiy c a y c n p a B J b e H H M

H2S

H H H T P O 6 E H 3 O I

A H H H T P 0 6 E H 3 0 J I

o x j i a f l H , n p w q e M y c e ÄHHHTPO j e Ä H f t e t b e AejiHMHqHO n 0 H 0 B 0 M3ÄB0jn

33CHTH c e 3a

H 3

npeKpHCTajiHcaHH

N0T0M

c e

NPENPHCTAJIMIIE

H3

BOÄE.

T.

T.

114°.

IlpHHOc

TeopHCKor.

xohe Ä A ce H3ÖerHe P A Ä ca C Y M N O P B O Ä O H H K O M M O J K C Ä A ce Kao p e Ä y K U H O H O c p e Ä C T B O T A K O I ^ e T C X H H H K H mwpujyMcyjKpup,}

rioTnyHa pe,nyKunja HHTpo je,nHH>eH>a Koja caapiKe BHiue HHTpo rpyna h3boäh ce Ha HCTH HaqHH Kao H KOÄ moho-HHTPO ÄepHBaTa. AKO ce naK no^H-HHTpo ]eÄHH>eH>e xohe aa p e a y K y j e n a p u H j a ^ H O oHjia je K O P H C H O a a ce ynoipeöH a M O H H j y M c y ^ t j j x H Ä p a T . 1 EWIHIKH nponwc: Cobenzl, pädie 2 H3Ä., KHJ. I, d p . 470.

Chem. Ztg. 37,

299

(1913);

BHÄH H

Ulimann, Enzyklo-

III,

Hmpoje,NHH>eH.a H H,HXOBH peayiaiHOHH

3

N 0

\

+

3 NH

4

C6H(

SH =

•NO 2

HesacHheHH cpeacTBo

2 H 2 0 + 3 S + 3 N H'3 ,

T3KBHX HHTpo jeaHH>eH>a,

HacueHTHor ßoaoHHKa M o r y aa ce npoMeHe;

6OHHH

HH3

H apyre.

y

TOM c j i y i a j y

rBOiKtje ( H ) - x n j p o K c n Ä

apcaHHJiHa KHcejiHHa). xnapoKcnaa,

+ •NH.

H a p o i H T e M e i o s e 3AXTEBA p e a y K u n j a K o j e ÄejcTßOM

HJIH H r B o >K f j e y

P e a y x u H j a ce H3BOÄH TaKO,

Koje caapwe

Kao na np.:

npHMettyje ce npaxy

rpyne,

aaaexHaHa Kao

qecTO

rpyna,

peayKUHOHO

( y n o p . npenapaT V I I , 5,

aa c e y n p n c y c T B y aaicajiHja

(KaaHjyM-

HaTpHjyMXHÄpoKCHaa, 6apnjyMXHjipoKCHÄa) n y c f H aa p e a r y j e H3MepeHa KOJIH-

qnna tjDepocyji(})aTa Ha Ma-repHjy

Koja c e p e a y K y j e .

ayKyje

aMHiio6en3ajijiexHj,

o-HHTpo6eH3aaaexna

a M H II o u H M e T H y

y

H a Taj naiHH Monce Ha np. o-HHTpouHMeTHa

aa c e p e -

KHcejiHHa

y

K H c e JI H H y .

MHiteHHua aa ce y HaineM o n i e a y a o ö n j e % BHjmia,

141

•NO2

2

C6H4(

npoayKTH

TeopHCKH M o r y h e KOjiHMHHe

m-HHTpa-

noiKe a a j b e p e a y K y j y

Hero

HHTaKma HHTpo r p y n a . P e a y K u n j a /n-anHHTpo6en30jia y KHceaoj cpeaiiHH a o B o a n a o

ra-ijjeHHjieHÄHaMHHa:

NH„ TeximqKH

Ba>KHe

Bn3siapK0B0

aßOBa-ieHTHe 6a3e,

Koja npn ana30T0Ban>y

a a j e MpKy

6ojy

w-4>SHHJienaHaMHH c a y n a i 3a aoKa3HBaH>e TparoBa

MpiKe c e npeMa ycJiOBHMa

r p y n a ce

HaKHaaHO

oaßojH

noMohy

aueTHJioBaH>eM.

nocTHhn Behn npHHOc cpeacTBa

H H-

o- HJIH

3a canoHH(j)HKauHjy.

c e a o o n j a Taiioije na j e a n o c i a B H H j H Hanau, peaKunjoM p-HHTp0xji0p6eH30.ua

aa c e a o ö n j e

HHTpoßaibeM

xjiop6eH3o.ua) H aMOHHjaKa Ha B n m o j T e M n e p a T y p n

noa

npHTHCKOM. O

aKTHBHUiyheM a e j c T B y N 0 2 - r p y n e

M jeaHe

Ha x a a o r e H y n o p . CTp. 89.

H H a i e c.na6 6a3Hii.HTeT aMHHO r p y n e K o a aHHJiHHa jaKO c e CHH>KaBa Hiirpo r p y n e . Cßa Tpn HHTpaHHJiHHa c y cacßHM

cjia6e

Beh yjiacKOM

6a3e, K o j e Ten p a c T B o p e n e

y BHiiiKy KHcejiHna a a j y COJIH. /IOK c y HHTpaHHJiHHH o ö o j e H n HHTeH3HBH0 HapaHiiacTO Hcyro, aoTJie c y H>HX0ße COJIH

y IHCTOM

CTaH>y

ßesßojHe.

JaKO 6aToxpoMHH y T H u a j

(KO]H c e

Hcnojbaßa y TOMe aa 6oja nocTaje 3aracnTKja), K o j e c j i o ö o a H e aMHHO r p y n e Bpine y HHTpaHHAHny, y n o p e l j e f o y ca, y MHCTOM c i a f t y , c K o p o 6e36ojHHM HHTp0ßeH30Ji0M, n o m y n o aaKJie Mime3aBa

CTBapaH>eM

COJIH,

npejia30M

He3acnhenor

TpoßaJieHTHor

a30Ta

y

aMOHH-

33THM aojia3H p-

H Haj3aa

j y M H H C H c T e M. O a TPN

HHTpaHHJiHHa o - j e a H H j e t t e j e

HajcaaöHje

6a3H0,

m-jeaHtteiie. Oßa HHfteHtma n o K a 3 y j e o a n o c e KOJ'H c y ßAIKHH 3A u e j i o K y n H y apoMaTCKy x e M H j y H K o j y CMO Beh paHHje H3HejiH, Kaa j e 6HJIO penn o aKTHBHpaay x a a o r e H a y c j i e a HHTpo r p y n a y o-

H / j - n o j i o w a j y : HauMe aßa cyncTHTyeHTa y o- H p - n o j i o w a j y y T H i y MHoro BHiue JeaaH

Ha a p y r n , n e r o c y n c r a T y e H T H y m - n o j i o i K a j y . 3aaoBOJbaBäjyhe o6jauiH>eHie 3a OBO j o m HHje

OpraHCKo-npenapaTHBHH

142

aeo

III, 4

HaljeHo, M a aa ce 4>6HOM6H M e m e ÄOHeKJie oöjacHHTH TeopwjoM Thiele

o O Ä H O c y Kojn BJiaÄB

H 3 M e ^ y nojicmaja 1 , 2 h 1 , 4 : A

A / \ B 1 2

A

1

43

sy •2

2

43

43 N / ' B

Heje^HaKH

6a3HUHieT T p n HHTpaHHJiHHa

je o c o Ô H H a COJIH cjiaÔHX 6a3a —

KHcejiHHe

— OÄHOCHO aJiKaJiHja —

pacTBOpa BOÄOM HacTaje

Moxce

Äa ce n o n a g e OBHM ornenou.

Onima

Kao H OHHX cjiaöHX KHcejiHHa, na ce O H e c a M O y BHUiKy nocrojaHe y BOÄCHOM pacTBopy. FIpH pa3ÖJia)KeH>y TaKBor

xnÄpojiH3a

Ha o c H O B y 3aKOHa o aejcTBy Maca. y OBOM cjiyqajy

OBaj ce ({leHOMeH HcnojbaBa y nojaBH «cyie 6oje, K a p a K T e p n c T H i H e 3a 6a3y H Haj3aa, nouixo cy HHTpHHHJIHHH TeillKO

paCTBOpHH y BOÄH, y H>HXOBOM H3flBajaH>y y OÖJIHKy KpHCTaaa. y

KOJIHKO je caaönja 6a3a, y TOJIHKO je MaH>H ÄOÄaTaK Bojie n o T p e ô a H .na ce ,H3a30Be xHÄpojin3a. Orjiefl: P a c T B o p n

Mory y

CBaKoj

cyMüopne CHnajy ce

no

Memajyhn

200

ÄeJiHMHqHO

H H J I H H C K 3

ml

ocTaje

co

o a C B a T p w HumpaHumna — koj'h c e HaóaBHTH — y e n p y B e T a M a y n o 3 mi KOHI¡, C T a K J i e H H M iuTannheM. B e 3 Ó o j H H c e p a c T B o p n 0,5 g

BOAe, Koja

H3ABaja

/7-j e a h ffa e ä e

no

jiaóopaTopHjn

mcenune, y

ce

ocTaje

h3

ce

myTO

Hajia3H y

oóojeHor

pacTBopeHO,

nexapnMa. pacTBopa,

ajin » y T O

O-HHTP3HHÍHH

HeuiTO

jaqe

6a3HO

o ó o j e H O , a o k r n - n h t p a-

6e36ojHa.

4. Ì > e H H ^ X H f f p O K C H J i a M H H 1 y n e x a p y o a 2 JiHTpa AEÖEJIHX 3 H A O B 3 noMeiua c e p a c T B o p O A 20 g Huiuaflopa y 400 ml BOAe H 40 g c B O K e ACCTHJiOBaHor mmpoôemona H y H e c e c e ( H a j ö o j b e ApseHOM uunaTyjiOM) y TOKy 40 MHHyTa 6 0 g ¡¡unica y Upaxy (HajMaKbe 7 5 % - H o r ) y 3 crajiHO C H a a t H O Meiiia&e. T e M n e p a T y p a caApacHHe y n e x a p y c e n p n TOMe OApJKaBa H c n 0 a 10° yÖ3UHB3H>eM KOMaAHha JieAa y CMeiny. n o u i T O c e caB ijhhk y H e c e , M e m a c e j o u i 10 MHHyTa — TaAa T p e ö a MHpHc H H T p o 6 e H 3 0 ^ a A a j e H u m e 3 a o — h o u e A n OAMax ¡¡UHKXUMPOKCUA Ha H y q y n o M o h y BO^eHe n y M n e . I I o t o m c e 4>n^TpaT ( p a c T B o p I ) cuna y n e x a p . KauiacTH u h h k o k c h a n e p e c e Ha H y q y c a 400 ml b o a c 3 a r p p j a H e Ha 45° T3KO, A a c e Hyq nyHH b o a o m He n p H K J b y q y j y h H r a Ha BaKyyM, naacjbHBO n p o M e m a h TaAa Ten ueAH n p a t 3 k o c n a ó o M B a n y y M y A a BOAa noJiaKo npoJia3H. T e n Ha K p a j y c e A o ô p o o a e A H n o B e h a B a j y h n BaKyyM, a OCT3T3K Ha (JjHJiTpy c e H c n p e c y j e ct3kji€hhm 3 a n y m a q e M ( p a c T B o p II). y 0 6 a BOAena pacTBOpa, y c b s k o m n o c e Ô H o , n o T n y H O c e p a c T B o p a 120 g c h t h o HCHTiteHe KyxuwcKe com, npH q e M y ce (peHiinxunpoKciiJiaMUH. H3ABaja y c h t h h m KpncTa;iHHHHHHM n a x y j b H i j a M a . f l o c h e 1/2-qacoBHor C T a j a a a cycneH3Hje y JieAy A o ô p o c e oiieAH Ha B a K y y M h TaAa n c n p e c y j e Ha n0p03H0M nopijeJiaHy. n p e K p H c r a J i H c a i t e M m Majio 6eH3ona y3 AOAaT3K 1

E. Bamberger,

B. 27, 1347 (1890); A. Wohl.

B. 27, 1432 (1890).

HnTpojeÄHH>eH>a

üewpojieyMewpa BpeMe

ÄOßNJE

n o c r o j a H

T o n j b e i t a

81°.

y

3 a

npeHHiuhaBaita.

ce

c y n c T a H u a

Aajby

H3

y

c y b I

ce

je

MHCT

n p e n a p a T

6 e 3

7 5 — 8 0 %

o ä

je

qacTHjH;

o 6 a a i y q a j y

HCKO T a m c a

HapOHHTör T e o p u c K o r .

yocTajiOM

pacTBopa.

H

HiviHija.

y n o T p e ö J b a B a

OÖHHHO

HajöojbeM

MCKHX

n p o A y K T y

n p e p a i j y j y

y

n o m y H O

n p e n a e T e H H x

o m

143

npo^yKTH

ApoKCH^aMHH

cjajHHx

^ H ^ T p a i a

ce

I X H

-'

n p e p a ^ y

3ajeAHHmHXOBH p e a y K U H O H H

HHiiiTa

He

H e n p e K p H C T a j m c a H a

HCKOJIHKO

AaHa

a

£,a

ce

He

pa3JIO)KH. Tpeöa ÄOÄHP c a

na3HTH,

aa

4)eHHJixH,npoKCHJiaMHH,

KOIKOM. K O Ä H e K H X

ocoöa

napowTq

OH H3Ä3HBA x e u i K e

Ka« je

y

pacTBopy,

e K 3 e M e , ÄOK c y

oneT

He

Äol^e

apyrn

y

cacBHM

HeOCeTJbHBH. Kao" Bpjio noKa3ao

ce

noroaHo

cpeacTBo

[Willsiäiter, CJIHIHO

Boaa

y

HHTpo

jeaHH>eH>a

ajiKoxoJiHOM

y

apnjixHÄpoKCHjiaMHH

p a c x s o p y

H TO H a

xjiajuio

B. 41, 1936 (1908).] uHHKy

y

npaxy

Oßaj- a M a . i r a M H c a H H rpn3a)

3a p e a y K u H j y

aMOHHj'yMcyjiij)XH,npaT

noroflan notaje

ce

je

nojiaKO

oaroßapa

CTaBJba

BehHHOM

Kan

no

Kan.

oTnpnjiHKe

Koje

TaMHO. HHCTH

ce

nocjie

npenapaTH

CynpoiHo jeaHH>eH>e;

Bell

ce

jo6nja

y

je

y

y

pacTBopy;

pa3JiniHTO

npaxy

XJIOPHÄOM.

Hajöojbe

HJIH a J i K 0 X 0 J i H 0 M

aejcTBO

UHHKOM

HapoqHTO

KpaTKor

Mory

eTapcKOM

ca

jia c e

y

cTajana

iieiHCTOM y

oßjiHKy noipeöHa

KOÄ p a 3 H H x

HeyTpajiHoj

cTaiby,

33TB0peH0M

nyxe

caiyßajy

OCHORHOM j e a m b e f t y ,

OIIO

y

HÍHBHHHM

—

HHTpo

cpe^HHH

H

3ay-

xHflpoKCHJiaMHiia.

4>eHHJixH,n.p0KcnJiaMHH, jeÄHH>eibe,

H. Wislicentis-y

PeayKUHOHO

OHOM

Ha c i e n e H y

ajiyMHHHjyM H a r p i m e H

(npeMa

TaKolje 3a p e a y K U H j y

jeÄHibeH>a, ce

a e j i y j e TaKolje

ajiyMHHHjyM

BpeMeHa

Bpjio

cyny,

y

P-HHTp0T0Jiy0Jia

ca

necTaöHJiHO óojehn

ce

eKCHKaTopy.

p-TOJiHjiXHÄpoKCHJiaMHH

peÄyKunjoM

je

pacnaxa,

UHHKOM

je y

cacBHM

npaxy

y

nocTojaHO KjbynajiOM

ajiKoxojiy. A p h JI x H ä p o K c h JI a M h H H KHcejiHiiaMa Ba3aymnor

y

y

ajiKaJinja H3iiehe

HHTp030ÖeH30Jl

HaJia3H

+

0

KOHÄeH3yje ca

Metjy npoAyKTHMa

H3a3HBa

ce

H3.nBajaibe

aa

ce

Koje

ce

pacTBapajy

Meiba

noÄ

ymuajeM

Ba3ayxy ce

ce

üejcTBOM

> CcH

Kao

y

HCHHCTH MHpncy

MHOI-HM

H

2

0

npeMa

a 3 0 6 e H 3 0 J i a .

cjiy-

H KOJ'H

jeÄHaiHHH:

2

y a 3 0 K C H Ö e H 3 0 J I ,

(jjenHJixHÄpoKCHJiaMHHa.

H cTBapaite

napoHHTO

(Bamberger)

• N O +

pa3Ójia>KeHHM ( f i a K T o p a H TO

a y T O K C H i i a u n j a

(j)eHHJIXHÄpOKCHJiaMHHOM

pacnaaaH>a

Boje

5

Kao

y Tpn

CBOMe o n i T p o M

ajiKajinja ce,

KOJH c e 0 3 H a i a B a

2

OKCHanuiy

KOHCTaTyje n o

B o . n o H H K c y n e p o K c H . a a

CgH5 • N H O H

oßaj

Ha

pacna,naH>y.

OBOT n p o u e c a ,

T e i e y 3 HCTOBpeMeno c T B a p a a e

ce

6a3e,

KO]h M o w e

KojH j e

n o B e h a ß a 6p3HHa

riOUlTO c e

cjiaöe

amcajinja H KncejiHHa.

n n T p 0 3 0 6 e n 3 0 j ¡ ,

4>emiJixHÄpoKCHJiaMHHy

qajeBHMa,

cy

COJIH. < t > e n H J i x H J i p o K C H J i a M H H

KHceoHHKa,

npenapaTH y

rpaaehn

ílopea

PeayKuHja

Tora ca

TO

.nejcTBO

KHcejiHHaMa

aouHHje.

,OH K a o H caM xnapoKCHJiaMHH,

Oniefl,: Ha

Bpx

'Orjiefl,: e H o

Jie^OM 1

H

y

OBy

pacTBopHTH

cpeópotuimpama

CTBopa

H o

H c n H T a r a

H o m a

CBH a e p H B H T H T H n a

y 3

ocoÓHHy y

2

AOAaTaic

n p e i v i e i i i T a i b e

fl1.

2,2

CMeuiy

Bambreger,

g OA

(1/50 10

mi

ml

MOíia)

KOHI(.

B. 27, 1552 (1890).

Ha

T ö r w e

R •

H CBMH c y

(peHUJixuapoKcumMUHy— BOAel

HeKOJiHKO

cyMüopne

A o a a

—

ca

y3eTH

je^HOM

O K C H J I 3 M H H 3

ce

¡cácenme

Kann

pa-

aMOHujam.

Kann

( J J C H H J I X H A P

6a3e

p e a y K T o p H .

n o c T e n e H o H

3 0

g

y

y 3 Jie^A.

p-SMHXJIA^eH>e

OpraHCKO-npenapaTHBHH fleo

144

Pa36jia>KN AOK

npoóa,

ce

Kojoj Beh

HU¡üp06eH30Ji,

KOCO

CO6OM

HA

aojié

OAHOCH

peaKiíHjH

ynop.

2 0 0 AOA^T

caMO

BOflH p a c T B o p e H o r 3A

ca je

mi B O A C H K y B a c e A O T j i e ( 1 0 — 1 5 pacüiBop óuxpoMama He M H p n r n e

Ha XUHOH.

ónxpoMaTa, NOCTABJBEH

CTBOpeHH VIII,

1.

III, 4

Ox^al^eHOM

Ta^a

ce

y

OcraTaK

y

YAYBABA

HaqHHy

O

6aJioHy

ao^a

BOAEHA

CTBapaiba

HcnHTaTH

napa,

XHHOH3

na

Há

2 g

ce

Kojn c e npeTxcm,HO

óajiOH,

K0H^EH3AT0P,

XHHOH.

pacTBopy

MHHyTa), BHuue

BE)KE

Koja

npn

y

ca

0B0j

aMonujan.

HapoqHTO Tpeóa HCTahH npoMeHy, Kojy n p e t p :e apMXH,npoKCHJiaMHHH aejcTBOM MHHepajiHHX KHcejiHHa, OCO6HTO Kaa c e rpyny

cjioóojiaH,

HacTaje

3arpeBajy.

npeMeuiTan.e

y

AKO je P-nojioiKaj

H30MepaH

y OAHOcy

Ha N H O H KOA (fieHHJi-

p-aMHHO(})eHOJi, na np.

XHiipoKCHJiaMHHa npeMa jeaHaHHHH: H /

OH

\

/

V

— >

N H O H

NH

2

Ha OBOJ HmepecaHTHoj peaKUHjH nowHBa nocTynaK KojHM c e .nnpeKTHOM pe,nyKUHjoM HHTp0306en30^a a o 6 « j a BancaH nojiBprHe

p - a M H H o $ e HO JI Kao Meljynpoflyia 3a 6 o j e . FIpii TOMe c e

ejieKTpo;IH3H aJiK0X0JiHH pacTBop

KHcejiHHa;

y3HMa c e ojioBHa KaTo.ua.

HHTp06eH30Jia

KOMe c e

floaa

KOHU. cyMnopHa

O B a peaKUHja ,noKa3yje fla c e tfieHHJixH.npoKCHJi3MHH

HHTepMeflHjapHO CTBapa KaKO j e TO Beh paHHje HanoMeHyTO H npn pejiyKUHjH HHTp0óeH30Jia y

KHcejioM

pacTBopy. V OBOM cjiyqajy j e 3 6 o r BejiHKe 6p3HHe npeMeniTaita,

HCK^yqeHa

peayKunja HiiTpo6eH30Jia no anHJiHHa. y ropiteM

o r j i e i y p-aMHHO(j>eHOJi

HHje H30Ji0BaH,

Beh j e OKCH^aunjoM

npeBeAeii y

XHHOH. AKO j e p - n o j i o m a j npeMa N H O H - r p y n w 3ay3eT, KCHJIAMHHA, flojyuie

Kao Ha np.

KOA p - T O JI H JI X n a p o -

TO h e KaTajiHTHHKO aejcTBO jaKHX KHcejiHHa a a AH a p y r y p e a K u n o n y cjiHKy.

ximpoKCHJiHa r p y n a h e TaKohje na c e npeMecTH Ha yrjbeHHKOB aTOM y p-nojioneH>a: CH

H3C

3

OH

I Y

\

\/ i

ii

N H O H

OBaj „XHHOJIHMHH"

NH

HMa xHHOHAHy

HMHHO r p y n y ,

Koja j e Bpjio

Majio nocTojaHa

npeMa KiicejiHHaMa H Koja c e xH«poJiH3yje Ha aMOHHjaK H 3 a M e ! t y j e KHce0HHK0M: H,C

OH

H,C

I I

H2 °

\/

II NH

KpajftH

nppflyKT

npeMenrraita

O H

I I

\/ II O

je

HajnpocTHjH

XHHOJI,

jiaKo pacTBapa y BOAH, Koja j e HacynpoT xHHOHy 6 e 3 6 o j H a napaTHBHO «oónjaibe TeuiKo.

cynciaHua

Koja

ce Bpjio

(Bamberger), a MHje j e npe-

Hmpoje.uHtt.eFba H H>HXOBH PEJIYKUHOHH N P O A Y K T H

III, 4

Or^e,n:

H H T p o s c x ^ e H H J i x H A p o K C H J i a M H H

apoKcujiaMUHa

pacTBopn

AO na

jie,n;oM O^Max

ce

^eHOM

npHJiHHHo

h

CyncTaHua Hujam

ce

TajiOÄH

CTBopHe

6p30

Hcyrne

mvie,

Ha

Koje

ce

y

H ôatcpoBe

H

co. com,

oa

1,4

oae^e

Ha

OBe

g

g

(penujixu-

jaKo

BaKyyM,

Äo6njajy

TajicmeaeM

TaKoi^e T 3 B .

H30HHipaMHHH

ae-

Hcnepy

59°.

TonjbeH>a

BOAH

ca

F e —

Kao H

ÜMO-

cyBor

y

n o H a r n a c e

O6;IHK:

R • CH2 • C =

NOH

H (1890).

xeMHje

10

146

aeo

OpraHCKo-npenapaTHBHH

BeH30Ji0B0 ]e3rpo, KOÄ Kojer H>eroBe Tpw cycejiHe ÄBoryöe Be3e HajnoTnymije H3pajKaBaJy 3acHheHOCT He aonyiiiTa npeMeiiiTaH>e TaKBe BpcTe. OB^e je NHOH-rpyna H3Ban ]e3rpa, MHCTO „apoMaicKH" KapaKTep je3rpa ocTaje caiyBaH. Cjihhhh oähoch iHHe pa3yMjbHBHM, aa ce äo caaa joui HHje Morao äo6hth „ajiH^aTCKH aHHJIHH" THna R•CH = C — I NH2 5.

HHTp0806eH30n

12 g CBOK6 cnpaBJbeHor

(peHUJixuapoKCUJiaMUHa pacTBop« c e

UITO

Moryhe ópace, yHOcehn r a nocreneHO y aeAOM o x ^ a ^ e H y CMeiuy o a 5 0 ml

cyjuuopne mcejiune

h 2 5 0 ml BOAe. T a ^ a c e OBaj Ha 0° oxjiaijeHH

nycTH Aa Tene npHJimiHO

pacTBOp

6 p 3 0 h3 JieBKa 3a Kanatbe y 3 AaJbe x;iaijefbe h

Myhnaifce peaKUHOHor 6ajioHa,

y pacTBop o a 12 g HaiïipujyMÔuxpoMama h

2 0 0 ml BORG, KOJ'H je TaKO^e npeTxoAHO oxjiaijeH JieAOM. ÄBaja Huüip0306eH30Ji y ücyTHM

Y c K o p o c e H3-

KpMCTajiHHimHHM naxyjbHuaMa.

Ha Ma^oM Hyqy, Hcnepe a b a nyTa BOAOM, Tajior c e 3a u e ^ e i t e yHece y óajioH H ./iano HcnapjbHBH

Oue^H

3ajeAHO ca

HHTpo3o6eH3o;i

ce

xaprajoM npeAecrn-

jiHiiie BOACHOM napoM. 3 e ^ e H e nape KOHAeH3yjy c e Beh y K0HaeH3aT0pcK0j ueBH

Kao CKOpo 6e3ÔojHa KpHCTaJiHa Kopa, noja c e Ha Kpajy,

HCKjbyHH BO^a 3a xjiaijeK>e, OueljeHH

Moace Aa h c t o i i h

KHcejiHHe).

na>KjbHBHM a o b o a o m

HHTp0306eH30Ji c e Hcnpecyje Ha n0p03H0M

y B3KyyM-eKCHK3T0py H3H3A KdJlLflljyMXJlOpiiaa npHHOc je 8 g.

3 a OApeijHBafte

ocyniH.

HHipo3o6eH3o;i

nape.

nopiiejiaHy h cyixiH

(He H3H3A KOHIJ. CyMnopHe TaqKe

Tonjbeiba

jeAHa n p o ó a cyBe cyncTaHue y e n p y B e ™ ca Ma^o eïïipa CTBopa) H noHOBO

noiiiTO ce

Ton«

ce

Hcnepe

ce

(3e^eHa 6 o j a pa-

Ha 6 8 ° AajyhH

3 e-

ji e h h pacTon. FIpeKpHCTajiHcaH

h3

ABOCTpyKe

kojih^hhc

amoxojia

MOJKe Aa

ce

AOÔHje y ancojiyTHO i h c t o m nocTojaHOM oôjiHKy. ApoMaTCKa H H i p 0 3 0 je,aHH>eH>a Mory TaKoije .na ce ÄOÖHjy 0KCH_naunj0M npiiMapuHX aMHHa, ana je caMO jeAHO 0kchä3UH0H0 cpeACTBO n03HaT0, Koje je 3a OBy peaKUHjy noroaHO, HaHMe cyjicjioMOHqnepKHcejiHHa (Cûro-oBa KHcejiHHa): C6H5

NH2 + 2 0

C6H5 • NO + H 2 0

OrJiefl,: 1 18 g c h t h o cnpameHor mjiujyMüepcyjKpama

H3Meiua c e iiito

j e M o r y h e ócube y nopueaaHCKOM aBaHy y 3 A o ö p o xjiatjen>e JieAOM ca

15

ml KOHif. cyMûopHe icucejiune. f l o c h e jeAnoqacoBHor c f a j a a a cnna c e C M e i u a Ha 1 0 0 g NE Aa h xjiaAehH HeyTpaJimiie ca KpucïïiajiHOM COROM. Y OBaj pacTBop nycTH c e Aa Te^e 1 0 0 ml amuimace BOW ( 2 , 8 g y 1 0 0 ml b o a c ) , npH qeMy c e , noc;ie KpaTKor BpeMeHa Huïïipo3o6eH3on H3ABaja y jKyTHM naxyAHuaMa.

r t o u i T o c e npoMeiuaHH pacTBop h 3 6 h c t p h ,

h HHTp0306eH30Ji

npeAecTHJiHine

boachom

napoM. O a

oaeAH c e Tajior OBora c e AoôHje

HeiuTO BHiue Hero i n t o OAroBapa nojiOBHHH ynoTpeôJbeHor aHHJiHHa. 1

Caro, Z. f. ang. Ch. 11, 845 (1898); Baeyer,

B. 33, 124 (1900); 34, 855, (1901).

je

HNTPOJEJIHFTEHIA h híhxoBh peayKUHOHH npodyKTH

Ochm cacBHM Mano

H3y3eiaKa

rpyna Be3aHa 3a T e p u H j a p H H

nocroje

caMo HHTposo je.nHH>éH>a, koji koJhx j e

ibpctom

h HCT0njbeH0M peljHBafbe

MOJieKyjicKe

(Piíoiy)

(H3C)3 • C • N O .

c y CTaH,y cKopo cBa HHTp030 jeAHH>eH>a CTany

nJiaBa

TewHHe

flHMOJieKyacKH.

NO-

yrjberoiKOB aTOM, nao koa HHTp0306eH30Jia. y aJiHtjMTCKOM

p e j i y npeTCTaBHHK j e Ha np. H H T p o a o H a o ó y T a H y

147

hjih s e i e a a .

HHTp0306eH30jia

NO-rpyne

flBajy

6e36ojHa\

y

pacTBopy

Be36ojHH o6;ihk je, KaKO noKa3yje ojiy

TeiHoj

unjaHOBojiOHHqHoj

KHcejiHHH

MoaeKyjia c e Hajia3e y jia6aBoj MeljycoóHoj

Be3n, Mowfla Ha HaiHH npeMa j e a H o j on HaBejieHHx (jiopMyjia: C6H5-N = 0

C6Hs • N — O

II • N => O

C6H5

HflH

t I O—N-C

6

H

5

Ka.ua ce pa3opw KpHCTajiHa c i p y K T y p a TonjbeH>eM hjih pacTBapaH.eM HacTaje jihcouhjaunja y o 6 o j e H e

nojeAHiiaMHe

Mojieicyjie, Koja ce noBehaBa ca noBHUiefteM

TeMnepaType.

OflHOCH c y cacBHM CJIHKHH Beh I103HaTHM OAHOCHMa KOfl a 3 0 T . H H 0 K C H . a a : (C6H5NO)2 Tpyna N O

Be3ana

2 C6H5 • N O ;

npexcTaBJba

(N02)2 ^ Z Z l 2 N 0 2

HajaKTHBHiijer Hocnoua 6 o j e ( x p o M O í j j o p ) , KojH no3HajeMo.

nao

ca hckhm PAAHKAAOM, koj'h H H j e y CTaH>y .na a T c o p ó y j e c b c t j i o c t ,

M j e NJIABH

HHTp030yrjb0B0,H0HHK.

H nopei

uito cy H H T e H 3 H B H 0

Tora

jeaHibeiba HHcy 6 o j e , j e p FBHMA nejiocTajy „ayKcoxpoMHe" r p y n e

H3o6yTHJi, OHa

oóojeHa,

HHTp030-

(Ha np. N H 2 , O H ) ,

noje

c y noTpeóHe PAAN BE3E ca bji3khom. HHTp030-rpyne

n o i c e h a j y y MHoroM na a w e x H j i H e r p y n e , t o he pehn,

aKuHje, K o j e ce oaHrpaBajy > C = 0 ,

aji,nexH.na, ycntn

koa

cnoco6HocTH

peaKiinone

BehHM^aeJioM Mory ,na ce n p e n e c y Ha A B o r y ó y Besy — N =

Káo

npHMep

Ba t o HaBemheMo

XHApoKCHJiaMHHOM.

KacHHje

K0HaeH3auHjy

na pe-

;iBory6e Be3e

O.

HHTp0306eH30Jia

ca

$eiiH;i-

HHTpo3o6eii30Ji p e a r y j e Taicolje h ca XHiipoKCHJiaMHHOM h 4>eHHJixHApa-

3hhom, ho y t o HeheMo OBAe fijiniKe aa yjia3HM0. AJIAEXHAH

pearyjy

ca

npiiMapHHM

AMHJUIMA

h

a a j y T3B.

a30MeTHHe

(ZZ/U^OSE

6a3e) Y3 H3ABajaH>e Boae (CTp. 137), Ha np.: C6H5 • C = H

O + H 2 N • CgH5

> C6H5 • C = N • C6H5 + H 6CH3HJIHiieHaHHJIHH

HHTp0306eH30JI H 3HHJ1HH flajy Ha CJIHiaH HaiHH CgH5 . N = Ornefl mcejiune

:

J c a h o m mi

AOAaje

óJiaroM 10

2

jiHTapa

ce

3arpeBaiby

MHHyTa

Ha

BOAe,

paHyacTO

O + H2N • C6H5

npe;ia3H

boachom npH

Bpjio

Ao6po

Soja

KaA

JincTnhnMa.

a^Koxo^oM~H ocyrneH Moace

y

ce

anujiuna

y

ce

3aracHT0

Koje

ox^a^H

N . C6H5 + 3 mi y

AOAa

Ha

H3 M a j i o

cuphemne

amoxona.

ripn

OCTEBH

ce

joiu

hcko^hko

MHJIH-

a306en30Ji

y

(JwjiTpy

n o p u e j i a H y TOÜH c e

npeKpHCTajiHiue

ce

HCKpHCTaaHiiie onpaH

H20

rjiaifujame 1 0 mi

HapaHyacTy.

Kjbyqa,

Oue^eH,

Ha n 0 p 0 3 H 0 M

Aa

N =

HUü¡p0306eH30Jia

KynaraJiy

qeiuy,

upBeHHM

1 g

a306eH30Jl.

-> C 6 H 5

pacTBopeHor

pacTBop

H2O

Ha 6 8 ° .

ca

Ha-

50%-HHM A3o6eH3o^

a^K0X0Jia.

Ha oBaj H3HHH Mory Jiaico aa ce no6n)y h y noópoM npnHocy MeuioBHTa (HecnMeTpHHHa) a3ojeflHH>eH>a. H3paflH no aaTOM ynyTCTBy Ha np. p - M e T H J i a 3 0 6 e H 3 0 J i H3 HHTp0306eH30Jia H p-TOJiyHflHHa! 1

H3y3eTaK

j e na np.

/?-HHTpo3oaHMeTHJiaHHJiHH,

0NeMy c^HiHe 6a3e, a TaKoije h BehHHa 2

A.

Büeyer,

nceyioHHTpoaa.

B. 7, 1638 (1874). 10*

148

OpraHCKO-npenapaTHBHH «eo

KoHjieH3auH]H aJwexHAa ca peaKTHBHOM Kojoj HacTajy He3acHheHH k c t o h h , na np.

mcthjihom

C 6 H 5 • C = O + H S C • C O • CH S H

hjth

MeTHJieHCKOM rpynoM, npH

> C 6 H 5 • C = C H • CO • C H 3 H 6eH3ajiaueTOH

oaroBapa aHa.iorHa peaKuwja apoMaTCKHx HHTp030je,nnH>eH>a. Ona 3axTeBa Hapomito noKpeTJbHB aTOM BOÄOHHKa h 36or Tora He Monce aa ce H3Beae ca o ö m u n M k6tohhm3 Kao luto j e auetoH. IlpoÄyKTH cy, Kao iüto je 6e3 flauer pa3yMjbHBO, a ä O M e i H H H . floMohy OBe KOHÄeH3auHje je 6 h m oMoryheHa cHHTe3a 1, 2, 3 - T p H K e i o H a ( F . Sachs), Ha np.: CH3

CO • C H 2 • CO • C H 3 + O N •

/

'

N

(CHs)2

aueTH^aueTOH CH S • CO J

->

C= N •/ CHs

H

»°

>

C H 3 - CO

• N (CH 3 ) 2 +

H20

CO CO • CO • CH 3 4 - H 2 N < ^

• N • (CH,) 2

TpHKeToneiiTaii riocaeÄfta (})a3a peaKUHje 3acnHBa ce Ha TOMe, äa ce a30MCTHHH acJctbom KHcennua jiaKo pa3fla5«y Ha KapöoHHJiHa je,nHH>eH>a h npHMapHe 6a3e. FIpaKTHHaH UHJb KOHÄeH3auHje jiokh y TOMe, iia ce MeTHJieHCKa r p y n a npeßefle y > C = O. H c t h eeH>e Koje ce Äoönja caapiKH l e r B o p o B a J i e H i B H a30T h cjiHiHO a30TÄH0KCHÄy, noHauia ce Kao c.no6o.naH paÄHKaji. Kao luto (JiopMyjia noKa3yje, OBaj' ce h3boäh H3 a30TÄH0KCHÄa TaKo, uito ce jeaaH O y obom 3aMeHH ca Äßa C G H 5 : H5C6\ ^ H5C6/

OrJieff: c e ca

nana jaKor TpjbaibeM »cyTHX

1 g

PacTBop

KynaTH^y.

CTaKJieHHM

KpncTajia.

H 3

1 g

4

)

e

H

upßeHH

uiTannheM

A30Kcu6eH30Ji

J

I

X

H

^ p O K C H J i a M H H a

AOÄa ce y 3

KajiujyMxuapoKcußa

)KyTo

H

mUip0306eH30Jia

(peHtuixuapoKCiuiaMima,

pacTBopa (1:1)

Ha b o a c h o m

ÄH(})eHHJia30T0KCHÄ

A 3 0 K C H 6 e H 3 0 J i

HHTp030ÖeH30Jia. noMerna

= 0

1 0 ml

amoxom

MyhKaite

hcko^hko

h 3arpeBa h c k o ^ h k o

pacTBop

ce ox-na^H,

H3ABaja peaKUHOHH ce t o n n

y

B e h Ha 3 6 ° ,

h

npoÄyKT pa^o

MHHyTa

npH neMy ce

y

ce

oöjiHKy

H3Äßaja

y

HnTpojeAHH.eH.a h h>hxobh peayKUHOHH npoayKTH

149

o ö ^ H K y y j b a H3 n p e c H h e H o r

p a c T B o p a . n p e K p H c r a j i H c a B a H > e M H3 Majio

ax-

Koxojia

( c a q y B a T H KpncTa^ic 3a n e j m o B a H > e ) Ä o ö n j a

ce

HAH üempojieyMempa

CBeTJio a c y r o , c K o p o

6e3Ó0jH0

jeÄHH>eii>e.

Cjia6o o6ojen>e a30Kcn6eH30Jia y nopeljeity ca u p b e h h m a306eH30Ji0M jiaKiue ce MOJKe pa3yMeTH npeMa d a p o j (jjopMyjiH (I), Hero npeMa OHOj, Kojy je Mecro H>e Äao Angeli (II). I.

H5C6 • N -

N • C6H5

II.

H5C6 . N = N • C6H5

O

O

MeljyTHM iHfbeHHua aa ce HecHMeipHmiH MepHa

o6jiHKa

a30KCH6eH30jiH

jaBJbajy

y

ÄBa

H30-

(Artgeli), R • N = N • R'

h

R • N = N • R'

Ä

•

O ojiiiociiMa a30KCHÖeH30Jia npeMa a30- k XH,npa306eH30Jiy npenapaT.

C6H5 • N = N • C6H5 II O roBopiihe ce y3 Kayh«

OßÄe heMO joui noMeHyra HHTepecaHTHO npeMeunaibe, Koje npeTpnw a30KCH6eH30Ji ÄejcTBOM kohu. cyMnopHe KiicejiHHe; npH TOMe Haciaje p - O K C H a 3 0 ö e H 3 0 j , 0CH0BHa cynciaHua khccjihx a3o-6oja (Wallach). C6H5 . N = N • C6H5 II O

> C0H5 . N = N • / \

6. X H f t p a s o ö e H s o j i h a) Ha

öaJioH o ä

npeBa

ryMeHor

asoöeHsoji

X H A p a 3 0 6 e H 3 0 i

ca

BoMHa u e ö

koco

Be>Ke c e

Ha r o p e

KpaTKHM

nocTaBJbeHHM

TaKO a a c e öajioH M O » e ; i a K o c h 3 } k h o

a a MyhKa.

je 3aTBopeHa nayTeHHM 3anyiuaHeM h y n p a x y , n c v r p e ö a H 3a p e a n i j H j y .

cjiyjKH A a c e

P a c T B o p H c e 5 0 g HampujyMxuflpOKCiiMa. pacTBop ce y

3 a j e A H O c a 5 0 ml amoxona

öajiOH.

Ys

OH . /

1 JiHTpa , n o 6 p o c e y ^ B p c T H y j K H HacTaBaK n o

o a TaHKHx ueBH ( c j i . 2 9 ) .

poKor

N

CHa>KHO M y h K a i t e

h 41 g ao^a

ce

y

c e ct3jihhm

1 5 0 ml B O ^ e

CaapJKaj ctaje

Tonao

H joui

( 7 3 MOJia) Hump0öeH30Jia Hajnpe 6 — 8 g

numa

yHece y

öypHa

üpaxy pe-

ÄOAaBaH>eM unHKa y n p a x y peaKUHOHa CMerna

o a p j K a B a Ä a CTa^HO K J b y q a . f I a 3 H c e Ha TO, ,a;a p e a K u n j a ö y p H a , a^H c e

HacTaBKa

y ö a u y j e uhhk

H>y

h , HenpecTaHO Ä a j b e M y h K a j y h H , n y c T H c e , ,n;a c e n p B O 3 a B p n m aKunja h Ta^a

uih-

K0H,a;eH3aT0p0M,

B e p T H K a m a ijeB

Kpo3

AmiiHuy

KOMa^nheM

He ö y ß e

cyBHine

H3ÖeraBa a a c e H>eH t o k x j i a l j e i b e M npeKHHe. ce

Sajicma

Hajnpe

cßeivio m y r , k3ä norpeÖHa

o6ojn

upBeHO ( 3 3 0 6 e H 3 0 J i ) ,

H3j3a,n;

no-

kojihmhhs p e ^ y K i i n o H o r c p e ^ C T B a C T y n n

150 y

OpraHCKO-npenapaTHBHH

OKO 1 2 0 — 1 5 0 g

ÄejcTBo. flOTpeÔHO j e

peaKitHja n p e JKHBO

neo

(75%-Hor)

3 a r p e B a c e Ha BOACHOM

BpeMeHa n p e c r a H e ,

npaxy.

AKO

KynaTH^y

Koje

uHHKa y

Kjbyqa. HeonxoÄHo

je,

ó a j i o H a oApJKaßa y ca opraHCKOM CMeuiH,

Aa

ce

ôa^oH

c ^ y j K H 3a H c n n p a i t e

Ueaa

caApjKHHa

(npeTxoAHO

HcruiaKHe

óa^OHa j o u i

noracHTH

ca 5 0 ml

Bpyher

cacBHM

n^aiweHOBe

y

KOJH

ajiK0X0;ia

I^HHKOBOT n p a x ä .

Ha e H M y h n a eTap

ce

KojH ce

xHApa306eH30Jia 10 g

(=3,2

ôpoMa

nycTH

ml)

OA 6,0 g N a O H y 7 5 ml H 2 0 ( 7 5 ml 2 n - N a O H

pacTBOp

y 3 xJia^etbe jieAOM H O B a j p a c T B o p 9,2

g.

10

xnnoöpoMHTa

(1/20 M o a a ) y

MHHyTa;

HcnapH H A O Ó H j y npeKpHCTajiHcaHH

ce H3

eTapcKH

60 ce

ca

Aa

pacTBopoM

ml eïïipa y MHJIOM a e B K y 3a OApacTBop OABOJ'H OA B O A e H o r ,

HapaHyacTO Majio

noMeuia

ce

pacTBopa)

upBeHH

amoxojia

Tone

JIHCTHÍIH Ha

68°.

a306en30Jia, flpHHoc

je

KBaHTHTaTHBaH. T a K o l j e BHiueqacoBHHM n p o B o i j e i t e M B a 3 A y x a K p o 3 ajiKOxoJiHH p a c T B o p . XHApa306eH30Ji,

KOMe j e A O A 3 t o

a j i n a j i n j a , H a c T a j e a 3 o 6 e H 3 o ; i ca

AOÖPHM

npHHOCOM. 2. rpeBa

y

jQ,H c n p o n o p U H o H H c a H> e M : enpyBeTH

Ha

MajioM

naajueHy

UpBeHH p a c T o n c e AaJbe naacjbHBo no^He Aa Kjbyqa.

ripa

1—2 g AOK

3arpeBa

ce

ce

xuapa306eH30Jia He HCTOÌIH.

CBe AOK CTBopeHH

oxaatjeiby Aoônja ce nojiyqBpcra

3a-

HapaHijacTO ÜHUJIUH

cMerna

He

ijpBeHor

151

HHTpo]e^HH>eH>a H H>HXOBH peayKUHOHH npoflyKTH

III, 6

A 3 0 6 E H 3 0 J I A H SHHJIHHS. Ba3a ce MOHce C K C T P A X O ß A T H BOÄOM H ÄOKA3ARA noMohy peaKunje ca XJIOPHHM KpeiOM, a a306eH30Ji ce Moace ÄA npeKpacTa^Hiue H3 amoxojia. A K O x o h e Aa ce H3o;iyje H 2HHJIHH Kao T a i c a B , npnjiHKOM p a j a ca BHiue xHapa306eH30Jia, TO ce OH OÄ a306eH30Jia OÄßAJA noMohy pa3ÔJia)KeHe rjiatiujame cuphemm Kucemne H IIOHOBO ce ocaoöaija H3 pacTBopa aiiewawa noMohy KOHijeHTpoBaHor pacTBopa XHÄpoKCHÄa. EKCTpaxyje ce eTpoM HTÄ. A 3 0 6 e H 3 0 f l j e ca xpoMotj)opHOM r p y n o M

—N = N— ociioBHa cyncraHua a30-60]a,

Bpjio j e nocTojaH H He pa3^a5Ke c e npH ÄecTHJiauHjH.

OCHM Torà, Kao KOÄ BehHHe Ä p y r a x

a3o-jenHH.eH>a, N = N - r p y n a j e j a n o yHBpuiheHa H3Meijy 06a apoMaTCKa j e 3 r p a . H a Taj H a m m c e o6jamH>aBa nocTojaHOCT a 3 0 - 6 0 j a . n p e M a TeopHjH Tpeöa Äa n o c T o j e ÄBa C T e p e 0 H 3 0 M e p H a

a306eH30Jia:

H

Çe 5 H

N = N

N= N

A6Hs

C6H5 C0H5 ifuc-asoöemon OßA JE H30MEPNJA

tupaHc-a3o6emon

TEK NPE KPATKOR BPEMEHA EKCNEPIIMEHTAJIHO

NOTBPLJEHA; YCNANO CE,

0CBETJBABAH>EM PACTBOPA A3O6EH3O;IA ÄA CE NPEBEAE CIAÖHAAN (TPAHC-) O6;IHK ÄEAUMHIHO Y

quc-oójMK h ÄA CE OBAJ rana 0ÄB0JH aicopnunjoM (Hartley)

(YNOP. CRP. 12).

A306eH30Ji Äaje ca KOHueHTpoBaHHM KHce^HHaMa upBeHo o ß o j e H e COJIH, HITO ce MOJKe yTßpÄHTH npe^HBaH>eM cyncTaime COHOM KHCCJIHHOM. XHÄpnpafteM ce NOHOBO ÄOÖHja XHÄpa30ßeH30Ji. ÄejcTBOM B0Ä0HHKcynep0KCHÄa HAH a30THe KHcejiHHe Moace ce aÄHpaTH O H HacTaje a30KCH-jeÄHH>eH>e. O CHHTC3H acHMeipHiHHX apoMaicKHX a30jeÄHibeH>a »3 HHTp030-jeÄiiH>eH>a H npHMapimx aMHiiä 6HJIO Je paHHje roBopa. H a T C M n e p a T y p n T o r u b e t t a pa3Jia>Ke c e

H5Cg —Ni'H HN—CgH5

IÖI

H5Ce — NIM HN—ÇeHs

xaapa3o6eH3o

H3C6 • N

—

II +

H5C6 • N

JI

npeMa jeÄHaiHHH :

H2N • C6Hs HON • C6H5

y a 3 0 6 e H 3 0 J i H a H H ji H H. Kaciinje (VII, 6) he 6HTH roBopa o cacBHM aHaJiorHoj pea K U H j H KOÄ ( } ) e H H J i x H Ä p a 3 H H a ; T H n H q a n n p H M e p 3a o B y p e a K U H j y j e C H O H T Ü H O

pa3-

JiaraH>e B0Ä0HHKcynep0KCHÄa Ha KHceoHHK H BOÄy: OiH

OH

0:H Í H

O

HÖH

O

HÖH

CJIH^HO OBOM npouecy npncycTBO n j i a T H H C K H X M e T a n a KaTajiHTHiKH yôp33Ba cnoHiaHO pa3Jiarait>e XHÄpa3o6eH3o;ia.

H

B) B e H 3 H Ä H H H 3 X H Ä p a 3 O 6 e H 3 O JI a

9,2 g xunpa.306en30Jia pacTBopa ce y IIITO je Moryfce Maite ewpa H y 3 MyhKaite nycTH, £ a Kanjbe y 10 mi JieaoM oxjiaijeHe OKO 7-n cone mcejiune ( K O H U . KHcejiHHâ pa3Ô^aHceHa ca HCTOM 3anpeMHH0M BOße). Ben3UMUHXJiopxuapaïïi ce H3ABaja KpHCTajiHHHqaH H nocjie ÄOÄaBaKba 50 ml KOHU. COH& KHcejiHHe H CTajaH>e 1/2 caTa peaKUHOHa cMeuia ce oueAH Ha BaKyyM H n e p e COHOM KHCC^HHOM HCTe KOHueHTpaunje Kao H r o p e H ca

152

OpraHCKO-npenapaTHBHH a e o

MaJio eTpa. npHHOc je 9—10 g. XjiopxHApaT ce mojkc npeKpHCTajiHcaTH H3

Bpejie

AOAaBaiteM

BO^e

J\A 6H

CE AOÖHJIA

coHe

c^oöoÄHa

KOHIF. HAMPUJYMXUAPOKCUFLA cnpaBÄ.eH

Ha TOIUIO

He

Aoópo

H

MOpa a a

6y^e

Mopa

CTBop

Hcnepe

ÖHCTap;

Äa c e

npeMeuiTaite 3UHUH

H3HJia3H H3

Ao^a ce COJIH,

coHe

ripe

je

o q e A H c e Ha

pacrBop

jiyacHHe

AOAABAIT>A

MAJIO

KOJH

KHcejiHHe H

HCKpHera./iHcaHa H3ABojeHa 6 a 3 a

CO^H

pa-

npoue^a. MOACE

AA

ce

H3 MaJio AJIKOXOJIA. T a q n a T o n j b e n . a xeMHiap

pa3ÖJia>KeHe

paicTBopy.

c j i y n a j y Aa j e H c n p a c T a ^ i H c a o x j i o p x H A p a T ,

6EH3IIFFUN

CJIOÓOAHH

6a3a

pacTBopy

KOHU.

Heimo

BOAOM.

y

0X.aaijeH0M

HCIIITO

6eH3H.HHHCKa

OABHiiie

y3 äoä3T3k

6 p 3 0 o x ^ a ^ e H Ha 1 5 — 2 0 ° ; ^anyyM

KHCCJIHHG

XH,npa3o6eH30Jia

H Koje je

H30MepHH

y

H3a3BaHO

M

NPEKPHCTAAHIIIE

BPEJIE

BOAE

HJIH

122°. Koje

6eH3HÄHH,

KaTajiHTHiKHM

flejcTBOM

je

1846

r.

MHHepajiHHX

OTKpHO

pycKH

KHcejiHHa,

npo-

NA naJjy e H e p r e i c K H C H p p M a u i H H j e , T j . 3 a c H h e H H j e cTaifae. O ß a j n p o u e c MoaceMo a a yßpcTHMO y Äpyre a H a j i o r H e npouece, KOÄ KOJHX c e y r j i a B H O M p a j i H o TOMe, a a cyncTHTyeHT Ha a30Ty H 3 M e H H CBOje M e c T O ca jejiHHM H-aTOMOM y je3rpy, H TO BehHHOM c a OHHM y / ? - n o J i o H < a j y . T y c n a f l a n p e M e i u T a t t e (})eHHJicyji(})aMHHCKe KHceaHHe tjieHOJi y

Te>«H>e M O J i e K y j i a ,

y

cyjicjjaHHJiHy

(cTp. 144),

KHcejiHHy

3aTHM a u e T a H H ^ H Ä a

P-XJIOPAUEIAHHJIHÄ

/

y

(IV,

5),

-> H a C • CO •

• CO • CH S

H

C1 •

> N . CO • CH, -/ C1

H

y

p-aMmio-

iV-xJiopaueTaHHJiH.ua

^ > - N H

2

NH • CO • CH,

OCHM Tora OBae ÄOJia3H H npeMemTaH>e apoMaTCKHX H H T p o 3 a M H H a , o KOjuwa he nacHHje 6HTH roBopa, Ha np.:

\

-> ON:

:— N • CH 3

\

• N • CH 3 H

NO

Ha HCTH HaiHH OABaja ce y 6 e H 3 H Ä H H C K o j p e a K u n j H , rpyna HN • C 6 H 5 ca H Be3yje Kao H 2 N • C 6 H 4 - H a MecTO y p-nojio>Kajy, Koje Je BOÄOHHKOB aTOM HanycTHO.

a30Ta

>

NH — N H ,

/ _ _ > - N H rioTpeöHO je ,na ce noÄByqe, aa ce MOÖHJIHH ocTaun He OÄBajajy Kao „CJIOÖOÄHH paÄHKajiH", Beh ce OBO noMepaite rpyna .nemaBa y nojipyqjy MOJieKyjicKHX cHjia B e 3 e . CJIHMHOCT Koje

CMO M a j i o i a c

30Jioßa jeHH Bara

je3rpa

ocTaTaK

npeMeiHTatta Kao

3ay3eTH. T a a a 3axBaTa

cBojHM

apoMaTCKHX xHÄpa30-jeÄHH>eH>a ca peaKunjaMa H3MeHe,

KOÄ

napajiejiHe no

H3HejiH, ÓHBa j o m npaBHJiy

a30T0M

0-aMHH0ÄH(})eHHJiaMHHa,

o-nojioiKaJ Ha

jacHHja,

Kaa

cy

p-n0Ji03KajH

H e Ä 0 J i a 3 H ÄO C T B a p a H > a Ä H ( j ) e H H J i - 6 a 3 e ,

np.:

npeMa

apyroM

a30Ty;

Tano

o6a

6eH-

Beh

OÄBO-

HacTajy

ÄepH-

153

HHTpojeÄHftefta H H>HXOBH PEAYKUHOHH npojiyKTH

— NH

H

3

C - /

^>-NH2 —

\ N H

— NH

H

3

C/

O B a j c e OÖJIHK n30MepH3auHje 03HáiaBa Kao c e u H i H H C K o BeH3HÄHH

H aecjwHHjiHe

6a3e

npeMeiuTaite

H AH3HH3HAHH,

TOJIHÄHH

(P.

Koje c e

Jacobson).

 o ô n j a j y na

CJlHMaH HaiHH H3 0-HHTpOTOJiyOJia H 0-HHTp0aHH30.ua, -NH

CH3(OCH3) Ha BejiHKO c e npoH3Boae y HHflycTpnjH

2

CH3(0CH3)

6 o J a , Kao BaiKHH Meljynpo,nyKTH 3a Äoönjaibe a 3 0 -

6 o j a , Koje ÄHpeKTHO 6 o j e naMyieH>a HMa He caMo HayiHH Beh H TexHHqKH BeoMa Be^HKH 3HaHaj. HcKopHiuhaBafte ynbOBOÄOHHKa, rioie.no jfc ca oTKpnheM aepHBaTa 6eH3o;ia,

HHTpoBaaa;

peaKUHje

0M0ryhH.ua Je ÂOÔHjafte

KOJN c e Ha;ia3e y KaTpaHy KaMeHor y r j t a , peaynuHja

a H H JI H H a

HHTporpyne y aMHHorpyny KOÄ

y TCXHHHKHM

pa3MepaMa, Kao no-

jia3Hor MaTepnjajia 3a MHoroöpojHe 6 o ] e H cjjapMaueyTCKe n p e n a p a i e ; H>eMy c e npHKjbyqyjy XOMOJIOrH Ro

TOJiyHÄHH,

ÄOHHK B e s y j e 3a

Ha({)THJiaMHH

KC1IJIHÄHH,

CTBapana

a H H JI H H a

HHTporpyny,

HTÄ.

H3 HHTPO6EH30JIA ÄO;ia3H xaKO, HITO c e peaKTHBHH BO-

KHCCOHHK c e nao BOM

OÄBaja H Haj3aa

c e Beine

BOÄOHHK.

To HHje jeÄHOCTaBan npouec, Beh T e i e npeKO cepwje nHTepMejiHjapHHX (J>a3a.

fO

+ 2 H

C.H.

I H

N o

H20 > CBH, . N O

NOH

HHTPO3O6EH30JI 'H

+ 2 H >

M/ NI \OH

r H > C5H5 -H2O

+

2 H

NH,

ß-lJjeHHJIXHÄpOKCHJiaMHH LUTO ce noÄ YCJIOBHMÄ ÂOÔHjafoa xHapoKCHjiiïtoHH,

aHHJiHHa He HaHJia3H HH na HHTpo3o6eH30Ji HH Ha

HMa CBoj y3poK y TOMe, UITO je 6p3HHa peayKUHje

«ajieKo Beha, Hero JIH cawor HHTpo6eH30Jia (F. y c^e^HJER

neyTpajiHOM npoayKTa

HJIH ajiKaJiHOM

XH.npnpaH>a,

pacTBopy

TepHja,

Koja

MOJKC a a Bewe

noMepajy

ce

OÄHOCH y KopncT OH c e ÄOÖNJA

(J)EHHJIXHÄPOKCHJIAMHHA.

6eH30Jia, KojH c e cycneH^yje y pacTBopy LIHHK y n p a x y MOWE a a pa3Jia)Ke

Boay,

aMOHHjyMXJiopHaa H p e i y n y j e CTBapajyhH Z n ( O H ) 2 ,

ocjioöotjeHH

MeljynpoayKaTa

OBHX

Haber).

UHHKOM y n p a x y .

Ka.N j e n p H c y r a a

BOAOHHK. 3 a ì o j e noaecaH

y

2H20 +

0

2

XHÄpOKCH.iaMHHS.

Mo>Ke,

npn npaBHjinoM

(M.

TO h e Traube):

Zn(0H)2+H202

HauieM c j i y i a j y na MecTO KHceoHHKa CTyna H H T p o 6 e H 3 0 J i

ripH TOMe ce penyicuHja

HeKa Ma-

MOJieKyjicKH,

pehH OÔHQAH KHCCOHHK, KOJH npn TOME npejia3H y B 0 Ä 0 H H K C Y N E P 0 K C H Ä Zn +

npeTno-

H3 H m p o -

pajiy,

aa

3aycTaBH

(HannuiH jeÄHaKaja

cnna

ce

aHXHÄpHÄa)

h

ÄO^a ce nocTeneHO HOBe KO^H^HHe n e n a qeTKy

45

ml

(1/2

aoTJie,

miHBa H3Haa c y M n o p H e

e aaraHO

Teqe

CTpyKy

äo

KHCEJIHHE

Tpaje

oko

H3 ^ e B K a

10—15

MOJia)

äok

g

150 y3 ce

6en30Jia,

KHceJiHHe, y 3 MHHyTa.

npn

3anpeMHHy

neMy ce

MyhKa&e

PeaKijHOHa h

ca^oflaBaiteM

kojihhhh3,

ÄOÄ'aTa

3a OÄßajaite y 3 M e m a f t e

qeTBopocTpyKv

öenaona

üyuubme cyMüopm mcemne boäom h . n o ö p o M y h n a i b e ,

Te«iHe

x^a^e&e cßana

hs

cMerna xjialjeibe

Ha x ^ a ^ H O

Koja y

He p a c T B o p n . nycTH

ce,

jieÄOM y

3acHheHor

noC.ynaa Tpo-

pactBopa

Cyji(}>OHCKe KHceJiHHe Kyxuwace

KojH ce Ha^a3H y n e x a p y . f i o c h e KpaTKor BpeMeHa

COJIU

ce HatnpujyMOBa co 6en30Jicyji(p0HCKe a

HapöiHTO

155

.JiaKo,

oiiiTpHX HBHU,a;

ano

ce

y oöJiHKy cjajHHx

mcemne

3haobh

qaiue

Tpjbajy

Tajior

Aoöpo

Hcnpecyje

miyTeHHM

KJieHHM 3anyuiaqeM H Hcnepe Asa nyTa ca Ma.no 3acHheHor cojiu.

jiHCTHha,

cTaKJietìHM uiTannheM

n o o i e AyJKer c r a j a i b a CTBapa c e r y e r a KpncTajiHa

Koja c e oue^H Ha BawyyM, XHHjCKe

mnpa\a

Kama,

hjih CTa-

pacTBopa

C o c e o c y n m Ha B a 3 A y x y Ha (J)H^TapxapTHjH

hjih

Ky-

Ha no-

p03H0M n o p u e ^ a H y , cnpaiiiH c e h 3arpeBa y c y o i H H U « Ha 110°, a o k ce He AOÖHje cyBH npax. f l p H H o c OKpyivio 100 g (caApJKH N a C l l ) . PaflH npeHHiuhaBaita aücojiyüiHor J\a. c e

aoÖHje

npeKpHCTajinine c e 5 g

cnpoBor

npoAyKTa

( c y ji H Aeo je o6aBHjeH

3MHJ3CTOM

OAOBHOM

BpeMe HcnycTH ce H3ABojeHa KyBaft>a

CTBOPHAO

ce

OKO

UEBH, K P 0 3

1 8 ml

KOjy

UYPH

BOAA.

C

BPEMEHA

Ha

y Ma.rcy MeHsypy. flocJie 5-qacoBHor

BOAS

BOAE,

Koja

NOTHIE

ACJIOM

H3

CYMNOPHE

KHcejiHHe, a ACAOM H3 peaieH>a n o m y H o

OÄBaja O H - r p y n a

90

na

— BepoBamo

o.nroBapa npouecy ca JCÄHHM aTOMOM

-N02

MecTo CTynajy rpyne

H>HXOBO

cip.

BHÄH

KHcejiHHe H Be3yje

OÄHOCHO

-S03H. H3

npeixo^Ho naciyna aamiHja Ha

] e « H y ÄBoryöy Be3y 6eH3o;ioBor je3rpa OTnpHJiHKe npeMa cxeMH:

H

% / H

H

H

H/ \

H

HSOjH

4" HO V

H

HÖH

y

aflH(})aTCKOM pejiy

H

H

H

noHOBO cTBopw CTaöHJiaH apoMaTCKH

6eH30Jicyjiiji0HCKy

oJieijiHHH, Koje

V

H

MetjynpoflyKT y yrjiacToj 3arpaÄH H3 T e u f t e M CHCTeM, H3Äßa]a BOÄy H iipejia3H y

ÌSOoH

-H20> H

KKcejiBHy.

CTajiHO MopaMO na nopeÄHMO

ca ÄepHBaTHMa

6en3o;ia, noHauiajy ce y npHHUHny HCTO. ETHJICH ajinpa, ÄOÄyuie Ha HHCKoj TeM îepaTypn, (OKO 50°/ 0 )

KOHueHTpoBaHy cyMnopHy

KHcejiHHy Äajyhn

eTHJicysinopHy

KiicejiHHy,

npeMa :

CH„ = CH, ¡2

CH3 — VCH j l l 2 • O — SOsH ,

r

v^llg

2

j a M e y3 A p y K i n j e pa3JiaraH>e H 2 S0 4 -MOJieKyjia. OBH peaKUHja He M O « e aa ce ocTBapn KOÄ 6en30Jia H3 oneBHÄHHx pa3Jiora, j e p oHa Mopa na 6 y a e H3pa3HTO peBepcHBHa: AKO ce naK eTHJien noÄBprue aejcTBy 30Jia, cy^i(J)OHOBaHH naciajie

nywjbHBe

npoayKT,

aJiKoxojicyji(})OHCKe

cyMnopHe KiicejiHHe, OHÄ3 HacTaje Kao H KOÄ 6en-

Haiuie T3B. K a p ö H J i c y j i i ^ A T ,

KHcejiHHe

eerepHc|jHKOBaH>eM

ca

KO]H ce

H3BO.AN H3 Hajnpe

H2S04 h

HaKHaÄHHM H3ÄBa-

jafteivi B o j e .

CH, = CH„

CH 2 I

•CH 2 I

O

y

CH„ — CH2 I O - SO, H

--> CH„ OH •

(KapÖH.icyfltfiaT)

S02

cyuiTHHH cacBHM aHa;ioro p e a r y j e eTHJieH

JiHHe, npH leiwy nacTaje H H T p o - e T H J i H H T p a T

ca CMeiuoM a30THe

H cyMnopHe KHce-

(BHÄH c i p . 135). KaKO ce Äoßnjajy ajiKHJi-

cyji(j)OHCKe KHcejiHHe ? JlaKoha KojoM cy^c{)orpyne CTynajy HHTpoBafta, To-iiyoji

H

OÄ npHpOÄe

npncyTHor

y apoMaTCKa jeÄHH>eH>a 3aBHCH

cyncTHTyeHTa.

EeH30Ji ce

ÄOCTa

HCTO Kao H KOÄ

TeuiKO cyji({)OHyje,

(feHOjiH H aMHHH. Tewe Tene cyji(j)OHOBaH>e 6eH30Jicyji(|)0HCKe KHcejiHHe. OßÄe ce Mopa noT-

HaijíTajiHH Heimo jiaictue, Hap04HT0 JiaKo

koä HHTpo6eH30^a

häh

Äajbe cyjie

noMohH peaKUHja noBehaiteM caapwaja S 0 3 y cyMnopHoj KHcejiHHH. nouiTO cy

N02

H

SOsH

cyncTHTyeHTH

II peÄa,

TO

HOBH

cyncTHTyeHT

HÄe y /n-nojio5Kaj. BHCOKO npoueHTHH ojieyM npeBOÄH 6eH30Ji Haj3aÄ y ifoHCKy

KiicejiHHy.

ÄOHHUHMa y

Xji0pcyji(})0HCKa KHcejiHHa K0HÄeH3yje ce ca apoMaTCKHM yrjbOBo-

apH;icyji(})oxjiopHÄe.

H3 HaiJrrajiHHa (})OHCKa

KojH yjia3H,

6eH30JipHcyji-

ce H3B0Äe Äße

cyj«j)OHCKe

KHcejiHHe

KHce^HHa:

SO.H

CC-KHCejIHHa

ß-KHcejiHHa

H

TO

a-

H

ß-Ha(j>Ta;iHHcyji-

160

OpraHCKo-npenapaTHBHH jieo CyncTHTyuHja

Kojn c e O Ä J i H K y j e

KOÄ

Ha(}>TajiHH0B0r

je3rpa

IV, 5

BpuiH ce 6e3 H3y3eTKa y

a-nojio>Kajy,

xajioreHa HJIH HHTpor p y n e BOAH H C K J b y n H B O ÄO A-aepnBaia. OBO je T a n o t j e c ; i y q a j KOÄ cy;i({)OHOBaK>a. A K O c e Ha(J)TaJiHH cyjicJjoHyje H a HHHKe H a Hai})TaJiHH h c y M n o p H y KHce^HHy. PaBHOTejKa H3Mefjy cyji(j)OHOBaH>a h xH,npo;iH3e HaifTaJiHH -(- H 2 S 0 4

cyjuJjoncKa KHcejiHHa -f- H 2 0

f

Ha Hamoj peaKUHOHOj TeMnepaTypn (170—180°) 3a cc-KHcejiHHy Jie>KH BHiue Ha jieBO, ÄOK ja ß-KHcejiHHy jaKO Ha «ecHO. A;IH nouno je y peaKUHOHOj CMCUIH yBen npHcyTHa H a-KHcejiHHa, TO Mopa TaKolje H ß-KHcejiHHa iia no.mie)Ke xn,npo;iHTnqKoj paBnoTeatn. ZloHCTa npw TonJbefty ß-Ha4>TaJiHHcyji({)OHCKe KiicejiHHe ca cyMnopHOM KHcejiHHOM (Koja caapjKH Boae) aoöHja ce Majia KOJiHiHHa H30MepHe a-KHcejiHHe. Ilo3HaTH cy CJIH4HH OÜHOCH KOÄ ( j i e H O J C y j ^ O H C K H x K H c e j i H H a H npe CBera a H T p a x H H O H a , KojH y CBOJHM peaKUHjaMa cyncTHTyunje noKa3yje H3BaHpej;Hy CJIHMHOCT ca Ha4)TanHHOM. AHTpaxHHOH ce Tewe cyji({>OHyje H CTHM je y Be3H, .aa noBHiueHa TeMnepaTypa, Koja OBjje Mopa na ce npHMeHH, oAMax ÄOBOÄH ao ß-KHcejitme, Koja je Ba^uia Kao nojia3HH MatepHjaji 3a CHHTesy aJiH3apHHa. MHÄycTpHja je nnaK Hawjia nyTa H H a m m a Äa aolje H ÄO a H T p a x H H O H - a - c y j i ( J ) O H C K e KHcejiHHe, Koja paHHje HHje ÖHJia npnCTynaqHa. ÄoflaTKOM » n i e peaKUHja cyjic{)OHOBaH>a Hjie KaTajiHTHHKH y npaBuy a-cyncTHTYUHJE* (R. E. Schmidt). KOÄ

A H H H H ce iiapoMHTO jiaKO cyjieM cßor cyji({)aTa (neneibe). To Hac noTceha Ha npeTBapaH>e aHHJiHiiaueTaTa y aueTaHHJiHÄ. y CTBapn Je Bp.no BepoBatHO Äa nacTaje Hajnpe aHajioraH npojiyKT, cyjiijiaMHHCKa K H c e j i H H a , KOÄ Koje je cyji(})0HOBaHa aMHHO-rpyna. KOÄ 0Be, npeMa no3HaTHM npiiMepHMa: npe.na3 ({¡eHHJixHApoKCHjiaMHHa y p - a M H H O c j j e H O ^ , (JjeHHJiHHTpaMHHa y p - H H T p a H H J i n H , cyjiifio-rpyna npe.na3H y p-noJioiKaj. NH *

—NH • NO»

NO2

N H 2 • H,SO.

npHMapHH aHHflHHcy^tjjaT Ä0Ka3

3a

/

(})eHHJicyji(i)aMHHCKa K H c e j i H H a

\—NH,

cy^^aHH^Ha

l-Ha4>THJiaMHH-4-cyjiaHHJiHe

KHcejiHHe

y c J i o B H M a pa.ua,

KHCejiHHy

npeJia3H Ha BHiuoj

(Hat})THOHCKy

H a c i a j e n p n cyfl(l)OHOBaH.y

TeMnepaTypn

ce

Kao

Mef)ynpojiyKT y

HHÄycTpHjn

a3o-6oja

H TO

o-jeflHH>eH>e y

peÄyKunjoM

c y ^ ( } ) O H C K e K H c e j i H H e . B e n H K H TCXHHHKH SHA^aj H M a j y n p e C B e r a (jjOHCKe

KHcejiHHe

Äa ce ÄHa30Tyjy

HATJJTAJIHHOBOR

HJIH T a K o l j e

Kynayjy

peaa

H TO y

y

KHcejiHHy).

KOJiHHHHaMa, K o j e He n p e T C T a B J b a H e K H B e h n H H T e p e c . H a n p o T H B , M e i a H H J i n a ÄOÖHja

KHcejiHHa

OBaj TOK p e a K U H j e n p y w a C C - H a ( J ) T H J i a M H H , iiija cyji(J)AMHHCKA K H c e j i H H a ,

K o j a MO>Ke a a c e H 3 0 J i y j e n p w 6namM

Flopea

S — N H • S03H

—h2O •

a M HH o-

He3H3THHM KHcejiHHa

m-HHTpo6eH30Ji(H OKCH-)

cyji-

n p B O M p e a y jeÄHH>eH>a Koja M o r y

ca ÄHa30jeÄHH>eHjHMa.

Oß^e

npHnajajy

HajBaiKHHje

a30-Ö0je. 1

y cjiywajy aHTpaxHHOHa H3rjieAa aa ß-cyji(}>OHCKa KHcejiHHa He HacTaje npeMeuiTaaeM

H3 a-KHcejiHHe.

161

Cyjiyjy ca N0 2 . Obo ce hckop H i u h y j e Ha np. n p n ÄOÖnjaiby n H K p H H C K - e K H c e j i H H e . n p n cyjKjjOHOBafty a-Hac}>TOJia S O s H - r p y n e ce JiaKo yBOÄe y eroBa 7-cyji(jjoHCKa KHceJiHHa npnnaAajiH c y paHHje HajßawHHjHM 5KyTHM öojaMa 3a ByHy. CyjujioHCKe KHceaHHe apoMaTCKHx yrjbOBoaoHHKa He Mory jiaKo Äa c e H30Jiyjy, 3 6 o r cBojs BehHHOM BejiHKe p a e T B o p j b H B o e T H y boah^h Majie TeHÄeuHje 3a KpncTajiH3auhJom, 6 a p koä npocTHx qjiaHOBa 6eH30JioBor peAa. OHe c n a a a j y y H a j j a i e K H c e j i u n e opraHCKe xeMHje h cBojoM kohct3htom acjiHHHTeTa caMo c e Majio pa3JiHKyjy oa j a i m x MHiiepa^HHX KHcejiHHa. h b n x o B e ,3eMHoajiKaJiHe cojih c y yrjiaBHOM pacTßopjbHBe y boah h Ha oBoj ocoöhhh noiHBa h>hxobo ocjio6aijaH>e oa cyMnopHe KHcejiHHe, Koja j e koa y o 6 n l a j e H o r HanHHa Aoöiijatta y ß e x npncyTHa y BHumy, uito j e paHHje koä c n p a ß j b a i b a ß-Hac)>TajiHHcyji({)OHCKe KHcejiHHe ynoTpeßjbeHO. M3 3eMHoajiKajiHHX cojih Aajy c e JiaKo y cbhm o i y i a j e B H M a aoöhth ajiKajwe cojih, KyBaaeM ca ajiKaJiHHM KapöoHaTHMa. OHe n p e j i a 3 e aJiK3JiHHM TonjbeibeM y i f e n o i e , uito heMO KacHHje npenapaTHBHO Äa H3BeÄeMO. BpejiHM pa36jiaH C0H5§C1 + HCl

MepKamana

n0H0B0

ce

Äoönjajy

c y a ^ o a c K e

KH-

c e JI H H e. V.

AJIflEXHflH

1. « J > o p M a j i , n e x H f t 2 O A B O ^ n a ijeB 10 cm,

öa^ioHa

caBHjeHa Ma;io

3a ^ p a K U H O H H c a f t e

Ha r o p e ,

H3ByqeHa j e

o a 2 5 0 ml,

npw Kpajy

,a,y>KHHe OKO

y Kanwaapy,

OTBOPOM 1 — 1 , 5 mm yHyTpaimter npe^HHKa h cnojeHa je n p e i c o

ca

riayTeHor

3 a n y m a q a . c a je^HOM ueBH OÄ TernKO T o n j b H B o r c r a i m a ayiKHHe OKO 3 0 cm ( c n . 5 2 ) . BaicapHa

cüupajia,

c e 6 cm y ^ a ^ e H a

OÄ K a n a j i a p e .

yiviOM,

,n;y>KHHe 4 cm,

K o j a j e y ß y n e H a y ixeB, Hajia3H

U,eB j e y n p a B j b e H a

ropibHM KpajeM c n o j e H a j e

Ha BHiue IIOÄ MAJIHM

ca K0HAeH3aT0p0M

cpe^Hie

BeaHHHHe

y n p a B ^ e H H M BepTHKajiHO Ha AOJie ( n o M o r y h c T B y 3MHjacTH K 0 H a e H 3 a T 0 p ) . H a k> cy n p H K j b y q e H a jej;aH 3a ApyrHM ABa p e i i m r a e H T a , KOJ'H c y 3a BpeMe orjieAa

AyöoKo

3apoft>eHH y CMemy

3a

xjia^eK>e.

Kparna

A p y r o r p e u H n a e H T a Be3ana j e ca BOAeHHM IIIMPKOM. y 3apoft>eH

IIITO j e M o r y h e BHiue

y Bo^eHO KynaTHJio,

1

OHOM, Koja j e YÄAJBENA OÄ N H 2 - r p y n e .

2

Tollens,

oABOAHa ueB

(JJPAKUHOHH öa^IOH, 3 a r p e j a H O TAWO HA

B. 19, 2733 (1886). 11*

OpraHCKo-npenapaTHBHH

164

46—47°, iuana

CHna

ce

1 0 0 ml

CTaoeHa

QEB

B03Myx.

Ka^a

ca

pajia,

noieTKy

y

ce

THMe

Aoceace

6jiH3y

OTnoqejio,

naacjbHBO,

CBe

npeKO

H CT3BH

Memujiamoxojia

Koja

aeo

ah3

3arpeBa

H Kpo3 ce

naaMeHOM

Ha u p B e H O M

AOK

ryMeHor

Kojy

ce

3any-

ycncaßa

ôanapHa

ycnjaiby

He

CIIH-

otnoHHe

p e a K U H j a . T A ^ a c e MOpa

Ba3AyuiHa

TaKO Aa

Aa

CTpyja

pery^Hiiie,

cnnpajia

H 6e3

Aa-

j b e r AOBo^ett>a T o r u i o T e o c T a H e CSCBHM c . n a ycnjaHa.

üp«

Ta-

KBOM y p e ^ a j y

He

AO-

jia3H

AO

eK-

60

yonuiTe

cn^03Hje. HHCKoj

TeMnepaTypH

KynaTHJia Ban>e Cji

cyBHiue

Ha

3a

3arpe-

(42—44°)

AO-

CTHÄe c e AOAyuie r p a -

52

HHua

eKcn^03Hj'e

CMe-

me MemrcajiKoxoJi — Ba3Ayx, a m imaiueH AocneBa caMO AO KanHJiape, jep BejiHKa 6p3HHa CTpyjaaa y o B o j , c n p e n a B a B p a h a a e n j i a i u e H a . ( Y N O P E A N ca 6yH3eHOBOM JiaMnoM, KOA Kojer Bpahaite naaiueHa HacTyna caMO npn cyBHme cJiaöoM CTpyjaay). noiiiTO

je

caB

MeTHJiaKoxoji

1 1 0 — 1 1 5 m/ 3 0 — 3 2 % - H o r MaJiAexH^a MAJIO

Moace

Aa

ce

ncnapHO,

pacuiBopa jom

o6a

peuHiweHTa Majia

tpopManaexum;

yxBaTH

y

TpeheM

caApace

KOJinmiHa

peunnHeHTy

y

(|)op-

KOMe

HM3

BOAC.

Cjieaeha pacM3Tpan>a caApJKe HCKOJIHKO ranaKa, HA Koje Tpeôa o6paTHTH na5KH>y npw H3Boijett>y peaKijHje y racHoj (j)a3H. 3 a ÄEXHÄPOREHOBAH.E 1 MONA METHJIAJIKOXOJIA noTpeöHo j e HA 1 3anpeMHHy AJIKOXOJIA

MCTPHCKA cMerna Mopa AAKJIE a a c3äp>kh HJIH 2 8 , 5 % MeTHjiajiKoxojia.

Ba3Äyxa, THcuH, xojia CTyöa.

M o p a AA c e TeMnepaTypa

6 y « e 28,5 °/0 RIPHTHCUH

Landolt-Börnstein,

Mojia KHCGOHUKS, ÄAIAIE

2

Ha 1 3 a n p e M H H y MeTHJiajiKoxojia 2 L I 2 3anpeMHHe

riouiTo c e 3 a n p e M H H e ojiHoce

ncnapaBaH.a TAKO nojiecH,

OÄ aTMocifepcKor napa

1/

3ANPENHHE icHceoHHKa HJIH 2 V2 3anpeMHHe BA3AYXA. CrexHO-

npHTHcna,

nao NAPUHJAJIHH

npn-

M NPHTHCAK nape METHJIAJIKO-

«ANJIE JIA H3HOCH OKO 2 1 0 mm pa3HHM

HCHBHHOR

no3HaTHjnx

MaTepwja

npn

Physikal.-chem.

Tabellen,

5 H3Ä. 1 9 2 3 H ÄONYHCKE cBecke 1, 1 9 2 7 ; II,

TeMnepaTypaMa

Hajia3e c e

y:

1 9 3 1 ; HI, 1935. Ca OB A e H3a6paHOM JCAHOCTHBHOM anapaTypoM He nocTHiKe c e n o r a y H o 3acHheH>e Ca napaMa MeTHjiajiKoxojia, OT/Ä Ta HeujTO BHina TeMnepaTypa. O Ä p e i j H B a i t e MajiÄexHÄa, y

5

MepHOM

ml

c a A p >k 3 j a pacTBopa,

50

ml

ml,

AO&a. c e 3 0 ml OKO 3%-nor

XOAHO T 3 1 H O

öa-noHy.

OÄ

HeyTpa^Hiue

n-HawpujyMxuflpoKCuaa

H

A O Ó H j e H o r

y3eTor

Tora

ce

pacuiBopa y

npHcycTBy

npoMyhna.

iwneTOM,

20

ml

CT3bh

p a c T B o p a AonyHH y

ce

BOAOM

epjieHMajep

OA

KOJ'h c e

BoaoHutccyüepoKCuaa, 4)EIÌ0-'I4)TA''IEHHA

(Jiop-

H

noTOM

AO 250

npeT30

ml

V, 2

nocjie

Bonomina, AöBeAe

KpaTKor

Koje Äo

BpeMeHa

nocTaje Bpjio

Kpaja.

a^KajiHja 2 CH Aaje

npeMa 0

2

+

H

NaOH,

cnoHraHO

H Koje ce

pacTBop

3arpeBaH>e

Haj3aA

KpaTKHM

ce Ta^a T H T p u m e

pa3Bujawe

3arpeBaH>ÇM

c a n-conoM

A O A a B a i b a TajieHHa. Y n o T p e ö j b e H a

2

0

2

+

2NaOH

(popMcuiaexuaa. T O 2 0 ml

0,675 g

—

y3

165

mce-

KOJinqHHa

jeAHaiHHH:

KOJIHIHHY

2 2 , 5 ml

noiHite

ôypHo

Ox-rcaljeHH

M H O M noc^e n0H0BH0r

mg

_

AjlÄexHÄH

AKO

( = 2 ml

4)opMajiAexHÄa,

-v

2 HCOONa

je

Ha n p .

npBOÖHTHor

TJ'. p a c T B o p

je

npw

-f

+

2

peaKijHjH

pacTBopa) 33,8

H2

H

2

0

yTpoiueHO

caapacn

22,5 . 30

npouenraH.

NPH OBOJ Bpjio 3 H a i a j H o j peaKUHjn cTBapa c e aAHunjoM 2 Mojia H 2 C O

Ha BOÄOKHH-

c y n e p o K c n a MetjynpoÄyKT KOHCTHTyuHje:

H O H 2 C • O • O • CH 2 OH Ä i i o K C H M e i H a - n e p o K C H Ä , KOJH ce TaKofje Moaie aa H30Jiyje H y KpncTajiHOM oÖJiHKy, aJiH Kojn ce noMohy ajiKaanja HCOÖHIHO JiaKO pa3JiaiKe Ha t j i o p M H j a T H BOÄOHUK: HOH2C

0

0 - CH20H

+

2 NaOH

• 2 HCOONa +

2

H2 +

HsO

[BjinjKe o OBOMe BHÄH A. 4 3 1 , 3 0 1 (1923)]. O OÄPELJHBAIFAY ({¡OPMA^AEXHAA ca

AMOHHJAKOM

BHÄH V , 3.

ripocTH ajiÄexHÄH pearyjy ca HeyTpajiHHM cyfltJiHTOM Äajyhn C O M aJiÄexHÄCyMn o p a c r e K H c e j H H e ; npn TOMe HacTaje cjioöoÄiia 6a3a, i n j a THTpamija oMoryhyje TaKOtje KBâHTHTaTHBHO OÄpel)HBaH>e. 2. H3

a.

Ai^eTa^AexHA1

eTHJia^Koxo^a.

JiHTpa

c a iiiHpoKOM

öajioH

Äy^er

ÖO^HOM

BpaTa c a

BoHHa j e i ; e ß Be3aHa

Hajöo^be

U6BH,

Aoöpo

npeMa

JTTÏI

TT U

KOM. O a o 3 r o

xjiaAftaKpo3

3anyuiaq

HacTaBKOM

noc/iyjKH H no

AHuinuy.

ca

KOCO H a r o p e n o c T a B j b e -

MeHH

ö a a o H OA IV2

CJI. 5 3 ; M c m e a a

yqßpiiiheHHM

HHM

BejiHKHM

j e , AA c e y3Me

^

"

ry.-

ca

Ase

p y n e y j i a 3 e c T a r a e H a ijeB 0,4cm yHyTpaiuiter npeqHHKa,

Kpo3

BOAH H3 (Ca

Kojy

ce

y-

ne^HHHe

öoije

peAyKUHOHHM

BeH-

THJIOM)

YRJBEHAHOK-

C H A , H jießaK 3a K a n a i t e ca

AyroM

H3ByweHOM

UeBH. KOHAeH33TOp j e Ha

Ca. 53

r o p f t e M K p a j y Be3aH c a C a C l 2 - u e B H U - o 6 j i H K a cpeAfte Be/raiiiHe, Koja CTOJ'H y bê3H c a 3MHjacTHM 1

flejiHMHHHo npeMa: Werihelm, Z. ang. Chemie, 36, 546 (1923).

J. Am. Soc., 44, 2653 (1922) H Fricke

H

Hovestadt,

166

OpraHCKo-npenapaTHBHH

aeo

ycnpaBJbeHHM K0HAeH3aT0p0M (CJI. 53). H a a cy Haj3aA npHiobyqeHa je^aH 3A A P Y R H M ASA peiimiHeHTa, O A K O J ' H X C B 3 K h ca^paca 100 ml ancojiyTHor empa H K o j n cy CTaBJbCHH y c B O K e n p u n p e M ^ e H y CMemy JieAa H KyxHibCKe COJIH; nbeHa TeMnepaTypa H E cine A A ce nonHe 3a B P E M E O R J I E ^ a H 3 H A A — 10°. Y ueBH n p B o r K0HAeH3aT0pa, K p o 3 K O J ' H B p ^ o jiaraHo cTpyjH BOAa OA OKO 26°, J I O K H T E P M O M E I A P , B E 3 A H BpimoM Y ^ B P R N H E H O M ropit>HM 3anyiuaqeM, qnja ce Kyrjia Ha;ia3H Ha c p e j H H H ueBH K0HAeH3aT0pa. C b e B E 3 E

A N A P A T Y P E M O P A J Y A O Ö P O Ä A

3 a n T H B a j y .

3MHJACTN

KOH-

onepaunje Hanaja B O A O M O A 5 — 1 0 ° , 3 H M H A H P C K T H O H3 BOÄOBOAA, a y T O I T J I H M AaHHwa ce B O ^ a nponyniTa Kpo3 3MHjacTy U E B , Koja ce cnojba xjiaÄH JieAOM.

£ E H 3 A T O P

ce

3A

B P E M E

Y öa^OH ce CT3BH caaa 125 ml emujiamoxojia (2 MOJia) H TpèhnHa CMeiue OA 150 ml ( = 270 g) cyMüopne mcemne H 250 ml BOAe H 3arpeßa AO Kjbyqaita. Y iviaBHoj K O . J I H ' I H H H pa3ÖJia)KeHe cyMnopHe KHce^HHe, paCTBopn ce 200 g HaUipujyMÔuxpoMaïïia y 3 AOAaBaite 100 ml BOAe; OBaj ce pacTBop, joui Tonao, yHece y jieBaic 3a Kanaite, nnja ce ueB noTnyHO HanyHH. rioiiiTO ce C T 3 B H JieBaK 3a Kanaite, nycTH ce Aa iteroBa caAP>KHHa H C T H ^ e yMepeHOM 6p3HHOM y ajiKoxo.RC, K O J ' H TaMaH KJbyna; HacTaJia peaKUHOHA TONJIOTA

MHHH A A J B E A O B O I J E I B E

TONJIOTE

H3JIHIUHHM.

Y M E P E H O M

CTPYJOM

yrjbeHAHOKCHAa O A B O A H ce H3 KJbyqaJior pacTBopa CTBopeHH ajiaexua H TaKO ce caqyBa OA Aajbe oKCHAauHje. (f-beroB HanoH nape je Ha TeMnep a T y p n y K0HAeH33T0py join AOBOJbHO BejiHK Aa cnpeqn KOHAeH3auHjy npn 6p30M CTpyjaiby; OBO ce AeinaBa TeK y jaKo pacx^a})eHHM peuHnneHTHMa.) XLOBOIJEIBE pacTBopa ÔHxpoMaTa pery^Huie ce TaKO Aa CMeina C T S J I H O Kjbyna, n p n qeMy TepMOMeTap y ueBH KOHAeH33Topa Tpeôa Aa noKa3yje TeMnepaTypy OA 2 5 — 3 0 ° . AKO

p a c T B o p ÖHxpoMaTa n p n

CBOM

ncTHuaH>y H3 jieBKa He 6 H Morao a a caBJia.ua

THcaK Kojn BJia.ua y a n a p a i y p n , TO c e y COO-BOÄ

yMeTHe T - u e ß H H>eH

npeKO KOMajiHha r y M e H o r u p e B a , c a T y ô y c o M jieBKa 3a K a n a t t e . JiHua, p a a n 3aTBapaH>a n p n a o n y f o a B a i b y JieBKa 3a

npn-

6OIHH Ien KHnoB anapaT, Ha Kojn Mopa

a a c e cTaBH

ycnpaBHa

ueB,

HanyiteHa

pa3ÖJia)KeHOM

COHOM

KHCCJIHHOM,

a a 6H c e

caB'jiaaao npHTHcaK. floche

30

MHHyTa

ce

yrjbeHAHOKCHA

H3

PEAKIJHOHE

BeHTHJi

Tpeöa

npoBOA«

C M e i n e .

T a A a

Aa

joui c e

je

10

AOAaBaibe

ÓHxpoMaTa

MHHYTA, A a 6 H c e c a B

OABOJE

PEUHNHEHTH

H

3aBpineHO,

A^AexHA

TCK

OHAA

anu

HCTepao 3 a T B o p H

C02-6oiie.

n o u i T o ce aueTajiAexHA pacTBOpeH y eTpy He Aa 0AS0jnTH OA paCTBapana (JjpaKUHOHOM AecraJiaunjoM, T O ce O H npeBOAH y K P H C T 3 J I H H a j i A C X H A a M O H H j s K . CaApJKHHa oôe HcnHpsjiHiie ce C T H B H y M3^IH nexap A ^ ô e ^ n x 3 H A O B 3 , K O J ' H ce X J I S A H y CMeuiH 3a x ^ a ^ e a e H yBOAH ce racoBumu aMonujaK H3 qe^HHHè 6 o u e ; Kao aeB 3a yBO^eite c ^ y m n npaBa G a C l 2 - a e B , U H J H ce i n n p n A Ê O A y ô o K O ypoHH y T C H H O C T H qeinhe noKpehe TaMO H 0B3M0 Aa 6 H ce pa3ÔHJiH C T B O P Ê H H KpncTa^H. C y A ce noKpnje

AwexHaH caxaTHHM

CTaKJioM

óaKapHOM

Mpe>KHuoM.

167

ca pynoM Ha cpeAHHH, 36or

eTpa

npoSymeHHM

ncnapaBa

KOJ'H

KapTOHOM,

cBe naaMeHOBe y

HJIH 6JIH-

nOraCHTH.

3HHH

Ha pacno^o>«eH>y He CTOJH 6oua ca KOMnpuMOBaHHM aMOHHjaKOM, TO ce rae pa3BHja H3 KOHU AMOHHJAKA 3arpeBaH>eM y óajioHy (33KJIOHHTH ruiaMeHHK cneu.Hjaj]HOM MpeXCHIIOM); 3a cyuieite Mopa ce npHKJby HanyfteH HBPCTHM KaJiHjyMXH.npoKCH.noM H CBOKHM HerameHHM KpeioM. íloTpeÓHa KOJiHiHHa NH3 H3pa4yHaBa ce Ha cjie,nehH HaHHH (M3JIH BHIUaK). /la ce He 6H cyBHiue aMOHHjaKa pacHnajio, H3paqyHa ce KOJIHKO 6H ce jiHTapa aMOHHjaKa yTpouiHJio, aa 6H ce Be3ajia OHa KOJIHHHHÍI aJiAexn.ua, Koja ce oieKyJe Kao HajBehH npiiHoc (60 £). 60 g ajmexH.na je 60/44 = 1,36 rpaM-MOJia H oaroBapa 30 JiHTapa (3auiTO?). C o63HpoM na yTHuaj npHTHCKa H TeMnepaType, LUTO I H H H npocenHo 10°/0, ÓHhe lame noTpeÓHO oTnpHJiHKe 33 JiHTpa aMOHHjaKa. PeryjiHine ce cTpyja aMOHHjaKa H3 6oue je^HOM 3a CBaraa npn6jiH>KHO TaKO, aa ce MacoBHHKOM TaKy nocjie

g.

pacTsopH

ce 2 5 g

PACXJIA^eHa CMerna OA 3 0 mi

BOAC H

Kpo3

AecTH./iHiiie Ha

CaCl2-ueB

cnojbHnj TeMnepaTypH Sjiaro 3arpeBa,

ajiaexuaaMoK0M}eHwp0BaHe

KynaTn;iy;

BOACHOM

U-o6jiHKa,

H 33THM

KOJH

BpeMeHa, a n o ce qyBa

noja

ce npn

ce KOHAeH3yjy y

nape

HHCKoj

3MHJ3CTOM

K0HAeH33T0py A o S p o r AejcTBa. ^ A 6a c e aueTajiAexHA caqyBao OA ayTOKCHAauHje,

anapaTypa

3 6 o r BHC0K0r

ce npe AecTH^aiiHje

HanoHa nape

aueTa^AexHAa,

HanyHH

ca C 0 2 ,

aJiH

ce t c k ,

Ha Kpajy onepauHje

npoBeAe

oneT Ha cacBHM KpaTKO BpeMe JiaraHa CTpyja C 0 2 . ÍIOHITO ajiMexua Ha 21°, Mopa peuHnHeHT, Aa ce A o 6 p o x^aA« ca OmeAH

Kojw

KOJ'H

je npeKO sanyuia^a Be3aH c a

CMCUIOM

Tpeóa

Aa c e 6)

H 3

JIEAA

H

Kjbyna

KOHA6H33TOPOM,

COJIH.

H3BeAy,

fla™

c y Ha cTp. 1 6 9

H Aa^e.

AUETH;IEHA

Masa rjiaBHa MeToaa onHcaHa non a) aoJia3H je^HHO y o63Hp Kao npenapaTHBHa MeTOfla, HaBemheMo TaKolje TBXHHHKH aaaeKo Ba>KHHjH nocTynaK x n a p a T a u n j e aueTHjieHa; Tpeóa^o 6H ra TaKolje H3BecTH^c BpeMeHa Ha BpeMe.1 1

O B a e aaTH n p o n n e j e pa3pa^eH y xeMHCKoj jiaóopaTopnjH y

feTHHreHy.

168

OpraHCKO-npenapaTHBHH .neo

g oìcuBUHor oKcuaa

5

CMeuiH

oä

pacTBopn

ce

HajßehHM

KOHU.

1 1 0 ml BOAe H 5 0 ml.

cyMüopne

AeaoM

y

joui

mcemne,

Bpyhoj

CBe c e

CTHBH

B e j i H K y K p y u i K y 3a M y h n a a e (CJI. 5 7 ) h H C K O B p e M e M y h K a c a aiiemujienoM, K o j H j e c n p a B J b e H h 3 K a j m n j y M K a p Ó H A a , n p e q H u i h e H c a 3 a K H c e j b e H H M pacîîïBopoM ôuxpoMaïila H ôaKapHuwpaïïia H y x B a h e H n p e K O 3 a c H h e H 0 r p a y

CTBOpa ripe

K y x H i b C K e COJIH y

Myhnaifea

Mopa

EßeHTya^HO y

ce

ce

CTHKJIGHOM r a c o M e T p y ,

Ba3Ayx

MO^ce

ycnpaBHO yqßpuiheHoj

ca

C

H

ce

Beace

2

,

2

ryMeHH

TaKoije

rioc^e

ca^pMCH

8 — 1 0

JKHBy.

y

KOJ'h

Babo-OBOM

Kpo3

nacoBa

nao

H3ABaja

OBO

ce

jeAHH>eibe

npeöauw

yBoljeibeM

OBa

ce

onepaunja

je

niTO

noA

ca

OnHcaHO.

ewpoM,

a)

ajinexunaMOMijaica

oôjiHKy

npHHOC

5—6

50 £

OnHcaHO

HacTynH &o

187°.

C 0

2

,

uifleMOBaHe

Kpefle,

H HCTepyje,

Joui

130°

Tonao

jiHCTuhHMâ

BOAe

CHTHO

(TepMOMeTap

6eH3oeBa

h3

joui

qßpero

je

Majio

HcnapaBaiteM

euipa, H cana

je

40 g

Aoöpor

ce

Ha

CTBO-

cKJionjbeHa

nocTaBH

Kao

6a-

y

3arpeBa

TaaoHceite

je^aH

ajiAexHAa

UITO

y ¿by).

Bpyhe

o

paHHje

je

Kjbyqajie

HcnapjbHßa npeiuao

ano

je

y

6öixy

ca

3a

Taqna

boachom

33THM

3anyuiaq,

caaóe

y

yjbaHOM

Oßa

ce

napoM.

H (JwjiTpaT

ce

Tonjbes>a

oijeAH 121°.

eKCTpaxyje ce

AOAa

eiapcKH

Majio

qßpcTy

KojH

Ha

BeH-

ce

Aßa

pacTBop

no Ma^o

Tex-

CTaKjieHHM u i T a n n h e M , y

ce

cjajHHM

napoM.

napoM,

öqßpcHe

CTaßn

Be3aH

boaçhom

Hyq

npoAyKT.

AOK

ce

caTa

oxjialjeH>y H3Asaja c e y

Meuiajyhn

noiuTO

4

Kpo3

KOHyeHTpHine

npax,

je

KajiiiujyMKapóoHama (HJIH

ce

BOACHOM

noTpeÔHO

He

peaKunje.

Kojw

yBo^eae

6eH3annexun

BOAe. ca

y3

je

xjiop,

c e h 3 B 3 a h óajiOH h3 y j b a H o r

ueAH npH

0He

ßajiOHy,

MepMepa)

CMeuie,

UITO

cyB

TeivinepaTypa

HacTaBKy y

nao

AOivie

ce

aejcTßa,

Ta^a

óajiOHy

hsihh, CBe

AOK

g tanoyueaor

pacïûBop HalûpujyMÔucyjKpunia, aamiuoHO jewH>eH>e ajiaexum H e MyhKa

Koje

pa3Jia>Ke

Koja je

Aa

HCTH

ce

HHqKH

eHepraqHO

je

84), h

Kao cnope^HH

h3

HeuiTO

Ha

(cTp.

cnpaineHor y

y

ltucemva

KojH

aueTH^eHa;

H KOJ'h c e

pacTBopa,

KyBa

mcemnoM.

H npenpHCTajimue

KHcejiHHa

yBo^eaa

xJialjeite.

HCKJbyqHBO

H 150

o c T a T a k

XlecTHJiaT, ca

paAH

KOHU. COHOM

3aKHcejiH

JiHTapa

anapaTypn,

ce

OA

öemajixjiopuA

HJIH

KynaTHJia

nyTa

noracHe

yBoijeibe

6eH3ajixjiopH,n,a

yBOAH

Te>KHHe

ce

ml

Ha

y

3a

HB

K0HfleH3aT0p0M, 500

10

.HoBOJbHo

6eH3n;ixJiopHAa

Oßue

KynaTH^y

3oeBa

sa

HCTOBpeMeHo A e c m a n u i e

eTapcKor

niojiyojia

CHpoBH

ca

ao

CMema

nape;

cMeuioM h3

noBehaite

ycnpaBJbeHHM

BaKyyM

qeB

cBptueTKy

H3BOAH

BEHBAJIFTEXDA

AOÔHjaiba

üoÖHjeHH

jaKo

Myhnajimui,

g.

Kjbyqajior

KOA

no

onHcaHO.

xjiaîjeH

3.

CTpyje

Ha

nouiTO ce Ba3Ayx

je

peaKijHOHa

BOAeHe

y

ca

JiHTapa.

unuiepMeMujapHO jefíuwewe

öesöb/wo

uejia

peunnHeHT

nonHe

ancopniwja

npo^a3H

ancopöoßaHO

ce

jieBKy,

cjih^ho

He

Kojn

M

ce

peHH ajiaexuM;

AOK

H3BpiiJH

6ouh AeöejiHx 3haob3;

3anymaq

noHHH>e

y

Aa

3anpeMHHe 1 0 — 1 5

aueTHJieHOM.

JKHUOM.

ycKopo

jiOHy,

noTHCHyTH

ce

c

Kauiy. BpeMeHa

EÍOTOM

CBe ce

Ha B p e M e

AjiflexHÄH

169

OTBapa, cße aok ce caB 6eH3a^aexHÄ He Beace (mhphcI), oueAH ce Ha BaKyyM, Hcnepe eTpoM h q ß p c T a co pa3^a>Ke OAMax y H o m e i t e M y pacmeop coae y B H i i i K y , H3 Kojer ce TaAa 6e3 qeKas>a oaioöotjeHH ajiaexua HCTepyje BOAeHOM napoM. üecTHJiaT ce eKCTpaxyje eTpoM, nocjie cyiueiba eiapcKor pacTBopa ca Ma^o CaCl 2 , eTap HcnapH h TaAa AecTHJwiiie 6eH3anAexufl. Tanna Kjbyqaita 179°. FIpHHOC 35—40 g (70% o a TeopacKor). 36or Be^iHKe o c c t a h b o c t h npenapaTa npeiaa K H c e o H H K y Mopajy

ce

cße

onepaijnje

Aa

H3BeAy

06jawn>eH>a

ca

Hhmch qjiaHOBH boäom; cpeÄftH c y

h

öp30

oraejH

a J i Ä e x H Ä a c y 6e36ojHe

ho

TaKoije TeqHH,

jeAHa 3a

3a

ApyroM.

V , 1, 2 h 3

tcihocth,

oiiiTpor MHpnca, Koje c e Mernajy

nnan y BOÄy HHcy BHiiie Jiaico pacTBop jbHBH,

äok jiokh 3H3tho

c y BHCOKoMOJienyjicKH MBpcTe KpHCTajiHe MaTepnje. T a i n a m t y i a i t a aaaexHjia HHHce Hero k o ä o a r o B a p a j y h H x a;iKoxojia: CH3 • CHO

Tanna Kjbyqaiba 21°

CHS • CH2 • O H CH3 • CH2 • C H O CH3 • CH2 • CH2 • O H

•

„

„

78°

„

„

50°

„

„

97°

ApoMaTCKH aji.aexH.nn c y n p n j a T i i o r Miipnca ( y j b e r o p n a x 6a.neMa, BaHHJiHH, niinepoHaji). Ha h i h

HajonmiHjH

flo6njaita

ajiÄexHÄa

cacTojw

ce

jiapHHx aJiKoxoJia Takoije m

KeToiiH.

IIoiiito

ce

cpeÄCTaßa, t o n p o u e c

OKCuaauHOHHX ce

Ka T a

ji hth i k h

bohohhk

npenapaTHBHO

H3rjie.ua Kao

y oay3HMait>y

hcto

BOAOHHKa H3 npHMtpHor aJiKoxojia (fl/kohol dehydrogenatus);

Mnax

h boaohhk

ÄOÖHjaHiy tjjopMa^aexHÄa (npeMa O. reHauHja),

a

npHMemaHH

Ba3jiyx

HMa 3a

3aaaTaK,

aa

Yqernhe

boäohhk h

caropn

noMohy Mory

naJia.HHjyM0B0r

no^HBa Ha pa3jiaraH>y BoaoHHKa

Loew-y)

ceKyH-

ajiKoxoJiH

noMohy

upHor Beh Ha x-iiaano, a ca öanpoM TeK npn noBHiueHo] TeMnepaTypH.

aTOMa

H3

OÄy3HMa

yrjiaBHOM

OKCHÄaimja.

pa3jio>Ke Ha ajj.nexH.He

jBa

Tano HacTaje

6 a K p a npn (lexnapoaa

ra Tano

yaaji>H 113 paBHOTeiKe: CH3OH CyncTaHiie

ceJbeHOM

ca

cyMnopHOM

TpocTpyKOM

khccjihhom,

H2C = 0 - f - 2 H Be30M

aanpajy

npocTHjeM c j i y i a j y cTBapa H3 a u e T H j i e H a

HC = CH

Oßaj

->

npouec

Ajiaexnan ce

HMa

BejiHKH tcxhhhkh aajbe

Ha aMOHHjanHH pacTBop c p e ö p a

y

pacTBopy TaKo

33kh-

c e y Haj-

peaxiiHja n o j a j e

rope

H2C — C H

O I1 HgO — S 0 2 jiano

Boae

>KHBa-(II)-coJiH.

caM a u e i a j Ä e x H Ä ,

H3Be«eHa.

H C = C H

ejieineHTe

HapoHHTO y n p n c y c T B y

H

| ( 5 HgO • SOsH 3Hanaj

C-CH + II O

3a CHHTe3y_ c n p h e T H e

oKCHÄHiuy h a e j c T B y j y

h emmoB

3

Kao

peayKUHÖHa

HgS04

KHcejmHe. cpejcTBa

pacTBop.

H c k o j i b k o Kann fyopMajinexuw hjih aifeüiajiaexiifla pa36jia}KH ml B O A e , A ö A a M a J i a K O J i H i H H a aMOHujannor pacüiBOpa. cpeöpa h n o A e f l H y 2 e n p y B e i e : y j e A H y c e K a H e hckojihko K a n w iiaüipujyMxüjupoKCUMCi; o A M a x c e H 3 A ß a j a M e T a j i H o cpeöpo. H 3 A p y r o r p a c T B o p a c e H 3 A ß a j a c p e ö p o TeK n o c j i e hciuto c T a j a a a Ha x j i a A H O , a S p a c e n p H 3 a rpeßaH>y. Ü K C H A a u H O H O acjctbo a M 0 H H j a » i H 0 r p e c T B o p a c p e ö p a c e A a K ^ e Orjieß:

ce

ca

HeKOJiHKO

170

OpraHCKo-npenapaTHBHH

3H3THO n o B e h a B a

pe^yKUHOHO

HaTpHjyMXHÄpoKCHßOM

AejcTBO

HacTaßaK

ripejia3 H3pa3 3a

3

—'C=0 H

€THaajiKoxoJia

CHpheTHo

/

>CH3

npeKO

epene;

HCTOBpeMCHO

KHcejiHHe

ajiKoxojia.

Hannie,

h Ta peaKunja npeT-

ca okcha3uhohhm

cpea-

Kojn je Haciao aaHunjoM BOAe, a He caM a ^ a e x n a , Ha np.:

CTBOM p e a r y j e a ; i A e x H A X H A p a T ,

CH

KapöoHCKC

AexHAporeHOBaH>a

HjO

HcnHTaTH

(Tollens).

pacMBop.

Ha

y cnpheTHy

oBAe HCKopnmhyjy

H„0

KHcejiHHy

ôaKTepnje ciipheTHe

jecxe

xcmhckh

KHcejiHHe aTMO-

ctjjepcKH KHceoHHK 3a Be3HBaH>e BOÄOHHKa. Ä a c e npn OBOMe He aKTHBHpa KHceoHHK, KaKO c e paHHje mhcjihjio B e h boaohhk,

Kojn Tpeôa na ce o m e n u , noKa3yje o n i e A ,

heTHe ÔaKTepHje TaKolje y o T c y c T B y

K H c e o H H K a,

KojH je 3aMen>eH

H3Bo^e cHpheTHy KHcejiHHy H3 aJiKoxoJia. X h h o h ce npn TOMe XHaporeHyje y CH3 • C H 2 0 H + 2 0 = < f

N = 0

+

H 2 0 - > CH3

y KOMe ciip-

xhhohom

COOH+2HOOH

3HaqajHa yjiora Kojy aueTajiAexHA HMa npH ajiKoxoJiHOM Bpeiby, H3pawaBa c e y Tone (C.

luto

Netiberg),

oh HacTaje

AeKapòoKcmiOBaiteM

h3

nHporpoîKijaHe

KiicejiiiHe

nao MetjynpoAyKTa: CH3 • CO • COOH

-> C H 3 • C H O +

C02

h luto Aajbe y cMHCJiy ocuoBHe jeAHaiHHe: C H 2 O H • C H O H • C H ( O H ) 2 - f C H 3 • C H O - > CH3 • CO • C O O H 4 - C H 3 C H 2 O H +

H„0

rjiHuepHHajijiexHÄ (xHApaT) y3ajaMHHM XHAporeHOBaH>eM h aexHAporenoBaiteM nocTajy

CTiiJiaJiKoxoJi

il iiodc kcuh-

MHiie nnporpoHiljaHe KHcejiHHe (ynop. VII, 8). AjiÄexHÄH BehHHOM noÄJie>Ky a y T O K C H a a u H j n , KHceoHHKOM.

V

OBOM CMHCJiy

npaBH

ajiaexHAHH

Be3y Hajnpe

aAHpa

He3acHheHH

aKTHBHy ÄBOryöy

Tj. cjeAHH>aßaH>y ca Mo/ieKyjici

2 CH3 • C = 0 OH

TaKo ayTOKcnaauHja a o b o a h Haj3aa a o ie nepKHcejiHHe KOA aueTajiAexnaa OBHM jaKHM 6eH3aJiAexHAa

Möwe c e Bpjio JiaKO A0Ka3aTH

OKCHAaUHOHHM KojH c e

CpeACTBOM

HapoiHTO

6 p 3 0 Be3yje

yxBaTH ca aHXHApHAOM cHpheTHe KHcejiHHe, I O —OH

+

(CH3C0)20

MOMeHTajiHHM H3ABajaH>eM joAa,

npOy3pOKOBaHO

>

y

paCTBOpy

ca KHceoiiHKOM,

Kao

Möwe nepKHce^HHa

6eH30Hji-aueTHjinep0KCHA

C0H5 • C = 0 I O —O

+ —CO-CH

Koje je

KaJIHjyMjOAHAa.

3

Koa Aa ce (Nef):

CH S • C O O H

AJIÄßXHÄH

171

O r j i e ß 2 : 1 ml C ß E J K E A O Ö H J E H O R aiiemajinexuna ce MyhKa H C K O J I H K O MHHyTa y U H J I H H ^ p y ca ryMetíHM 3anymaHeM, K O J ' H a o ö p o 3aTBapa. O Ä Tora ce n0Ji0BHHa cnna y Majio pa3Ö^a«ieHor paciüBOpa KajiujyMjouuaa, a Ä p y r o j noJiOBHHH ce .no^a 2 — 3 nyTa Beha KOJin^HHa Bo^e h ncnHryje ca JiaKMyc0B0M xapTHjoM Ha CTBopeHy cupheüiHy mcenuny. H a h a h e ce, B O A O M pa3ß^aaceHH ajmexH,a; nocjie Henor cTajan>a cKopo He H3Äßaja BHiue jofí H3 pacTBopa Ka^HjyMjoAHÄa. O r j i e f l 3 : 2 Kann 6eH3cuin,exüp,a ocTaße ce na c r o j e C T A K J I Y Ha B 3 3 ^ , y x y .

1 caT Ha ca-

xaTHOM

ripenapaTHBHo je HajöojfaH nyT oHaj Kojw B O Ä H OÄ n p H M a p n n x a j i K o x o j i a Ä O aji.nexH.ua, 6ap y aamJíaTCKOM peay. ílpocTH apoMaTCKH ajiiiexHAH ÄOÖHjajy ce ajiKoxojmoM canoHHtJjHKaunjoM apnjiHAeHXJiopH.ua R • CHC1¡>, KojH Hacrajy H3 yrjbOBOAOHHKa cyncTHTyunjoM ca xjiopoM (TexHHMKo aoßHjaibe 6eH3aJiaexnaa). O C H M Tora OBAe Tpeóa noMeHym eJieraHTny ramepMan-KoxoBy CHHTe3y, Koja Teie y cMiic.iy 4>punJi-Hpacßuicone peaKuiije, KOfl Koje apoMaTCKH yrjbOBOÄOHHK pearyje ca yrjbeHMOHOKCHAOM h HCl y npvicycTBy ajiyMHHHjyMXAopHAfl H KynpoxjiopHAa: /

\

H 3 C
a j e 124°. OöpaTHO, napajiAexHA MOJKe na ce noHOBo n p e B e ^ e y aqeTajiAexHA, a n o My c e AOAa h c k o j i h k o K a n n

kohij. cyMnopHe

KHce.iHHe h

AecTHjiHiue

ca HaMeiiiTeHOM k o j i o h o m Ha b o a g h o m Kynarajiy. no

OBoj MeTOAH MOJKe y c b 3 k o A o 6 a A a ce n p m i p e M H

c b e >k

aue-

TajiAexHA-

Orjiefl 9: Hena ce ca ^ h c t h m üapajiaexuMOM H3Bpiue paHwje noMeHyTe peaKUHje Ha aJwexHAe: ca aMOHujannuM pacïïiBopoM cpeöpoHumpaüia, (pyKCUHcyMüopacüiOM mcejimoM, öucyntpumoM. PeaKijuje cy HeraTHBHe. n a p a j i A e x H A je Ha ocHOBy oape^HBafta rycTHHe nape Tpmiep aueTajiAexHAa. noiUTO oh HeMa ajiiiexHAHHX ocoÖHHa c npaBOM My ce npnnHcyje cjieAeha CTpyKTypa TpocTpyKór UHKJiHHHor aueTaJia. CH 3 CH

/\

O

O

o (Ynope^H c obhm nojiHMepH3auHjy aueTHJieiia y 6eH30ji.) Kao wto cMO paHHje bhacjih, He3HaTHa KOJiniHHa cyMnopHe KiicejiHiie yTHqe h Ha nojinMepH3auHjy aueTajiAexHAa, nao h Ha AcnojiHMepn3auHjy napaji.nexn.ua. Ty nocTojH p a bHOTejKa, WHje ce ycnocTaBJban>e KaTaJiHTHiKH yöp3aßa kohu. cyMnopHOM khccjihhom. 3 CH3 • CHO ;

» (CH3CHO)s

H a cpeAHsHM TeMnepaiypaMa OHa je jano noMepena y AecHO. LLIto Ce h nopeA Tora napajiAexHA Möwe, Kao uito je rope noMeHyTO, Aa AenojiHMepH3yje y aueTajiAexHA noMohy cyMnopHe KHcejiHHe, pa3Jior 3a t o jiokh y TOMe, uito ce MO«e paBHOTe«e Ha OcHOBy 3 a K O H a o A e j c T B y Maca. KaA mh HaHMe y jeAHaiHHH C napajiA.exHA

r aiiCTaTAexiiA b

=

K

„

HenpecTaHO CMaftyjeMO BpeAHOCT HMeHHTejba ct3jihhm HcnapaBaiteM aueTajiAexHAa KojH ce y CTaH>y paBHOTe>Ke Hajia3H y Ma^oj kojihhhhh, THMe H3a3HBaM0 Tauol^e CMait>eH>e KOHueHTpauHje napajiAexHAa y KopHCT Aeno;iHMepH3auHje, Aa 6h ce noHOBO ycnocTaBHJia paBHOTeîKa. MaAa napajiAexHA CKOpo cacBHM npeoBJiaîjyje y CTaH>y paBHOTeate, nnaK, 3Öor BHCOKor npHTHCKa nape MOHOMepa, Moryhe je npaKTHiHO noTnyHO H3BpuinTH AenojiHMepH3auHjy. Ha HH3KOj TeMnepaiypn jaBjba ce joui jeAaH Apyrn nojiHMepHH oöjihk aueTajiAexHAa, jieno KpHCTajiH30BaHH M e i a j j e x H j t .

Or;iefl 10: y h c k o j i k k o MHJiHJiHTapa aiietBajiaexuaa, k o j h j e p a 3 6 ^ a « e H ca ABOCTpyKOM 3anpeMHHOM ancoJiyTHor empa, yBOAH c e xJiaAehH y CMeiiiH 3a xJiai)eH>e h c k o ^ h k o M e x y p a racoBHTe coHe KHcejiHHe. F l o c k e K p a h e r

AjiAexHÄH

BpeMeHa ce

n3ABaja

nocjie

CTynKOM

Mewajiaexua

ce

ue^etba ÄOÖaja

HOBa

MHpHca.

6e3

He

OB^e Aa

.naraHo

ce

noKa3yje

(Hantzsch); Oh

MeTOAH ce

Koje

hcthm

no-

je

peaKunje.

MeTa;iAexHA

ripw

cTajan>y

u i t o je 3HaK Aa cp

MeTa;iAexHA

OÄpel]HBaft>e

AOÖHjeH

Moaie

3arpeBan>eM

MOJieKy.ncKe

TejKHHe

TeTpaMO.neKy.ncKn

KpHCTaJiHe

(y

nojiHMep

pemeTKe

nö

Laue-

(Mark).

TexHHHKH

np0H3B0AH

T p e ö a pa3^inK0BaTH

oa

ajiAexHAHe

paBHOTe^Ka.

Aa

ce

nocrojaH h c b o k c

Ha aueTajiAexHA,

noTBpi)yjy h HcnHTHBaiba

to

Bragg-OBOj

MHpnc

AenoJiHMepH3yje.

je,

HHiHijaMa,

H3 ( J m j i T p a T a

KpncTajia.

hmkakbc

ycnocTaBJba

noKasa^o

kphct3^ihhm

eTpoM;

Kao h napajiAexHA

pa3rc>BeTHO

norayHO

(J)eHO^y)

je

ahbhhm

nepy

KOJinmiHa

MerajiAexHÄ o c e h a ce wnaK

y

Ha B a n y y M y

175

ia (XII, 8) (MexaHH33M?), M3Äa je TaMO XeMHCKH npouec ÄpyKiHjH. Katimapo-oBa peaKunja HHje cBojcTBeHa caMo apoMammiHM aaaexHAHMa; H op M a ^ a e x H Ä Moace y TOMe c M H c j i y «ejcTBOM jaitiix a j i K a j i H j a aa c e A H c n p o n o p m i O H H i n e y M p a B J b y

K H c e j i H H y

OÄ a a e i a J i a e x H Ä a HyTa

anAOjma

h

n a Haaajbe,

KoiiAeH3aiiHja

M e T H U K o n o g .

ULITO BHUIH

Kami3apo-OBy p e a K u n j y , ycjie« cBoje aaaeKo Behe 6 p 3 H H e He jiajy

ajiHiJjaTCKH a n A e x H A H , TO

je

3aTo

UITO r o p e

noieB

noiue-

npeoBJialjyje.

KOA aji,nexH,na ca aJiAexHAHOM rpynoM B£3aHOM 3a T e p u w j a p H H yrjbeHHKOB aTOM, KOA K 0 j n x anAOJiHa KOHAeH3auHja H H j e M o r y h a , H a c T y n a Kao 3 a M e H a Kanmapo-OBa peaKunja H y ajiHtjiaTCKOM peay. Tano c e r j i H O K c a j i H a K H c e j i H H a A H c n p o n o p i m o H H i i i e y r j i H K O J i H y H o K c a ji H y K H c e ji H H y, KaiiH3apo-oBoj p e a K U H j n cpOAHa j e pa3MeHa oKCHAauHOHor c r y n a a H 3 M e l j y a j i K O xojia H aJwexHAa noa AejcTBOM ajiyMHHHjyMaJiKoxojiaTa, Kojy je OTKpHO Meerwein? HeKH ajiaexna R • CHO pearyje ca Al (OG2H5)3 Ha Taj HaiHH IHTO ce cTBopH amOC 2 H 5 H I / iiHOHH npoAyKT R • C — Oal 1 . Oßaj npoAyKT ce y apyroj a

aoòhj'ch

boachom

cuieuiH

6 e H 3 0 H H a

K0Hi{eHïïip0BaHe a30ïïiiie

MHcre

sarpejaHOM

peaKiiHOHoj

je

OTBopeHOM

TOKHHOM

ABOCTpyKOM

AOAa

ôemouH

H 3

cBpinene

ce

nocne

BHiiie

Ha

xapTHjH

OKCHAaunje

BOAOM, nocjie

3a

qaca

oHBpmhaBaHba

nyTa

H3 a j i K o x o J i a .

9 0 %

IV2—2

cyiiiH

ue^eita

ueijeibe.

Tanna

TeopncKor.

Konaen3auH]a n p e i c ï a B j b a joui j e A H y

6eH30HHCKa

Hute-

pecaHTHy peaKUHjy aJiAexHAa, Koja ce y apoMaTCKOM p e A y AeiuaBa noA AejcTBOM KajiHjyMUHjatíHAa. B p j i o j e B e p o B a r a o Aa ce npH TOMe CTBapa, Kao MeljynpoAyKT, KaJiHjyMOBO jeAHH>eH>e UHjaHXHApHHa. O ß A e n o c T o j n , a H a J i o r a o Kao KOA 6eii3HJiuHjaHHAa ( V I , 8), noKpeTJbHB H-aTOM

KojH

y

ajwajiHoj

cpeAHHH OMoryhaBa

KOHAeH3aunjy, CJIHIHO aAOJinoj, ca ApyrtiM

MOJIEKYJIOM AJIAEXHAA

/OK H CgH5 • C < + O : C • C6H5

C 6 H 5 . C: O H

H \

OK C6H5 . C

H C • C 6 H 5 -KCN C 6 H 5 • C O • C H O H • C G H 5

CN TaAa

K0HAeH3auH0HK

/

C N

OH

npoAyKT

npe;ia3H y 6eH30HH

y3

oABajaite

KajinjyMuHjaHHAa.

KaTaAHTHHKo y i e u i h e KajinJyMUHjaHn.ua j e OICBHAHO. ripaBH pa3JiHKy H3Meijy OBe peaKUHje H UHjaHXHApHHCKe CHHTe3e! CJIHHHO 6eH3aAAexHAy p e a r y j y H>eroBH cyncTHTyuHOHH npoayKTH a H H 3 o H H), a H ypoji ( t j ) y p o H H ; AiiHAOHHCKa

cnHTe3a j e d o r a

HITO OBAe TepuHjapHH

Oßa

(POPMAJIJTEXHAA

jeAHH>en>a

Haciajy

e c T p e KHceAHHa, d o r a

veault,

Scheibler).

HapoiHio

KapaKTepHCTHiHa 3a apoMaTCKe

C-aTOM Ha j e 3 r p y He A o n y u n a

HHane caMa no ce6w npBa AecHJia. Beh KOA

HajnpocTHjn

( c î p . 175);

(aHH3ajiAexHA A a j e

(JjopMyjiHiun!). ajiAOJmy K0HAeii3auHjy,

npHMep

auHjioHHCKe

rjiHKoJiajiAexHA

joui y ajiHcjiaTCKOM p e A y

AejciBOM

H Kao cnopeAHH n p o A y K T KOA cHHTe3e

je

cHHTe3e

ajiAexHAe, Koja 6H c e cpejiH

HajnpocTHjH

HaîpHjyMa

CMO

auHJioHH.

HJIH KajiHjyMa Ha

aueTCHpfceTHor ecTpa (Bou.-

v, 5

AjiAexM.au

179

Haj3afl cy H y iKHBoj hejinjH HaljeHa noMohHa cpeacTBa 3a auHJiOHHCKy CHHTe3y, p 6 o JI H r a 3 e) KojH ycMepaßajy cjeÄHitaBaH>E Äßa MOJieKyjia ajiAexn.na y cMncjiy CTBapaita auHJioHiia. TaKO ce 6eH3ajiAexHÄ KOMÖHHyje y Kßacny KOJ'H npeBHpe ca MefjynponyKTOM nponeca Bpeita, aueTajmexHAOM, y (OITTHMKH aKTHBaH) 6 e H 3 a u e x o H H C6H3 • CHOH • CO • CH3. AKO ce AOAa caM aueTajmexHA, T O H a c i a j e a u e T O H i i (Neuberg). A U H J I O H H H Kao a-OKCHKexoHH CToje y H3pecHOM OAHOcy npeMa KeT03aMa. Kao H e H 3 H M H (K a

OBe, OHH peayKyjy

cpenum-OB

pacTBop H HCTO

Tano

npeBOAe

ce y

03a30He

noMohy

a 225°.

ÜOKajKH aMOHHj'aK

KOJH

HacTaje npn peaKLjHjn! opMy.flHiiiH peaKunjy!

HCTO jeanfteibe H a c i a j e H3 6 e H 3 H JI a ca cj)eHHjixHApa3HH0M, nao H ayioKCHnauHjoM 6 e H 3 a j i Ä e x H Ä ( t ) e H H j i x H Ä p a 3 0 H a (Busch), O cTBapaity 03a30Ha H3 a-oKCHKeTOHa (h a-oKCHajiÄexHua) 6nhe roBopa jom KOÄ VII, 6. FIpenapaTHBHH 3Haqaj aunjioHHa 3acHHBa ce HaTOiteHHUH,Aa cy OHH MeijynpoAyKTH npn ao6Hjaifcy MIIOI-HX 1,2-anKeTona. HajnpocTHjn apomaTCKH npeTCTaBHHK OBe rpyne je 6 e H 3 h JI (anajiorHH cy 3hh3hji, (})ypHJi H T Ä . ) , Kojn je HCTO TaKO Kao h ajiHcjjaTHqHO O C H O B H O jeÄHfteHie CH3 • CO • CO • CHS, AnaueTHJi (a H 6e3BOAHH rjiHOKcaji), wyTO oöojeH. Äo ÄHaueTHjia ce A0jia3H H3 eraJiMeTHJiKeTOHa npeno fteroBor MOHOKCHMa (v. Pechmann); Tpe6a HanoMenyTH iteroBy KOHAeiwaunjy y p-ICCHJIOXHHOII ((jjopMyjimiiH!)_ ZU ce o6e C = 0 — rpyne najia3e y cyceAHOM nojiowajy npon3Jia3n H3 cn0C06H0CTH ÄHKeTOHa Aa ce KOHAeirayje ca £j-(f) e ii H JI e H A H a M h H o M (xHHOKcajiHHH, Hinsberg).

O r j x e ^ : PacTBopH ce no 0,1 g öen3UJia a 6eH30una y enpyßeTH y 10 ml amoxojia H AO^a ce Ha xJia£HO HeKO-iHKO KariH pacüiBopa xunpotccuaa. OßMax HacTaje Ä H B H O u p ß e H O o 6 o j e f t > e , Koje npn Myhnaiby ca Ba3ayxoM mime3aBa, ajm ce n o r a e KpaTKor BpeMeHa noHOBO Bpafaa H MyhKaiteM oneT noHOBO mime3aBa. IlpoMeHa 6 o j e M O J K C Ä S c e geruhe I I O H O B H . Ka^a npn flajbeM AOÄaBaiby HeKOJiHKO Kann XH^poKCHÄa nojaBa 6 o j e H30CTaHe, 3Haqn HeMa BHiue 6eH30HHa y pacTBOpy. CacBHM quer 6eH3HJi He noKa3yje nojaßy 6oje. Oßa lyÄHa peaKunja noTHMe OTy.ua, IUTO 6eH30HH noA AejcTBOM ajiKajinja, npejia3H ÄejiHMnqHO y CBoj AHeHOJiaT, CTHJi6eHAHOJiKajinjyM C6H5 • COK :COK • CQHJ1. Oßa co Äo6njeHa y HapaHijacTOJKyTHM KpncTaJiHMa y OTcycTBy BOAe Aaje ca 6eH3HJioM upBeHH pacTBop oceTJbHB Ha Ba3Ayxy, Kojn BepoßaTHo cajipHiH p a A H K a JI 6eH3H.iKajinjyM, KOJ'H HacTaje n Be3HBait>eM MeTajiHor KajinjyMa 3a 6CH3HJI (Beckmann H Paul2, Schlenk s): C6H5 • C = C • C6H5 f C6H5 • CO • CO • C6H, I I OK OK npn ayTOKCHÄauHjH paAHKaji ce jeAHHM 6eH3HJiHy KHcejiHHy4. 1 2 3 4

ACJIOM

2 C e H 5 • CO — C • CeH, I OK oKCHAHiue y 6eH3HJi a ApyniM y

Scheuing, Ann. 440, 72 (1924). A. 256, 23 (1891). B. 46, 2840 (1913). Ynop. ,1. Weissberger, H. Mainz H E. Sirasser, B. 62, 1942 (1929). 12*

180

OpraHCKO-npenapaiHBHH a e o

peaKUHja

HajBawHHja jede

OrJiefl: ofl

KynaTH^y

g 6en3ujia p a c T B o p H g KajiujyMxuMpoiccuAa

51 5

10

MHHyTa

KajiujyMÓeH3UJiama pacTBopH y

AOAaje jiHMa H

xciMOJiora,

Kojy je Beh J. JlnÓHr

otkpho

npeMeiuTaH>e y 6eH3Hjmy KHcejiHHy.

CTBopoM

h

6eH3HJia h H>eroBHX

V, 5

Ha

Bpe/io

BejiHKe

oueAH

xJia^He

15

mi

Ilocne

Ha

mi amoxom, BO,zi,e h

ox^a^eiba

BaKyyMy,

Ha

KpncTa^Ha

ncnepe

BOAe. Flocjie u e ^ e i t a

noMeuia

3arpeBa

ca

BO^OM.

KOJiHHHHe

OHa

Bpejie

IlpHHoc

Moace HJIH

Bo^e

oko

4

£a

ce

Ma^io

nocne

cyrneita

Kauia

pacrBopy KpncTaBanyyMy

AHpeKTHo

6en30Jia.

H3

pa-

a^Koxo^a

ce 6 h c t p o m

npeKpncTajiHuie

ca

boachom ce

cyMuopna mcejima h AeJiHMimHO y Kucejiuna c e j o m H a B p e ^ o o u e ^ H H a

cjioóowa

150°.

y

10

pa36^ajKeHa

BpeaoM

Toiubeita

KJbyqaita.

Aoòpo

2 0 — 3 0 mi

H3aB0jeHa

ncnepe

ao

ce y

H3

Tam

jaBJba ce (Schelling)

anHUHOHH npoayKT 6eH3HJia ca jeaHHM M0JieKy.n0M KajiHjyMXH,npoKcn.na.

K o f l oBor

«0Jia3H .no npoMeHe

npoayKTa

KajinJyMa

aa

ce

K o j e je

Mecia,

H3a3BaHO

tokk>om

cmHivieAHo

HeytpaJiHme: C6Hb CGH5 • C ^ C O •

~/\

HO

¿Óe6 HH55

>. • C6H5 • C • CO

\

OKI

HO

eHaHTpeHXHHOH Ä a j e 6 m j i e H H ) i e H r j i H K O J i H y

OK

KHceJiHHy.

Ha h c t h HaMHH ((JiopMyjiHUiH). n p e M e u r r a i b e 6eH3HJiHe KHcejiHHe nrpa MHornx Ä p y r n x peaKUHja ( K p o K O H C K a O b o m Je Bpjio cjihhho T3B.

KHceaHHa,

3 \ c CHj/^l OH

3

c ^ 0 " 3 T V « OH

CH

S

Teie koä

nypnyporajiHH). npeMeuitaibe:

nHHaKOJiHHCKo

CH,

peaKiinjoM Koja ochm Tora y j i o r y

\/rC / | PH

C s

HO

CHa OH

IIHHaKOH

CH

3 X

>

> c — C ^

¿

H

,

• CHS

Ä

IIHHaKOJIHH H 0 B « e (JiopMajiHO H3MeH>yjy M e c i a O H ynoTpeóftaBa

ce

KOHU.

cyMnopHa

h ajiKaJiHH' ocTaiaK C H 3 ,

KHcejiHHa —

H3ÄBajaH>e

Boae

Ma.ua y CTBapn

H3Meljy

o6e

—

OH-rpyne,

n p o y 3 p o K y J e n p e M e i m a i t e j e a H e MeTHJiHe r p y n e . H a j 3 a Ä heMo noMeHyTH

JeÄHo y HOBHje BpeMe MHoro CTyjiHpaHo

npeMeuiTaite

Koje

T a n o ^ e n p w i a a a HCToj o6;iacTH, a K o j e ce 03HaiaBa, He 6aui cacBHM npaBHJiHo, Kao p e t p o nHHaKOJiHHCKO

npeMeuiTane.

CyuiTHHa o B o r npeMeurraiba MeTHJieTHJieH

i

j e c i e npe;ia3

y 3 H3ÄBajaH>e Boae:

npeMa H. v. Liebig,

B. 41, 1644 (1908).

nHHaK0JiHHajiK0X0Jia

y

reipa-

181

AjiflexHÄH

CH


C H 33

CH,

CH,

O B O M e je c p o ä h o h npeMeuiTaH>e ö o p H e o j i a h H>eroBHx aepHBata y t h i i K a M i j i e n a : CH

\

CH2 ch

CH

CH

C(CH8)2 2

/

\ CH»

/

ch„

- H 2 0> c h

2

c h

2

CHOH

/ c h

crcH3)21

1 . CH2

CH

/a

/ C CH.,

\C ( C H

2

c =

\

Cb

óopHeoji

JejiHHa

p e a m t H j e j e y T O M e i u t o ce,

H3Mefjy o6e

OÄHOcy n a m c t h j i

rpyny

npaBiijiy

He M ö w e y

Äpyra

obhm

Ba>KHHM

C h e m i e , 3,

c H c i e M H M a B p c x e KaMcJieHa h h j e a a H

C-aTOM

yiecTByje y

y

koJh

KibH3H

Auflage, Leipzig

cy

ce

OBae

t c h

Be3H.

O. Schröter-y

jkhbhhot

6eH3HJia,

apyra

caMO a a ÄOÄHpHy, M ö w e

Theoretische

(Hajöojbe

Stai

dinier):

H3JiaraH>e

Grundlagen

ce

M0Jieicy;icK0r

der

organischen

276. Bpjio Jiena p e a n u H j a

HaHMe H>er0B0 n p e B o l j e i t e

(B. 4 2 , 2 3 4 6 ( 1 9 0 9 ) ) .

oKcnaa

6 e h 3 il ji" (Curtius,

I, S .

moi-jih

h onrnnpHo

caMO j o u i j e ^ H a n p e n a p a T H B H O

Koja Tanolje nona3H o ä

npeMa

noMohy

JacHo

Hüchel,

W.

1940, B a n d

Oß;ie Tpeóa aa ce noMene MeiuTaH>a,

He3acHheHoj

3a OBaj ynbOBOÄOHHK.

paAOBHMa,

ce

b

Bredi-

T a i H i i j e o ö a ß e c T H T H H3 p a n o B a H. Meerweln-a.

npeMeuiTaita H a ^ a 3 H

äbo

H3MeJjy a h

ÄaTa (jjopMy.ua K a M ^ e H a , n p e T C T a B J t a , n a « c e 6 o J b e 3 a i \ n e , n a , caMO j e a a H

nperjieaHHjw HaiHH nwcaita O

ce b h ä h ,

Be3a, jep npeiia

HHKaKBa ÄBOCTpyKa

óhuhkjihihhm

Kojn j e 3aje^HHHKH 3a o 6 a n p c i e H a

nao u t o

o ä a , b Ka b , c . H a H M e

noMepnjia

He MOMíe H 3 n p o c T o p H H X p a 3 J i o r a a a e r 3 H C T H p a o b o m

ch!,

KaM({ieH

pa3JiHKa

CTpyKa Be3a y

)2

CH a

II CH,

c

3

X n i p s 3 0 B

HanpaBimi

C „ H r • C O • C • C•«eH ^s

ra

-->

caM)

y

6eH3Hjia

npe-

ÄHijieHHjRece

«exHnporeHyje

ä o a H a 3 0 - j e . n n H ) e H > a , T3B.

„a 3 h -

C6H5 • CO • C • C6H5

N • NHo

N =

N'

Ako ce OBaj 3arpeBa y OTcycTBy Ba3iiyxa h BJiare y 6eH30Jiy, OTuenjbyJe ce a30T, a ocTaiaK HHTpaMOJieKyjicKHM npeMeuiTaiteM npejia3H y ÄHeHHJiKeTeH: Cr.Hc

flo

oBor

C O • C • CbHk

oä

6eH3HJiHe

HHJixjiopaueTHJix^opHÄ,

noMohy

LUia je

a

H3

KHcejiHHe OBOra

5

o j i o B o i e i p a - a u e T í i T a , 2

c a H Ha CTp. 9 9

6eH304)eH0H

h H3ÄBojOTH

no

o6a

Èiattdlnger-OBOU

c e c a P C 1 5 npeBOÄH

aTOMa

Criegee-y,

h 6eH30(j)eH0H.

j a j i H e CHpheTHe KHcejiHHe n c n a p a B a i t e M neipojieyMeTpa.

ce

Koja

xjiopa

y

y K J i a a a j y ca

ä h cj> e uhhkom

y r Jb e h c y 6 o k c h ä ?

c e ^ H H a c j i h w h o niHKOJiy y C 0

Ma.io

\CrH

H H i e p e c a H T H o r K e T e H C K o r a e p H B a i a ÄOjia3n c e h n o c i a p o M

nocTynKy nojia3ehii ((jjopMyjimim!).

0 = C = C

Ä e x H Ä p o r e H y j e c e 6eH3HJiHa k h -

M 3 B e c T H o r j i e a Ha H a q H H K o j n j e o n w -

Ha T a j HaiHH,

uito ce nocjie

y BaKyyMy 3 a o c i a j m

yKJiaH>aH>a r j i a u H -

yjbacTH o c r a i a K j w r e p n p a

ca

OpraHCKo-npenapaTHBHH .aeo

182

6. Á A M U H j a ijHjaHOBoflOHHKa H a ajiflexHfl. B a n e M O B a K H c e j i H H a h 3 6eHsaJiflexHfla H H T P H J I ö a ^ e M O B e KHCGJIHHC. 15 g CBeace ÄecTHjioBaHor 6EH3AJIAEXUAA noMema ce ca OKO 50 MI KomjeHTpoBaHor pacTBopa HÜmpujyM6ucyn(puíüa y uhjihhäPY ca ryMCHHM sanyuiatjeM. C M e m a ce Mema CTaKJieHHM uiTanaheM cBe ÄOivie, a o k He o^BpcHe y Kamy aMuiiuonor je/ H wn>en>a C 6 H 5 • C — O H ^S0

3

h T3ßa ce noHOBO

CHa>KHO H3MyhKa.

Aahiíhoho

Na

jeÄHH>eibe ce oae^H Ha BSKyyiwy, ,no6po Hcnpecyje h ncnepe hckojihko n y T a ca m3¿io jie^eHe BOAe. Taí,a ce AO,naBait>eM HeiiiTo BOAe s a h u h o h o m jeÄHK>eii>y Ha^HHH r y c r a Kama h ä o a s oxjiaijeHH pacTBop o ä 12 g o n e r a r KajiujyMifujaHUw y 25 ml Bo^e. Elocjie KpaTKor BpeMeHa, HapoiHTO ji&ko n p n Memaity, Kpnera/iH ce pactBapajy, a nuwpuji óaaeMOBe mcejime ce H3Äßaja Kao yjbe, Koje ce y jieBKy 3a OABajaH>e OABoj« o ä Bo^eHor paCTBopa H OÄMax Äajbe npepa^yje. C a a o H H ( J ) H K a u H j a H H T p h ji a. H h t p h j i ce y nopae^aHCKoj 3£e;iH Ha Bo^eHOM KynaTHJiy HcnapaBa y 3 AOAaTaK leTBopocTpyKe 3anpeMHHe KOHl}£HUipOBClHe COM KUCeJIUHe C B e Ä O T V i e , AOK Ha n O B p i I I H H H T e H H O C T H He noHHy oöhjiho « a ce H3ABajajy KpncTajiH. PeaKUHOHa cinema- ce OCT3BH K& CTOJ'h npeKO Höh« Ha xJia^HOM MecTy, H3ABojeHH KpHCTajiH ce, nouiTO ce 3flpo6e H A o ö p o H3Memajy ca Maao BO^e, oue^e Ha BaKyyiuy H Hcnepy ca Majio Bo^e. H 3 (JjampaTa ce eKcrpaKiiHjoM ca eTpoM AOÖHja jom je^Ha Aajba KOJiHiHHa KHcejiHHe. C n p o B a ôawMOBa mcejima ce Hcnpecyje Ha T3H>Hpy o ä n o p o 3 H o r nopue^aHa, cyuiH H KpHCTajiH3auHj'oM H3 6en30Jia ÄOÖnja y ^hctom e r a i t y . Taqna Tonjbeiba 118°. npHHOC OKO 1 0 — 1 5 r. P a 3 a b a j a a e h h s i í t h b h c ö a j e M O B e k h c c j i h h ë Ha C B o j e a K T h B h e K O M n o H e H T e 1 . H a boächom KynaTHJiy Koje jkhbo Kjbyqa, 3arpeBa ce 1 caT y oTBopeHOM öajioHy CMema OR 10 g KpwcTajiHe 6aaeMOBe .¡túcenme h 20 g KpncTajiHor ifUHXOHuna ca 500 ml Bo^e, y 3 Bpao necTO MyhnaHse. f i o o x j i a ^ e a y npoueAH ce o ä HepacTBopHor, He HCimpajyhn BHiue boäom. y ÔHCTap pacTBop (a) yHeçe ce hckojihko KpwcTa^a iiHHXOHHHOBe coflH d-ôaaeMOBe mcemne (bhah HHMce) h oct3bh Aa ctoj'h, Beh

npeM3 noTpeÖH,

jeAaH

h^h

BHiue AaHa

Ha xJiaAHOM

MecTy

(6—8°;

jieTH y xjiaÄitSHH, 3hmh eBeHTyajiHO y n o A p y M y ) . n p H TOMe ce H3AsojeHa CHpoBa uHHxoHHHOBa co í/-6aAeMOBe KHcejiHHe oijeAH h3 B S K y y M y ((JjH^iTpaT Á Tpeôa c3HyB3TH) h npeKpHCT3JiHine H3 20-CTpyKe kojih^hhc Bpejie B O A e . A k o ce pscTBop neJiuyje ca h c k o ^ h k o KpncTajia iihhxohhhobc cojih d-6aÄeMOBe KHcejiHHe, t o he npH Ay^teM cTajaH>y, noA hcthm ycJiOBHMa Kao rope, a a HCKpHCTa^Hme 1

q n c r a j a co.

JXa c e AOÔHje cjioôoAHa

BHÄH B. 16, 1773 (1883) H 32, 2385 (1889).

í/-63í,eMOBa

183

AJIIIEXHÄH

KHce^HHa, pacTBopH c e

c o y Majio BOAe

npe^HUIHEHA

He3H3THOM BHEiKy, npH MCMy c e

T3JI0JKH

I^HHXOHHH

AOAa

H

y

AMOHHJAK

c e oueAH

KOJ'H

nocjie

H

npeKpHCTa^HcaBaiba H3 pa36jia>KeHor aJiKoxojia Moace Aa c e ynoTpeÖH 3a Omen.

HOBH

Í>H^TPAT,

3âKHcejiH c e COHOM

KOJ'H

oMOHujyMOBy

CAÄP>KH

co d-ôaaeMOBe

KHcejiHHOM H e K C T p a x y j e eTpoM.

HcnapaBaita eTpa, 3arpeBa

Ha

BpeMe

HCKO

Kucemne,

OcT3T3K c e ,

nocjie

KynarHJiy Ha caxaTHOM

BOACHOM

CTaKJiy, npH qeiay, Ka^a c e oxJiaAH, HCKpHCTajiHiue d-6añeMOBa

Kucemna,

Koja

c e n o c ; i e n p e c o B a f t a Ha T a i t H p y OA n o p o 3 n o r n o p u e j i a H a , npeKpHCT3JiHiiie óemojia

H3

joui

HJIH

6OJBE

4HCTa /-6afl,eMOBa nolje

OA

xjiópotpopMa.

H3

TANNA

He M o m e

KHCCJIHHH

JiaKO

KH

c n o ö o A H a KHcejiHHa

HHCTE

I/-KHCEJIHHE,

H

n o r o A H e KOHijeHTpauHje Y

cjiyjajy aa

ce

HeMa

aa ce

npHnpaBH

noroaaH

rope

ÄOÖiijeHor

pacTBopa

co.iu

C B e ÄO r i o j a B e T a b o r a .

CTojn

C B ; Ä O T . i e , ÄOK n e

je/ian

jan.

HE^HCTE

/-KHCEJIHHE

HcnHTaj

H

3a

nowny

co

Kan

no

3arpeBa,

aa

ce

HSHHHH

d-öaaeMOBe

nejmoBafte

(a) A O Ä a j e c e Ta,iia c e

Kan

3acnheHor CBe

ÄOK c e

H3.HBajajy

hsmhh;

KpiicTaJin,

y

A K T H B H e

nojaBy jiHHa

Aaje

6 a Ä e M o B e

CMHcao

poTaunje

d-(—)-njiTpaT l)eH>eM

4)HJiTpaT

ce

y

BpeMe OTBapa, jbHBO

Ha

BonoHiiKcyjKjjuaa 6OUH

ca

Bpe;io.

öpymeHHM

OCJIOÖOÄH o ^ o B a yBOce

OjioBocyjKpua sanymaieM,

oueÄH Ha H y q y ,

Koja

a

c e c BpeMeH3 Ha

j o i u MJiaK MyfaKa c a OKO 3 g CBeme e r a j i o j K e H o r H 6PH>k-

HcnapeHor

,na

cpeßpoKapöoHama,

6H

ce

yÄajbHJW

KOJH noTHqy o a p a e T B o p j b H B o e r a o J i o ß o x j i o p H A a npoÖH).

H3 npouel^eHor

pacTBopa y Koja je joui

yßoijeH

cyMnopBOÄOHHK

3aocTaje

noc^e

CBH

x^op-joHH>

(ncnHTaj y j e ß H o j M a ^ o j je^HOM

ncnapaBaita

KpaTKo

anamn

o ß o j e H CHpyn, KOJH TpJbaH>eM KpHCTaJiHiue H3 aücojiyiüHor

BpeMe

K a o TBMHO

amoxojia.

flocke

HeKor CTajan>a A o ö p o c e o u e A « Ha B a K y y M y , « c n e p e c a Majio a n c o j i y r H o r a^Koxo^a,

33THM

ca

aücojiyüiHUM

H cyiun y

ewpoM

BaKyyM-eKCHKaTopy.

flpHHOc 1 5 — 2 0 g. AjiaHHH MOHce Äa c e npeKpHCTa^HUie H3 HCTC KO^HMHHe Bo^e,

a^H

y3

ße^HKe

ryÖHTKe.

Bojbe

T p e o H o j KO^HHHHH K;byqa.iie B o ^ e H TOJIHKO a ^ K o x o ^ a , (y3

M,OK He n o ^ H e

je

c e p a c T B o p « y TaMaH n o -

c e ÄOAa Ha T e M n e p a T y p H K J b y H a i t a

KpHCTajiH3auHja.

TanKa

Ton^eH>a

264°

pa3^araK.e).

Ad 6 H 7. OßÄe aaTa Me-ro.ua uHjaHXHapnucKe cHHTe3e — peamiHja H3Metjy ßHcyjieH>e H H T p H ^ a 1-6 a A e M o B e K H C E J I U E E ca r e H T H 0 6 H 0 3 0 M TO OH npHna«a KJiacn ß-rjiHK03Hjxa, Jep ce ÄCJCTBOM eH3HMa eMy'ji3HHa pa3Jia»e Ha Äßa MoaeKyaa i\nyK03e, 6eH3ajiÄexHÄ H UHjaHOBOÄOHHqHy KHcejiHHy. Liebig je npBH ÄO6HO npnpoÄHy /-öaÄeMOBy KHcejiHHy pa3fla»yhH AMHRÄAJIHH ÄCJCTBOM KHcejiHHa. y rpynn uiehepa ynoTpeöHo je H. Kiliani UHjaHHXHjipHHCKy cHHTe3y 3a H3rpaÄH>y BHUIHX uiehepa. KapöoHCKe KHcejiHHe, Koje ce ÄoöHjajy canoHH^HKaunjoM HHTpnjia, Mory y oö^HKy CBojHX ,naKTOHa, aa ce pejiyKyjy y oflroBapajyhe aMexHÄe.

AjiAexHÄH CN I HCOH 1 I HCOH I HOCH

HC-O HCOH I HOCH I HCOH I HCOH I CH2OH d-rjiyK03a

HCOH I HCOH CH2OH

185

/CO I HCOH O I COH V I N:H I COH I COH

HC = 0 I HCOH I HCOH I HOCH I HCOH I HCOH

/

CH 2 0H

CH 2 0H d-rjiyK0xenT03a

KOÄ Harne cnHTe3e HHTpHJia 6a.neM0Be KHcejiHHe cTBapa ce acHMeTpnMaH yrjbeHHKOB aTOM H TO OBÄE nocTaje TaiHo noajejiHaK 6poj MOJieKyjia 06a aiiTHno.ua, Jep je BepoBamoha 3a 06a npoctöpHa oöjiHKa ncia: PhN OH PH

\ r C- = 0 Hy

W Phv

yV

H'

X

CN /CN S

OH

d- H l-o 6 .i H K ce pa3/iHKyjy caMO K p a c T a i H H U O Ô J I H K O M H c u e p o M c K p eT a i t a ; CBe apyre (|)H3HHKC H CBe xeMHCKe ocoöHHe cy HM noTnyno Here. A M I CO;IH o6e KOH(j)nrypaunje ca HCKOM OHTHIKH aKTHBHOM 6a30M He oflHoce ce BHiiie je^Ha npeMa apyroj Kao npe^MeT H JIHK y onneAaJiy H H3 Tora np0H3HJia3e H pa3JiHKe y 4>H3HIKHM KOHCTaHTaMa, Ha np. pacTBopjbHBOcm KaKO ce OÄBajajy paueMCKe 6a3e? EH3HMII ÄeJiyjy cneiiH(jjH4Ho na jeaHy oapehjeny KOHtfìHrypauHjy. H a TOMe ce 3acHHBa r/acmepoBO pa3JiaraH>e nHporpojKÎjaHe KHcejiHHe na ÓHOJIOUIKOM nyTy, n o M o h y rjbHBHiia ruiecHH, Kojn TaKohje M ö w e aa ce npiiMeHH Ha paueMCKy öa^eMOBy KHcejinny, 3aTHM napunjajiHo Bapeibe paueMCKiix nojinnenTH.ua no E. Fìscher-y H MHoroöpojHH apyrn npouecn.

8. nepKHHOBa cHHTesa U,HMeTHa KHcejiHHa h s S e H a a j i A e x n ^ a h CHpfeexHe KHcejiHHe 21 g (0,2 MOJia) âeH3ajiaexum, 3 0 g aHxuMpuw cnpheTHe KHC6JIHHC, o6oje CBeace ÄecTHJioBaHH H 1 0 g cnpauieHor 6e3Bomor HaïïipujyMatieniania (ynope^H CTp. 106) cwia ce y 6a;IOH Ha KOJ'H ce CT3BH iunpoK H OKO 80 cm ßyrH Ba3fl,yuiHH K0H^eH3aT0p, H 3arpeBa 8 c a r a y yjbaHOM KynaTHjiy Ha 180° (noneTH y j y T p y ) . I l o o i e CBpuieHe peaiojHje npepyna ce Bpejia peaKUHOHa CMeiua y BehH ôajioH, cnepe BOAOM H npoBOflH BOACHa napa CBe AOTvie, AOK h2 npecTaHe a a npeJia3H 6eH3ajiÄexHA. npH TOMe ce ynoTpeÔH TOJiHKO BOÄe, A3 CBa ifUMewHa mcejima npelje y pacTBop, H3y3eB MajiH ocTataK yjbacre HeiHCTohe. flpoKyBa ce t a ^ a pacTBop joui KpaTko CN I 1 HcT0BpeM°.H0 HacTaje aHranoaHa KOHcJmrypauHja HOCH, am He Kao npn cTBaI paH»y jeaiiocTaBHor paueMaTa y HCTO] KOJIHMHHH. Beh paHHje acHMeTpniaH Mojieicyji BpuiH ÄiipnryjyhH yrauaj, 3Ôor Kora je y T3KBOM cjiyqajy je,nHa OÄ o6e KOHijwrypaiiHje (j)aBOpH30BaHa.

OpraHCKO-npenapatHBHH ,neo

186 BPEME

ca

MA^io }KHB0THHJCK0R y r j b a

XJIA^eiby,

AOÖHje

H3ÄBAJA

I^HMCTHA

OÄMax A o ö p a

B p e ^ i e Bo,n;e. T a q i c a

H npoue^H,

KHC6JIHH3

y

Ta^Ka TonjbeH>a,

Toiubeita

133°.

nocjie

cjajHHM

nera

npenpHCTajimiie

FIPHHOC

ce,

JIHCTNHHMA.

OKO 1 5

NPH

AKO

ce joui

xrace

HE

jeAHOM

H3

g.

flepKHHOBa peaKUHja ce OÄHrpaBa npeMa o n u u e M npHHUHny ajiÄexHÄHe K0HÄeH3auHje, HaHMe y3 H3ÄBajaH>e KHceoHHKa ca Äßa aTOMa BOÄOHHKa MenuieHCKe HJIH MeTHjme rpyne. EKcnepHMeHTgjiHH ycnoBH 3aBHce OÄ peaKUHOHe cn0C06H0CTH OBHX nocjieÄfoHX. Y c a y q a j y Äa jeaan ajwexHÄ p e a r y j e ca ÄpyrsiM ajiÄexHÄOM HJIH KeroHOM, peaKunja a a e Beh Ha XMÄHO y npncycTBy KHceJiHHa H;IH aJiKaanja Kao KaTajiH3aTopa. Y cjiyqajy Äa ajiÄexHÄ p e a r y j e ca aHxHÄpHÄOM KHcejiHHe, noTpeöHa 'je BHCOM TeMnepaiypa H ajiKa^Ha co icao KOHÄeH3aUHOHO CpeÄCTBO1. Pa3^HKa y ycjioBHMa ä o m 3 H oiyÄa, UITO je y aHXHÄpHÄy KHcejiHHe peaKunoHa cnoCOÖHOCT MeTHflHe r p y n e (OÄHOCHO a-MeTHJieHCKe r p y n e ) He3HaTHa. KOÄ hH^HÖapHe KHcejiHHe Moixe «a ce H3BpuiH KOHfleH3aunja Ha o 6 e C H 2 - r p y n e . nojia3ehn OÄ He3acnheHHx a;mexHÄa, na np. uHMeTHor ajiaexHÄa, ynoTpeöHBiiiH OJIOBOO K C H Ä KAO KaT&DH3aTOp, ÄOJI.13H Ce ÄO BHIIieCTpyKO He3aCHheHHX ÄHKapÖOHCKHX KHCejlHHa, Koje H3ÄBajaH>eM 2 C 0 2 npe.na3e y oöojeHe „n o ;i H e H e" (R. Kuhn2). CH = C H 2 C6H5 • CH =

CHCHO

+

• CH =

C • !CO„!H

| CGH5 • C H =

CH • CH =

C

rioJia3ehH OÄ TpocTpyKO He3aCnheHor ajiÄexHÄa CGH5 • C H =

CH • CH =

CH

ÄOBOÄH OBa CHHTC33 ÄO 6 a K a p H O - u p B e H o r KOHjyrOBRHHX ÄBOCTpyKHX Be3a. MHCTO p O T H H MepaH

ajiHcjDaTCKH

C40H56,

JIHKONHB

H3C

6oja

nonneHH

nauinyaHa

11 H

CH • CHO

y rjbOBOÄOHHKa C 2 8 H 2 6 , Kojn caapnui oca«

MHHe H H T e p e c n H T y

M p K B e , CAÄPIKH

upBeHor

• CH =

rpyny

K a p o T H H Ö H Ä a.

KOHjyrOBaHHX ÄBOCTpyKHX rnnnKa

HMa

CSM

K a-

B e 3 a , ÄOK C HJHM

H30-

13.

CH3

H3C

CH3

C H : C H • C : C H • C H : C H • C : C H • C H : C H • C H :C • C H : C H • C H :C • C H : C H • / ' N —CH,

i

i

CH«

i

CH,

i

CH«

CHQ

„

1

" ^ L

H,C—J H

2

ß-KapOTHH

yrjbOBOAOHHUHMa je Bpjio 6jiH3aK npaTHJiau. xjiopo(J)H.na, KtanioijiHJi, ca H>HM H30MepHa wyTa'öoja KyKypy3a 3 e a K c a H T H H (Karrer). O ß a e npiinaÄajy TaKolje nojineHCKe KapöoHCKe KHcejiHHe K p o u e T H H H macfpaHa (Karrer) H upBeHH 6 H K c H H H3 op;ieaHCKor ÄpßeTa (Kuhn). IipßeHa 6oja ÄHBjbe nanpHKe Physalis alkekendi), 4 > H 3 a j i H e H , je ÄßOBaaeHTHH nojiHeH-a.nKoxoji ecTepn^HKOBaH ca najiMHTHHCKOM KHcejiHHOM (Kuhn, Zechmeister); TO je npaBH . j i H n o x p o M " , OBHM

C40H56O2

(Willstäiter)lu

IlpeMa BA>KHHM HCNHTHBAFTHMA Euler-A A , 3 K o j n noTnoMaMce p a i u h e i t e .

MHH y

Kalnln,

Helv. XI, 977 (1928).

1

BHÄH

2

Helv. X I , 87 (1928).

3

BHÄH

Javiiiier,

BL. 4 7 ,

H

OÄHOC c e

489 (1930).

Karrer-A

KapoTHH je Bpjio 6JIH3AK

BHÄH H3 c a e f l e h e

B H T

t j j o p M y j i e 3 a BHTAMHH

aA:

187

AjiaexHÄH

HGC

CHG

c H,G

;C — C H

= C H — C = CH — C H = CH — C = C H I

C — CH CH

Jia3e

H3

H

npHMeHy Kon

rpyne cy

ca

XHÄpHpatbeM

ajiKajionAHoj

ß-a p H J i n p o n H O H C K H X

xeMHjw

aJuiexMÄHMa,

Hero

Kao

KOÄ

KHcejiHHe

u

KOÄ

6jia>KHM

3HaiH

u a j i o H C K e KHcejiHHe,

ycjioBHMa,

aonyHy

p - a p H a a K p n a H H x

KHCCJlHHa.

K y M a p H H a

CHHTe3y

CHpherae

FIOÄ M H o r o

M3JIOHCKC

3a

h

K H c e o H e ,

peaKTHBHHje

ynoTpeöa

(Doebner),

3

n p y a < a B a w H o n o M o h H o cpe.ncTBo_.afl Ä o ö n j a f o e

HJHX

x n n y p H e MHoro

ÄeH30BaTH ÄHHa.

y

C H

2

OnwcaHa peaKunja K H C e j l H H a

C H 3

S

— C H „ O H

I

K H c e i i H H e

CTora ce Ha

np.,

IJepKUHOEe

o6e

Beh

OHe

Ha-

cajiHUH.na.imexHÄa.

H3

MeTHJieHCKe

Äajy

y

jiaKiue

KOH-

npncycTBy

peaKunje

3A

rinpn-

ajuicfiaTCKH

pea

Ha np.: , C O O H CH

• C H O +

3

CH

(COOH)

2

->

2

C H

- C H =

3

C / \ C O O H

>

CH

3

• CH = CH

KpOTOHCKa

• C O O H

+

C 0

2

KKCCJIHH3

I l o c T o j e Äße u H M e m e KHCCJIHHC pa3JiimHTe KOHcJjHrypauHje, Äpyroj

y

OÄHocy

Tpanc-o6jinKy

Me T Ha

uHC-TpaHC $yMapHoj

(oaroBapa

K H c e JI II H a

Haouepiije. KHce^HIIN)

OöimHa

Koje CToje jeaHa

miMeTHa

KuceJiHHa

KiicejiHHa

UHc-unMeTHa

30Be

npe.\ia

OÄroBapa

ce

a n o i i a -

II n o p e a n3oniepa npBH n y t J e HaljeHa y ÖHJBHOM napcTBy. CHHTe-

THMKH c e Äo6nja napu'njajiHHM Kaia^HTimKHM XHApnpatt>eM ca njiaTHHOM H H 2 113 IJJ e II H JIn p o i i H o i H e

K H c e j i H H G

C6H

• C =

3

(Paal),

C — C O O H

Ä H6 p o MUHMe T He

KHcejiHHe

T e 3 y

O-H H T p o c t i e H H J i n p o n H O j i H e

OÄ

Bayer-a

H3

c y Äße o c i a j i e UHMeTHe KHcejiHHe nojiHMopcjmii

OÖJIHUH A J I O U H M E T H E

Orjieji,: 6OUH

OÄ

ifUMeiüHe HOCH c a

Kucenme

OKO

y ml.

100

T A A A

c e

CBOKH BHÄH

H

pa3Ö^.

y H e c e

2 % - H H HHace),

ÄOK

CBa

n o M o h y

c ß e M y

(ciaBHTH DtcuBa

jieBKa

He 3a

M o p a

^ a

ce

jyMKapöOHama,

OKO

n o c r a H e

T a ^ a

HeniTO

M a j i a

y 3

—

c e

coHe

n y c r n

^ a

KOJiHHHHa,

He

TanHa;

OQEÄH

CMe

ce

na

JiaraHO

x ^ a ^ H .

o6e3ÖojH

joiu

K a o H

ce,

na

y j b e .

x a p T H j a

ce

CTp.

3 a n y m a q a AOßHJAAA

Ha

BOÄCHOM

CBe

ÄOTJie

TeqHH

KucemnoM,

MeTaji

n p «

XjialjeifceM

6.

H3

H

q e M y

TpjbaiteM BOAe,

KHcejiHHe

FIpHHOC

3a

ajiKajiHa.

(HAHHH

3 a r p e ß a

g

H3-

HcnHTyje

OTBapaibe

p a 3 6 ^ a » i e H o r

K a n pacüiBopa

H

Ha

T o n j b e i t a

10

3anpeMHHa

n p e K p H C T a ^ m i i e

Y n o p .

Majio

eraKJieHoj

TaMaH

o ß B o j H

COHOM

TaqKe

Y

3 a r p e B a T H )

O X M ^ a y

HHCKC

y

ce

ß a ^ e

3aKHcejin

B a K y y M y

3 6 o r

H

KOMA^NHÜMA

Ta,n,a

H3ABaja

p a c T B o p e H a

»3

pa3JininTH

MyhKaH>e

m

6 y a e

M y h n a i b e

n o

y 3

p a c T B o p a

Kan

K p a j y

H

ce

n o c T e n e H O

peaKiinja

H a

H p a c T B o p

KHcejiHHe.

ÄOAaje

M3JIHM

B O A y

H a j n p e

ao6nje

nouasajio

K H C C J I H H C .

Tano,

je^Ha

C T a j w o

250g.

ce

HHÄHTO-CHH-

KpHCTajiorpatjJCKH

p a c T B o p «

ce

—

y

Tonjiy

mcemna

o q ß p c H e ;

c a ^ p Ä H

y

o^Bajaibe

xuapoiiuMeüiHa

OHa

x a p T H j o M K a n a a i t e M

HawpuiyMdMajiraM y

U H M C T H 6

3 a n y m a H e M

naüipujyMXUApoiccuay

n o c T e n e H O

na

(Billmann).

HATPHJYMXHAPOKCHÄ

HCRIHTHBAHBE

K y n a T H ^ y

KHCEJIHHE

ö p y n i e H H M

(J)eHO^(J)TajienHCKOM

u e l j e f t e

c e

ca

Möwe

KHCCJIHHC.

T a i K e Tonjbeiba 42° H 58°

X I I A P O R E H O B A I T E ml

250

Koja

ÄßocTpyKHM OÄBajäfbeM H B r . BHÄH

8

p a c T B o p a

UepMaHranama.

Koja (47°)

g.

nampu-

OpraHCKo-npenapaTHBHH fleo

188 XnaporeHOBaite Ta^HTHMKH ( b . X I ,

ubmcthc

HaTpHjyMaMajiraM. Bpjio ca

óypHo

y3

nojaBy

6 , 5 g)

Ha

30°—40°

Hadaba

KOMaAnhH

ce

ce

3aui.THTe o a y

Ao6po

h y

ce

Ma^e

npcKafta

aiuajiraM

y

KOJiiHHHe

acHBy'.

jiOHau 3arpeBaTH

jeAHO c

Ka-

y

30 cm

HCHBy,

n o K p H j e TaibHpoM o a

jora Bpyh,

ApyrHM

KanejioM

300

noTanajy

ce y

hchthh

h

CBeMy

nojeAHHH

npH i e M y nopo3Hor

Majie

h

cpe^ite

ce

y

nopue-

KOMaAHhe h

qyBa

cyay. HaTpHjyMaMa^iraMa

ce

Hajóojbe

J\a

c e AO'Snje

cnpaBjbajy

HaTpujywa

cTaKJieHH u i T a n , k o j ' h y c n e A

h toksk

3arpejaHy

H3BeAe

paAH h o a

uiTariHh A y r

jiaHCKOM xeeeHCKOM J i O H u y ; B e h n KOMaü,nhn raqan

ce

g oicaBe y a B a H y H 3 p e 3 a H HaüipujyM ( y

KOUKHixe

aBaH

ce

3arpeje

je^aH 3 a ApyrHM

3axB0peH0M

Behe

Hajnpe

Mopa

Ha 3auiHa>eHH c T a K a e H H

6p30

jiaHa. O i B p a i H

Taico^e

>KHBa h H a T p n j y M p e a r y j y

miaMeHa. C x o r a

3aiiiTHTHHM H a o i a p r n u a .

BejiHHHHe

MO«e

khccjihhc

1).

concTBeHe

BHiue o a

3%-Hor

y

uopue-

HaóoAy ce

Ha A y -

caM

TejKHHe

aMajiraMa

KJima

Mopa

ce

n;iaMeHOM.

a, p-H e 3 a c H h e H a K a p ó o t i H J i H a j e a h h> e h> a (ajiflexHAH, k c t o h h , ecTpii h KHcejiHue) XHAporeHyjy ce Beh yo6H»iajeHHM peAyKi»ioi¡HM cpeACTBHMa, nao uhhkom h k h ceJiHHOM, HaTpnjyMaMajiraMOM, HaTpnJyMOM h aJiK0X0Ji0M, aok ABOCTpyKa Be3a yrjbeHHKa koa ojieHHa MO«e Aa ce 3acHTii caMo KaTajimHHKH aKTHBHpaHHM boaohhkom. Thieie o6jauiH>aBa OBy MHH>eHHuy a a h u h j o m 1,4, npH Kojoj ABOcrpyKO Be3aHH yrJbeHHK npeTCTaB^>a noAeciiy HanaAHy Taqny 3a boaohhk; \

I

I

2

3

\ c =C — C = 0

/ l

2 H

4

->

r \ H

1

1

>C — C = C — O H

\_/

M ABOCTpyKe Be3e 6eH30Ji0B0r Kap6oKCH^HHM rpynaMa. Taxo MOMie (Baeyer) 6 e H 3 o e B a k h c e ji h h a h h u h r u n a C T H p o ^ a Mory Aa

(Klages), Ha np.:

^ ^ > C5H5

9. P a j M e p - T H M a H O B a CajiHumiajiflexHfl

xuapoKCiiAd pacTBop

ce

Aa

TaAa ce

CT3BH y

Apyry cana

y

ce ce

neiuy

ce 1

80

mi

1 JiHTpa

hs

3aTBopn

a Aa c e

npoBy^e TeqHoct,

npw

|

ce npa

CH3

g naBpujyMt o i i j i o 2 5 g i H C T o r cpenona h

y3

3arpeBan>e

80

TOMe He M y h n a , — —

noTanaaeM

Aa y

qnja ce

Hajnpe

ó^aroM

KOHAeH3aTOp A o 6 p o r ^onTHua

je^ny

AejcTBa, a

3aMonn

y

np0^a3H0

B. 9,423, 824 (1876); 10, 1562 (1877); 15, 2685 (1872) HTA.

oóojH

Kpo3

TeqHOCT

TpehHHa K p o 3 i;eB K0HAeH33T0pa

MyhKafty

ce

6«

x^aAny

miyTeHHM 3 a n y i u a H e M c a A B e p y n e ; y

TepMOMeTap,

g xjiopcxpopMa

I

xjiopocJwpMa1

HCKpHCTajmme

BepTHKa;iHOM n o ^ o j K a j y

o a 60

/

H

>C — C — C = O

CH2 •CH2

(freHOJia h

pacTBopn

HaTpHjyM^eHOJiaT

óanoa

J

\ H

ctiHTesa

BOAe, T e m e c e AOAa Ha

o x j i a A H Ha 6 0 ° — 6 5 ° ,

cnpeqHJio BO^y.

oa

óajiOHy

->

npcieHa Konjyryjy ce Ha cmaj HaiHH ca cyceAHHM Aa ce X H A p o r e H y j e naipHjyMOM y aanoxo^y h i j u a j i H e k h c e ji h h e. Ajih h y r j b O B O A O ce xHAporeHyjy hcthm peAyKUHOHHM cpeACTBviMa

CgH5 • C H = C H — C H 3

y

1

upBeHO

h

npH nao

An&exuw

V, 8

6yp,e H3Meljy 65°

ij)yKCHH. PeryjiHiuyhH Aa TeMnepaTypa 6ajioHa y x./i3AHy

H^H

Bpyhy BOAy,

1 8 9

H

70°, noTanafteM

ce nocae 10 MHHyTa Apyra Tpe-

AOAS

hHHa, a nocJie AajbHx 15 MHHyTa ocTaTaK xaopo3K.

NO

oxjiaijeity

ce eTpoM H3ABOjeHH 3^AexHA, eTapcKH pacTBop cyuiH

M3JIOM

eKCTpaxyje

6C3BOAHOM

rnay6e-

H nocjie Hcnap3B3it3 eTps, 33OCT3JIH qncr a^AexnA AecTHJimiie,

POBOM com

npn qeMy OH npejia3H Ha 190°. IlpHHOC H3HOCH 10—12 g.

p-OKCu6eu3ajifl,exun, KojH He npeji33H C3 jiHiue H

H3

TeqHocTH

BOACHOM

Koja 3aocTaje nocjie AecTHJiaanje ca

Koja je Ha Bpe^o npoueijeHa

H

3acHheHa KyxHH>CKOM

napoM HCKpHCTaBOACHOM

COJIH,

napOM

qecTo nyT3

Ten nocjie A y ^ e r CT3jaft.a. HJITP3T ce eKCTpaxyje eTpoM noane ueijeits, T3K0 Aa Ce AOfiHje MOJKe

jOIU H3BeCHa KOJIHHHH3, K0j3 33jeAH0 C3

Aa ce npeiHcra npeKpncTajiHcaBsifceM «3 BOAe, y3

OHOM

npBOM

AOA3T3K

HCUITO

pa36ji3MceHe cyianopscTe KncejiHHe. TSHKS Tonjbett>3 116°. npHHOC 2 — 3 g. IlpenapaT

He

ycneB3,

aKO

OAMSX

y noieTKy HCKpHCTa;miiie HaTpn-

jyM^eHo^aT. OBa cHHT63a Mo«e jia ce npHMeHH yonune KOH cyncTHTyHcaHHX eHOJia, ajw je OHa BehHHOM cjia6or npHHoca, jep Haciynajy cnopejme peaKUHje; OHa noTceha BeoMa MHoro CBOJHM pe3yjiTaTOM Ha Kolbe-OBy cHHTe3y cajiHunjiHe KHcejiHHe (VI, 4) H Morao 6H aa ce noKyiua, aa ce 3 a iteH TOK aa HCTO oejaiiHbeibe, Koje ce K a o BepoBaTHo TaMo noKa3aJio: na ce, HaHMe, nyieM HBocipyKe H3MeHe xjiopoiJiopM Bewe Ha KHCCOHHK y3 H3«Ba]aH.e je^Hor Mo^eKyjia NaCl H Tana o6a npeociajia aioMa xaopa 3aMeHe KHceoHHKOM; Ha]3afl TaKo HacTaaH (JieHOJiecTap MpaBJbe KHcejiHHe npeTpnh npeMeunafte, Koje ojiroBapa 4)eHHaKap6oHaTy, y3 eMHrpHpaH>e ifopMH^-rpyne (y o- HJIH p-noao5Ka]: —O • C CI. '2 H

i - O N a + Cl • CC1. 2 H

\/

\ /

190

OpraHCKO-npenapaTHBHH aeo

H

NaOH

*

-O • CO

—OH CHO

IlpeMa jejHOM apyroM BepOBHTHHjeM o6jamii>eH>y aÄ Hpao

na

iBOCTpyKy

Be3y

6 H ce

xjiopo^opM

H Ta.ua 6H

j e 3 r p a,

MJBE

npouec

Hajnpe

nrnao

npena

ÄaToj jiaKo pa3yMjbHBoj cxeMn:

I /H

-ONa

|

>

=

OH

0

\C1

—CHO

\ / \ c H d o

3 a oßaj TOK naTeropHHHo roßopH imteHHua,

aa c y H30ji0BaHH

aanunoHH npo,nyKTH

Koj« 6H jeÄHHo M O M H Äa HacTaHy Ha aHajior HanHH, HaHMe H3 O- H p-Kpesojia

Auwers,

B. 35, 4207 (1902)). ripuMapHH

H3 O-K p e 3 o JI a

npoÄyKT

Moixe n0H0B0 na ce cTBopn, Kao UITO ce

ne

BHAH, s ö o r C H 3 - r p y n e aponaTCKor je3rpa: ^ ^ - O N a \C1 /CH

-CH,

X / -

/CH

3

X / \ C H C 1

Je^HHO ce OÄßaja NaCl

H HacTaje

S

% / \ C H C I

2

j e Ä H H> e H> e

THna

2

xHHOJia

Kao UITO nona-

3 y j e (Jjopiuyjia, npn ieMy ce Äpyra Äßa xjiopHa aTOMa He xnÄpojiH3y]y. KOÄ P - K p e 3 0 J i a

ÄemaBa ce a i w u n j a xjiopoifopMa Ha 1,4-no^oiKa]: NaO

C1

' O

O Na

I

||

I

->

I

II

».

/\

x

II

CH3 C H S C H Cl 2 O ß a peaKunja n p y » a jaK AOK33 3a TO, M Mtajy 1,4

H Äaje

CH3

CHC12

ce y 6eH30Ji0B0M j e 3 r p y a a n u n j a BpuiH y ncwio-

npHKjiaAHo o6jam[t>eH>e na ce

p-cyncTHTyunja

Koja je

TaKo

qecTo

y3

0-cyncTHTyu.njy Aernaßa TaKofje nyTeM npeTxoÄHe aanuHje 1,4 (ynop. d p . 97). HCKOJIHKO

OrneflH: xuapoKcuay; JeÄHa

HacTaje Kan

(pepuxjiopuAa

jKyTa

BOÄCHH

y

HaüipujyM-

co.

MHpncy npeoßjialjyje $eHOJi Kao cacTaBHH ¡¡.eo. CaJiHUHJiajuiexHÄ noAJie>Ke

ayio-

o6a

CBaKor

TBajaKOJi Äaje o-a^ÄexHfla.

hjih ajiKoxoaHH

JbyÖHHaCTO.

MHoro Maae Hero 6eH3ajiÄexHÄ.

ynopeÄHTH Kann

6o\a

pacTBope ce

HaüipvjyMOBa

ajiae-

OKCHiauHjH

KOJIHKO

camtfuJiajiMexuMa

pacTBop

XHJ,a HHTeH3HBHO y

Kann

HHTCH3HBHO

CT3BHTH

UITO

he

ce

Ha c a x a T H o c T a i « i o H O C T 3 B H T H

aa

CTOJ'H Ha B a 3 a y x y .

a j m e x H . u a Ha T a j ' H a q H H ,

no

He-

ca xjiopxxfiopMOM H aJiKaanjaMa BaHHJiHH ca C M Ö H M npwHocoM n o p e a

eHo;iH ripenta Perkin-oßoj MapiiH ((JjopMyjiHuui!).

VI. O E H O J I H

191

peaKu.njn H3 cajimui.iiaji.aexH.ua H HaTpnjyMaueTaTa nociaje Ky-

H EHOJIH . KETO-EHOJIHA

TAyTOMEPHJA

1. n p e B o ^ e H > e cy;i({)OHCKe K H c e j i H H e y (JieHoji. ß - H a t J r r o J i 1 IloTpeÖHe xeMHKajinje: 70 g (0,3 MOJia) HaTpHjyMOBe c o j i a ß-Haera AGJCTBOM cyMnopHe KHcejiHHe, Hajia3H iiinp^Ky npnMCHy y np0H3B0£H.n a3o-6oja. H3 ß-HacjiTOJia, aejcTBOM aMOHHjaKa noÄ npHTHCKOM Äo6nja ce jiajbe ß - H a t J i T H J i a M H H : C10H7 • O H + N H 3 = C10H7 • N H 2 + H 2 0 KOJH, KaKo caM, TaKO H y oSjiHKy CBoje cyji(}>OHCKe KHcejiHHe, Hajia3H TexHHiKy npHMeHy 3a ÄOÖnjaibe a30-Ö0ja. H a - H a ^ i T O j Äoöwja ce Ha HCTH HaqHH, ajiKajiHHM TonjbeH>eM HaipujyMOBC COJIH a-Hatt)TajiHHcyji(j)OHCKe KHcejiHHe, Ma.ua He y TaKO BBJIHKHM KOJiH^HHaMa

Kao ß-Hac})T0.ii. HanpoTHB a-Ha(j)THJiaMHH Äoönja ce aHajiorHo aHHjiHHy pejiyKuHjoM a-HHTpoHa(j)TaflHHa. A^Ka^Ho TonAeH>e ajiKajiHHx CO^H apHincy/[4)OHCKe KHcejiHHe cjiywn TaKo^e 3a tcxhh^KO Äo6HjaH>e iHctor (jjeHo^a h MHornx (jjeHoaoBHx flepHBata.

1 E. Fischer, Anleitung zur Darstellung organischer Präparate. 11 H3flaH>e, Braunschweig 1930. 2 HJIH HCTa KojiHHHua ß-Hatj)TajiHHcy^(})OHCKe KHceflHHe, Äo6njeHe npeMa O. N. Wiit-y. BHÄH

IV,

3.

OpraHCKO-npenapatHBHH

192. flouiTO

je

xaaoreH

xjiop6eH3oaa

Bpjio

MBpcTo

aeo

Be3aH 3a 6eH3o;ioBo

j e 3 r p o , XHApojiHsa jeBTHHor

npeMa

/

+

2 NaOH

->

^)OHa +

Na C1 +

H20

(K. H. Meyer

H3BojjbHBa j e Ha Bpjio b h c o k h m TeMnepaTypaMa h t o pa36jia>KeHHM ajwajiHjaMa h

F. Bergius).

XHapojiH3a jiaKiue y c n e B a , ano HHTpo-rpyne y

0-

hjih p - n o j i o w a j y ojiaöaBe

Be3y xaJioreHa; 0 TOMe j e Beh 6 h j i o r o B o p a Ha crpaHH 8 9 . Ro

4>eHOJia c e MOHce ä o H h

apoMaTCKHx

a mh h a

eHOJiH

Ha je^aH

oniuTH

Ha^HH,

nojia3ehH

npHMapHHX

oä

n p e n o ÄHa30HHjyM0BHX c o j i h (VII, 3).

c e Bpjio jacHO

pa3JiHKyjy

ocoöHHaMa h peaKUHjaMa o a

cboJhm

oöimhhx

ajiKoxojia aJiHij)aTCKor p e a a . O h h c e Beh y o c h o b h pa3JiHKyjy o ä npBHX THMe, u i t o c e ibHxoBa O H - r p y n a Hajia3H Ha j i B o r y ó o Be3aHOM C-aTOMy. C r o r a Möwe a a c e n o B y n e napajiejia H3Mel)y h>hx h cjih^ho rpaljeHHx eHOjia, nano t o n o K a 3 y j y c j i e a e h e (jjopMyjie. H H

\

H ~

H H

/

V

c

H~~DH

H

R

A

OH

(JieHOfl ripocTH

c /

H

H

\

Z

H2

H

/ •• O

eHOji

KeTOHH, nao aueTOH h c j i h h h h ,

HHcy

nocTojaHH y „TayTOMepHOM"

oöjiHKy

H 2 C = C — C H 3 . flocTaBJba c e nHTaH>e, 3auiTo h ifeHOJi He n o c T o j n y cjihhhom Keio-o6;iHKy, I OH HaHMe y oó^HKy

03HaieH0M c a A.

MHHe HeMoryhHM Aa n o c r o j e

Pa3Jio3H c y BepoBaTHO

aepHBaTH

h c t h nao h o h h ,

icojn

yonune

ä c j i h m h i h o — OBAe « B a n y i a — xHApnpaHor 6eH-

30Jia, KOjH 6 h 6 h j i h cnocoÓHH 3a npeMeuiTaH>e, a Ha Koje j e Beh BHiue nyTa yKa3HBaH0 (Ha np. III, 4).

Te»Hja

TpH ÄBocTpyKe

ja

c e BehHHOM

Be3e, h h h h

3acnheH

c h c t c m apoMaTCKor je3rpa

Aa ce x h a p o k c h j i h 3

rpyna noKa3yje

Kao

oaprni

ca

CBoje

cTaónjiHa h THMe ce

HcnojbaBa cneunjajiaH KapaKTep $eH0Ji3. eHOJiH c y

KHcejiHHe

jep c e O H - r p y n a , Kao k o a KapöoHCKHX KHcejiHHa, Hajia3H

Ha aTOMy ca ABOCTpyKOM Be30M. — C — OH

— C — OH

II O

II C

H

Ä o a y u i e , KHceo KapaKTep npocTHX (JjeHoaa TyunjoM y j e 3 r p y c a HeraTHBHHM

/\ HHje j a n o H3pa>KeH h pacTe TeK cyncTH-

cyncTHTyeHTHMa Kao N 0 2 h xajioreHHMa.

AjiKajiHe c o j i h

cJjeHOJia c y jaKo XHApojiH30BaHe y b o a c h o m p a c T B o p y h Beh y r a e H a KHcejiHHa h x n0TnyH0 pa3JiaHce.

Ha

OBaj

h h h h

Mory

ce

$eHOJH

o i b o J h t h

0 a

KapóoHCKHX

KHcejiHHa. Or^eff;

$-Ha(pmojia

y

yrjbenauoKcua

ce

yBOÄH

HaMpujyMxuapoKctiay,

y

He

cyBHiue

pa3Ö;ia)KeH

pacTBop

CBe Ä o r o Ä c e H3ÄBaja c j i o ö o A a H

ncicpuioji.

O H - r p y n a (¡¡eHOJia ce h y ApyrHM peaKitnjaMa n o K a 3 y j e peaKTHBHHja o a XHApoKCHJiHe r p y n e ajiH^iaTCKHX ajiKoxojia. OHa p e a r y j e , cynpoTHO OBHMa, jiaKO ca T a K o ^ e ca ApyrHM cpeacTBHMa 3a ajmHJioBaH>e, Kao

ÄHä3OMeTäH0M.

aJiKHJixajioreHHAOM,

a h a ji k h ji-

c y j i i j i a T O M , p e a r y j e Beh y BOjieHOM ajiKajiHOM pacTBopy, ä o k cjrajiKoxo.nH HHAH^epeHTHH h6ä

ycjioBHMa.

thm

BeH30HJiHH

aepHBaTH,

BeoMa c y noroAHH 3 a H»nxoBy HAeHTH(})HKauHjy OrJiefl: (7a

s)

y

5

y

ml

enpyßeTH

jaKHM p a c T B o p o M

ce

pacTBopn

ml HaiüpujyMxuapoKCuaa a

Boae,

TOMe ä o ä s

1/2

oä

Kojnx BehHHa

Aoöpo

(Scholien-Baumann-OBa

KpHCTajiHme

peaKunja).

MaJia KOJin^HHa KpHCTajiHor

6eH30ujixjiopum,

(penojia

3aajiKajiHiue

6 ^ a r o 3 a r p e B a y 3 MyfaKafbe

ca

KpaTKo

VI,

aHOJIH H eHOJIH

1

BpeMe

nJisMeHy. A k o

Ha

MyhKaite

h

Tpjbaite

6 e 3 6 o j H e

KpHCTaJie,

H c n p e c y j y

Ha

O r j i e Ä TonjbeK>a

Kojn

ce

o ä

TaibHpy

ajiicoxojia.

Ma^o

peaKUHOHa

j;a

n o M o h y

h

hcth

Ha

H a tjj t o ji h

cy

Hcnojbaßa

TOMe,

KapôoHCKHX ca

ha

CBera

uiaBajy

KojH

npenapaTHMa.

ce

HeKa

Tanica

Koja

Möwe oä

h

Kao

tjjeiiojiH

«a

ce

h

npHMCHH

npocTor

(JieHOJia.

Ha

To

aMHHe

ce

npe

äoöhth hctom mctoäom K a o e c T p n a j i K o x o J i a h H C l . T a K o l j e ohm J i a n o pearyjy

ca

Mory

CMeuiÓM

h

aMOHHjyMcyjicjiHTa

peaKUHjy

nocjieaity

yTHuaj

m e,

je

mhoto ôjihikh

iyroBann öpoMQM,

6 p o M

h

Tajior

npeina

ca

68°—69°.

KHcejiHHe

ß-Haeifca

OHü.a

npeKpHCTajiHiuy

Torubeita

ce

6eH30HJiH0r

o u e ^ e

xjmäh

cMeuia

iirranHheM,

iviHHe

T a q n a

MOJKe

ce

cTaKJieHHM

193

hjih 95°.

HOBr

pa3ÖJia-

cnocoôHocT, H>oj

—

HajöJiHwy

Thiele-ost T e o p H j e ,

T O M e (}>eHOJi MOHce a a 1,2 h

CBe 6e3-

pearyje

1,4.

OH HBr

— HBr

/ V •Br

X / ' HOBr

OH -HBr

HBr

Br

Ha hcth H3HHH pearyje apyrw h TpehH MOJieKyji öpoMa, CBe aoK 6pori He 3ay3Me cBa TpH npHBHjieroBaHa nojiowaja (o-, .o- h p-). A k o caaa Äejiyje qeTBpTH Br 2 , to he noTnyHo Ha hcth HaiHH, Kao luto ce oBÄe npeTnocTaBJba, aa ce aÄHpa y 1,4-nojioiKaj: ripaKTHKyM

opraHCKe

xeMHje

13

194

OpraHCKo-npenapaTHBHH HO

Br

Br;

Br

fleo

VI,

2

O

O H Br,,

^Br

Br2

>

Br HBr

N

Br

He Monte

30Ji0B0r a e p H B a T a . O a n c T a j e K p a ] H . n n p o a y K i X H H O H a , jiaKjie a e p H B a T

\Br

Br

N3r

il

Br M e l ^ y T H M o B Ä e H3ÄBaJaH>e

Br,,

BHiiie a a n o H O B o a o B e a e

no n p a B o r

„ t p h 6 p o m (J) e h o n 6 p o m " ,

ÄHXHjipo6eH30Jia.

T e x H H i K á n p H M e H a o p M a J M e x n Ä O M

3 mí T e ^ H o r (jienojia ( „ P h e n o l u m l i q u e f a c t u m " )

oä

6eH-

KeTo6poMna.

cone

K o j e n p n xjiaijetby

ce

a a ce y 3 ö y p H y

Kucejiune,

o^BpcHe

Ta/ia

y K p y T y Macy

y

riJiaMeH peaKUHjy

(BeuiTaiKa

o ji a), n o Ä ßjiarHM y c j i o B H M a

fymon

ÄOJIHO] K 0 H Ä e H 3 a U H ] H , y p-0

ce- a a j e c j e Ä H H H T H

ca (¡)0pMa;i,nexHÄ0M,

aHajioro

aJi-

KCH6eH3HaflK0X0Ji: O H

OH

I. +

o c h

2

I ch K o j H , Ha t o i m o n 3 A B a j a Bony TaKolje ce 4>eHo;ia,

OBjie M o p a

Koje HacTaje Beh

o h

2

h n o j i H M e p n i u e ce. noMeHyTH h jinpeKTHo

yBoljeae

npw 3arpeBan>y (JieHojia

iKHBe

y

ca ) K H B a - 2 - a u e T a T O M

6eH30Ji0B0

je3rpo

(Balbiano,

Pesci>

Dimroth) : A

-

O

H

A Hg(0 • C O • CH3)2

A h h 3

a) uieHHM

BpeMeHa

Ha

ml 1

Kao KojH

rpaa

H cHa>KHo

yjbe,

He

cnojH

HaTpnjyMXHflpoKCHAa.

Uli mann,

100

5

pacTBopH

6ouh

y

ca

TpehHHa

oa

26

qeiuy HacTaje

npa

g

auMeüiuji-

MeTH-iOBaite

h

y3

,n,ajbe M y h K a a > e

ocTaiaK.

3a

BpeMe MyhKaiba ce

Käß

boächh BHiue

aaKajiHO,

ycnpaBJbeHHM

ZI,a 6 H c e

A, 3 2 7 , 1 1 4 ( 1 9 0 3 ) ; 3 4 0 , 208,

pacTBop,

ao^a

KOMe

ce

ôoiia iuiHBa

ca^pataj

H3Jinje c e

K0HAeH3aT0p0M

AOBpuiHJia

(1905).

Ha

6pyToMe

2n-HampujyMxuapoKcuaa.

MHHyTa

pearyje ca

ml

je^Ha

Myhna,

pa3MaKy

oraymaBa.

ce

y

C H3

(JjeHOJia1

MOJia) c e

Hajnpe

OTnpwjiHKe

a y KpaheM

BpeMe

(1/5

(peHOJia

KaneaoM)

OAje^HOM

0HU30JI

M3JIH ô a ^ O H ,

MeTHjioBaibe

y3aHor

floche

TpehHHa,

20

19 g

no£

H TO

CTBopeHH

ca

(paAH

3arpeBaibe.

Apyra

y

0ji.

3anyuianeM

ÄO^a

cyji(païïia

c

H

^ y - H g O C O

2.

y3

O

+ CHS • C O O H

^

ce

-

>

H

ncnepe

p e a K i ^ a j a H ,na 6 H

ce

195

eHOJIH H eHOJIH

pa3opHo Ha

boaghom

KojH ca

eBeHTyajiHo

ce

Kynamny. y

caMO

CaCl

h

2

joui

n p n c y T H H ,HHMeTHJicyji4>aT,

Ilo

cjiynajy

Haj3a^

oxjiaíjeiby TeuiKor

ÄecTHjiHme.

HcnycTH

oasajaita

Tanna

ce

3arpeBa ce nojia

boachh

cjioj,

KJbynaiba

155°.

anu30Ji

—

eïïipoM

eKCTpaxyje

IlpHHoc

qaca

—

cyinn

90%

oä

TeopHCKor. Ha (J)aTa

aHajioraH

Ha 6)

H e p o j i H H

aHH30Jia, CTaHua,

caMO

ce

TaMKe

Witt, B . 3 4 , n o p H e

ce

ÄOÖHja

$ e h e t o n,

(ß-Ha^THJi-MeTMeiap).

Meitajy

Tonjbeita

3172

3 6 o r

C B e

HaiHH

^ejcTBOM

AHeTHJi-cyji-

4)eHOJi,

72°.

O

iteroBOM

IlocTynaK oähoch.

cTexHOMeTpncKH

je

T o

noTnyHOM

je

nao

koä

KpncTajiHa

hcth

cyn-

npenaiiihaBaity

bhäh

(1901).

B i J i H K e

o r p o B H O C T H

K H c e j i H H e ,

o n e p a i í H j e

n p e

c

c B e r a

ftHMa

H e y T p a j i H H X

e c T a p a

^ H M e T n j i c y j i ( J ) a T a ,

h 3 b o ä h t h

B p j i o

c y m-

M o p a j y

n a x j b H B O

c e

h

n o i

K a n e a o M l

MeTH^OBaHjC a h m e t h il c y n tj> a t o m yBeK ce H3BOÄH y aflKajiHOM pacTBopy. Oho y c n e B a H a p o n n i o ;iaKO ca KapöoHCKHM KHcejiHHaMa

(MeToaa 3a ao6njaH>e

aoK ajiHiJjaTCKH a;iK0X0JiH, Ha np. m e h e p i i caMO pacTBopy, a a j y e c T p e c a OBHM cpeacTBOM. T p e ô a HMam HOJiOM,

MGTHJiHe r p y n e ,

npeMa

TeuiKO

Ha

e c i a p a ) H c a 4>e-

h najôojbe y

yiny,

a a caMO

ajiKoxojiHOM

jeaHa

oa

oöe

jeanaiHH«: Mac -

CX

CcHsONa +

NaCX \ S 0

h3C -

C6H50 • CH3 +

2

o /

J>S02 H3CCK

npe;ia3ii Ha eHOJi. T e i ; a y w i i M aejcTßOM na T C M n e p a i y p i i Kji>yiaH>a H a j n p e cTBopeHH k h c c j i h MeTHJicy;i(| JaT a a j e c B o j y MeTHJiiiy r p y n y , ajiH c e t o n p e n a p a i H B H O BehHHOM He H C K o p n t u h y j e y HCToj

peaKUHjH.

TaKofye

ecTpn

a p h ji- (Ha n p . T o j i y o j i - )

cyjiijjOHCKe

KHcejiHHe

c j i y w e 3a aaKHJioBan>e 4>eH0.aa. KaKO c e cnpaBJba aHMexHJicyjitJiaT? EjieraHTHo

cpeacTBO

3a

Me™;ioBaH>e

o a KacHHjHx norjiaBJba h c k o p h c t h t h eiiojieTpH

3a OBy

c y Bpjio n o c T o j a H e

(jieHojia Je AHa30MeTaH,

ko]h he ce y

jeaHOM

CBpxy.

MaxepHje,

Koa K o j n x j e peaKuHOHa

cnocoôHOCT

6 e H 3 o a o B o r j e 3 r p a y n o p e i j e f o y c a (jjeHOJioM 3 H 3 t h o o n a a a . A j i K H j m e r p y n e c y B p a o MBpcTO Be3aHe.

H e M o r y a a c e y a a j b e a j i K a a n j a M a , a MHHepaaHuM KHceawHaMa T e n Ha b h u i o ]

nepaiypH

(y 3 a i o n j b e H o j

ueBu).

CpeacTBO

Koje

j e a ^ y M H H H j y M x ^ o p n a , k o ] h p e a r y j e npeMa oboJ C 6 H 5 • O • C H 3 + AICI3

ce najqeuihe

ynoTpeöaaßa

tcm-

3a pa3;iaraH>e

jeaHamiHH: > C6H50A1C12 + Cl

CH3

l

3H20 CgH5OH +A1(0H)3 + CaMO

ce

ajiHjiexap

! !

0 - C H

npn

2

3arpeBaH>y

- C H = C H

H30Mepn3yje /

2

\/ aoK

x

—Il

\/

eTpH eHOJia > C = C — ,

HeMajy OBy

y

2HC1

ajiHJi^eHOJi

(Claisen):

O) H CH2 • CH = CH2

ocoÔHHy.

R OR HapoiHTo

je

HHTepecaHTHa

y

HOBHje

BpeMe

oTKpHBeHa

ajiHcjiaTCKHx e i a p a ) , a a c e aejcTBOM M e i a a H o r n a T p n j y M a pa3Jia>Ky

o c o Ô H H a ' (¡leHOJieTpa (a h

(Ziegíer, Schorigin), 13*

Ha n p . :

OpraHCKO-npenapamBHH .neo

196

C6H5OCH3 +

2Na

->

C6H5ONa +

NaCH3

OA cyncTHTyHcaHHx (J)eHO./ieTapa HaBemheino aMHHo-AepHBaTe 3HH30Jia (A H H 3 H A H H) H (JjeHeTo^a ($eHeTHAHH). OHH ce AOÖHjajy a^iKH^oBaibeM HHTp0(J)eH0^a H HaKHaAHOM peAyKunjoM HHTpo-rpyne. o-HHTPOAHH30JIA

A^iKa^Ha p e a y K U H j a

BOAH ( n a o KOA HHTPOÖCH-

30Jia) xHÄpa3o-jeÄHH>eiby, K o j e c e ö c h s h a h h c k h m ÖH(J)eHH^6a3y (CTP.

Oa

6

Ba>K.aH M e l j y n p o A y K T 3a n . i a ß e

y

a30-Ö0je

153).

THH" H

„äh8hh3hähh",

npeMeiiiTajeM npeBOAH

p-$eHeTHÄHHa

ce

H3BOA6

no3H3TH aHTHimpeTHKyM

(I) H C^ARNA MATEPHJA „ ^ Y J I U H H "

C

2

0 - < ^

I /

— NH • CO • GHS

MeTHJiOBaHH POÄHHX

e KOHCTHTy0Apel)HB3ifce

n p a c y T H e y jeAHOM MOJieKy^iy.

MeTOAa,

na

H6C20eroBa n30Mepa; a^KajiHe cojih 6 h ä b k ^ c TaKoije Mopa^e na 6yny x h h o HÄHor THna. MeljyTHM m - X H H O H H cy y ueaoj apoMaTCKoj xeMiijn Heno3HaTH. Äajbe, nocToje joui MHoni npiiMepH cynciaHUH Koje npn CTBapan>y conn aoÔHjy 3aTBopeHHjy 6ojy, a npw weMy je TpaHccjJopMamija y TayTOMepuH x h h o h iicKa.yqeH.1. Tano cy ceKyHAapHe c o j i h

HfyTOMpKor aiiTpaxHapoxHHOHa upBeHe nao KpB (VIII, 6):

198

OpraHCKo-npenapaTHBHH .neo

/\ IJ

OH

ONa

X Y N Y N / ' I ONa Kao KpB upBeHa co

i OH , »yTOMpKo jeflHH>eibe

Ha]3aa cy TaKotje h ajwajiHe cojih npocTor ({¡eHoaa TaMHHje oöojeHe oä caMor cj)eHOJia. Oße MHH>eHHue ce jiojiyme cyöjeKTHBHO He Mory ympflUTH, Beh caMO HcnHTHBaiteM ancopnuHje y yjiTpaBHOJieTHoj CBeuiocTH. Flpn TOMe ce noKa3ajio jia ce ancopnmija HaTpnjyM(j)eHOJiaTa aajieKO BHiiie noMepa Ka bhâahbom .nejiy cneKTpa, Hero ancopnmija cjioöoÄHor aBa BHÄJbHBy npoMeHy K a 3aTBopeHH]eM T O H y , y obom cjiywajy oä 6e36ojHor Ka «e jeaHor H-axoMa H y3 HCTOBpeMeHO n o M e p a i t e ABOcTpyKe Bese. Taico M ö w e Äa ce yTBp.au, aa npn 6p0M0Bafby aueTona, Koje ce noKa3ajio Kao MOHOMoaeKyjicKa peaKunja, He cTyna y peaKUHjy HopMaJiHH KeTO-o6jiHK, Beh TayTOMepHH enoJiHHOÖJIHK, KOjn

y

HeMepjbHBO

MaJIOj KOHIieHTpaUHjH CTOJH y paBHOTe>KH Ca KeTO-OÖJIHKOM H

K0jn ce TOKOM peaKUHje cTajrno CTBapa. MoHOMOJieKyjicKH KapaKiep peaKUHje ce noKa3yje y TOMe, UITO ce BpeMeHCKH TOK peaKUHje I M ö w e aa Mepn, AOK peaKunja eHOjia ca 6POMOM (II) T E I E NEMEPJBHBO BCJIHKOM 6P3HH0M

(Lapworth).

ü,aKJie HMaMO jeaHa'uiHe: Br,

CH

3

-CO-CH

->

3

C H 3 . C = CH„

I

-->

OH

CH3 • CBr — C H

II

3

Br

OH

—HBr

> FIoTceTHMo MeTaJiHor

ce

CH3 • C O • CH2Br

oßfle, aa aueTOH, a H aueTajiAexna, npejia3H y OTcycTBy Boae, aejHJIH joui 6ojbe n o M o h y

HaTpnjyM-

rioKpeTJbHBOCT BOÄOHHicoBor aTOMa Be3aHor 3a C-aTOM, Kojn je cyceaaH C =

O - rpynu,

CTBOM

HaTpHjyMa

(y3

BoaoHHKa)

pa3BHjau,e

„e n o JI a T"

spjio PEAKTHBHH

aMH.na, y

na

np.

CH2 = C —

CH3

ONa

IIITO je y c j i o ß

joui HeKe

eHOJiHH OÖJIHK

3a npejia3 y

c e a K o c y 3a Taj HCTH C - a T O M

Be3aHe

yrjiaBHOM He3acuheHe rpyne. OBO je cjiyiaj KOA aueTcnp-

aKTHBHpajyhe,

heTHor ecTpa, KOA Kojer r p y n a — C O O R MexaHH3aM

noBehaßa

c HHT e 3 e

BpuiH TaKaB yTHuaj.

aueTcupheTHor

ecTpa.

n p e Hero UITO npef^eMO

Ha TayTOMepHe OAHOce KOA aueTCHpheTHor ecTpa, n0Tpe6H0 je a a yKpaTKO H3JIO>KHMO MexaHH3aM

iteroBor

cTBapau>a,

KojH

no«HBa ynpaBO Ha npHHUHny THBHa

MeTHJiHa

rpyna

je

aeuennjaMa

a JI A o JI H e

aAHpa

6HO npeAMeT >KHBe a n c K y c H j e .

K o n A e H 3 a u H j e.

Ha KapöoHHJi,

PeaKuuja

iloiiiTO ce npu TOMe peaK-

TO H y cjiyiajy CHpheTHor ecTpa paAH ce y

OCHOBH o aAHpaH>y y CMHCJiy jeAHaraHe. OR RO2C — CH3

OR

I + C — CHS

ROOC — CH2

I — C —

H O CßaKaKo

OBAe

jaKo

cMaaeHa

peanuHOHa

ijeH>y c ajiAexHAHMa H KeTOHHMa,

CH3

I OH cnocoöHocT Kap6oHHJiHe

H MeTHjme

rpyne, y nope-

H3HCKyje y i e u i h e ajiKajiHor MeTajia, KOJH je y CTaH>y Aa

n p e ß e A e ecTap y 3 pa3BHjaK>e BOAOHHKa y eHOJiaT Ha np. R O — C = I ONa

CH2.

206

OpraHCKO-npenapaTHBHH

VI, 8

jieo

CMaTpa ce na OBa] eHOJiaT M ö w e aa a n c o c y j e He caMO npeMa 1 ( R O — C =

CH.,)

0 +

Na+,,

Beh

H

npeMa

II

[RO — C — CH2]

—

+

Na

aa

H

+

„M e 3 o M e p H O r *

npeno

II O HacTaJe

oßjiHKa II

aanuHja.

T e o p n j H paaeHue TO 3HaiH, aa

I l o KjiacHiHoj

ecTapeHOJiai

je

T.iyTOMepan ca MeTajioopraHCKHM je,nHH>eH>eM RO—C =

CH2

— — >

RO — C

ONa

—CH2Na

O

H « a j e OBaj cnocoöaH 3a a a m i H j y Ha C O - r p y n y n p y r o r MOJieKy.ua ecTpa. Taaa c e y 3 H3jBaj a f t e ajiKoxojia cTBapa HaTpujyMOB aepHBaT

a u e i a i c a p h e T H o r

ecipa:

OR

I

R 0 2 C — CH„ — C — CH3

RO2C — CH =

C — CH3

I

I

ONa OßAKO TaKotje Kojw

cxBaiaH>e

OMoryhaßa,

He

HHM

Mo>Ke

na

Tona

ONa

peaKUHje

HMa

npeÄHocT

HAß

apyrHM

TeopnjaMa,

na

c e oöjaciiH e c i a p c x a KOH,neH3auHja ca HCKHM napTHepoM

ce

eH0JiH3npa,

Tano Ha np. KOH,neH3auHja

(¡uiyopena

ca

jep

OHO

peaKUHje, oK-caji-

e c i p o i i : CO • C02R

.

\ / \ + i i

y

i

HcupriHa ÄHCKycHja o OBOM n m a i t y B.

KH>H3H

Eistert-a,

(Y

— -

A

\ / \ i l

Ha ejieKTpoHCKO-TeopnjcKoj ÖCHOBH Hajia3ii c e y

T a u t o m e r i e und M e s o m e r i e ,

S a m m l u n g e h e m . und c h e m . - t e c h n .

Vor-

träge, H3Äatt>e F . E n k e , 1938. KOHAEH3AUHJA H3Meljy e c i p a H KeTOHa T e q e HA HCTH HAIHH. M3 Äßa Mo.neKyjia e c i p a n o c T a j y KETOHA

ß-Ä H K e T o H H.

JE«HH>eH>A, C6H5

YnoTpeöa

yonime

ecTpa

ecipn

6HJIO na OH p e a r y j e ca ÄpyrHM e c i p o M CO — CH3

H -f- C • OR

ß-K e T O K H c e j i H H e ,

MpaBJfce KHcejiHHe BOÄH ÄO

+ Na >

H3 ecTpa H

OKCHMEIAIEH-

6HJIO ca KCTOHOM:

H C6H5 • C O • CH2 • C • OR +

O

H

ONa

ZiÌ?^

C6H5 • C O • C H = C — ONa HaipnjyMOB nepHBaT oKCHMeTHfleHaueTO(})eHOHa

T e » K . a 3a eHOJiH3npaH>eM j e HapoiHTO jano H3pa)KeHa KOÄ 4>opMHJi-rpyne y ß - n o j i o w a j y . H H i p a i i o j i e K y j C K a aaHnHHCKe

H

nHMeJiHHCKe

CKHX KHCEJIHHA

K0HfleH3aunja

KHcejiHHe,

naje

e c i p a ÄHKapöoHCKHx KHcejiHHa,

ecTpe

UHKJHIHHX

pena

ß-K e T o K a p 6 o H-

(Dieckmann):

CH2 \

Q C'HH

DH, C H ,

CH2

CH2

CH — C O

\

COOR

COOR

ecTap aaHnHHCKe KHcejiHHe

+

ROH

\ COOR e e r a p uHwioneHTaHOHKapöoHCKe KHcejiHHe

VI, 8

H eHOjiH E c T a p hn^HÖapHe

KHcejiHHe

KHcejinne K0HÄeH3yje c e

Hncy

6eH30JHMa,

cyKUHHHJiohHJiHÖapHe

Baeyer-a

ecTap). B h ä h p a a o B e

o

KOJ'H 6 a 3 H p a j y Ha OBOJ CHHTe3H.

caMO e c i p w opraHCKiix KticejuiHa, Kojn c e j e a H H e c a eHOJiaTHMa K d O H a h e c T a p a

exe mh

a 3 o THe

ecTap

(l,4-ÄHKeioxeKcaMeTH^eH-2,5-ÄHKap6oHCKH

x m p o r e H O B a H H M npeMa

y

207

,CHnie3e

aueicnpheTHor

KKcejiHHe.

Ä H H> e ft a,

aaje

riocTynaK

npHHUHimja;iHO n c T e

R •CO •a n a

+

ecTpa",

Beh

KOJH BOÄH ÄO

TaKotje

ecipn

h

H 3 O H H T p O 3 O-

h

H H T p o-j e-

npoiiyKTe:

N • OC2H3

R • CO • CH„ • N • O C 2 H 5

°

ONa R •CO - CH =

>

a B o i a i c i e

H aci-

N

+

HOC2H5

ONa CBanaKO ix a K0HAeH3aunja aJiKHJiHHTpHTa H ajiKHJiHHTpaxa Hiije T a K O - o n u i T a Kao peaKUHja B a t a

aueTCHpheTHor

aci-

eetpa.

H3BeaeHa

HHTpo6eH3HJiUHjaHH.ua

CH2-rpyna

öeH3H^unjaHHjia j e ocTaJia

K o H C T H T y u H j a XHjipa3HHOM, .eHo^a, K o j a j e

pacTBapa

H a T p n j y M 0 B 0 r

npenapaniBaH

ß-K a p ö o H C K H X

a u e x c H p h e i H H

öHcy^ttiHTOM H a p y r u M

peaKUHjy;

je

CHHTe3a

npHMep

3a

OBy

npaßa i e p n -

peaKunjy.

„peaKTHBHa" 3 ö o r c y c e a c T B a r p y n a C 6 H S H C N .

e c x a p a

K a o npHMep H 3 a 6 p a h e M o KHce^y

PaHHje

ecTap.

Kiiceiitua OH p e a r y j e

H ß-Ä H K e T O H a.

Kao KÒTOH c a ijjeHHfl-

peareHCHMa n a K e T o n e ; c a p y r e

c T p a H e OH n o K a 3 y j e

c e y aJiKajinjaMa h a a j e c a cjiepHXJiopHAOM

öojeHy

peaKUHjy

KapaKTepiicTHiHa h 3 a ( j j e n o j i e . M3 OBor Ä B o j a K o r noHamaH>a paHHje c e H3Beo

3 a K j b y q a K , .na j e OH HJIH IHCT KCTOH, HJIH IHCT eHOJi H Äa c e n p e j i a 3 j e Ä H o r oôJiHKa y oôjamftaBao CTpyKType

yTHuajeM

ynoipeÖJbenor

pa3jacHHjio j e npaBo

heTHH e c T a p a a w p a Ha x j i a a n o

peaKTHBa. Teic KBaHTinaTHBHo

craite

noroAHHM ycjioBHMa, Ko^HiHHa

eHOJia,

KOJinmniy 6poi\ia,

peaKUHja, K o j a c e

TO 6HJIO H3Jio>KeHo KOÄ aueTOHa. C T o r a

y

aueicHpheiHOM

ecTpy.

Tano

HCTHTpucaH

npw-

Möwe

na c e c a p a c T B o p o M öpoMa o j i p c l j c i i o r TiiTpa KBaHTHTaTHBHo

caapwana

npyrn oaHoca

(K. Ii. Meyer, L. Knorr, 1 9 1 1 ) . A u e T c n p -

cTBapH

o r p a H H i e i i y

n n c y j e c a M o eHOJiHOM oöJiHKy, n a n o j e

HCTpa>KHBaH>e

pacTBop

nocjie

KpaTKor BpeMeHa T p o u m noHOBO 6poM, UITO 3H34h na c e x a n a y n>eMy noiioBO CTBapa e n o j i . M 3 T o r a c e MOIKC 3 a K J b y i n T H n a c e y p a c T B o p y H CHOJHB

OÖJIHK

paBHOTeJKe ÔHBa noA MeTHO T31H0CTH

noTpeÖHoj

h

nycTH

PacTBopa

HOBO

Aa

Ha

x^a^HO

IJIHKO

EHO^

CTBapa,

BpeMeHa

je

Aa

noHOBO

Kana

CBe

MetjycoÓHOj

6H

ce

Bpaha

p a B H o T e K H.

ycnocTaBJbafte

6p0M0M Tano e n o p o a a TO He CMeTa

ÄO,a,a

HCKO^HKO

npH^HHHO

6p30

äok

nomyHO

6oja,

^a

MO>Ke

OBe npn-

Be3ao

6H

y

ml aiieiûcupheîûHor ecïïipa paciüBopa (pepuxjiopuna

Kann

Kanjbe

upBeHO

h3

6poM;

o^Max

ce

TO

ce

eHO^

ce

mimesjia

^a

KeTO-eHOJiHe

oneT

nocjie

He no-

KpaTKor

^OÄ3TKOM

noHaBJba,

ápoM-aifemcupñeüiHu ecïïiap.

nocMaTpaK.e

pa3ÖJia>KeHa

(J)epH-eHOflaTa

nouiTo

oneT

nyTa

ónpere

oôojeite

paBHOTejKa,

TOJIHKO

He n p e B e ^ e

cyôjeKTHBHo

OKO 1/¡¡

Myhnaibe

ycnocTaBHJia

OBO

ecTap

y3

AOT^ie,

caj,a

ôpoMa.

aueTcnpheTHH OMoryhaBa

ce

KOJIHMHHH B C W ,

ßpoMHa Bona (1:10) Hume3He.

y

ycjioBHMa p a n a T H T p a u n j e

CBOK

KCTOHCKH

MeToae.

Ornefl: y

H a Ji a 3 e

aueTciiplieTHOr e c t p a

noÄ

oapean

AOK

HCKOce

Oßaj

caB

orjiea

TayTOMepHje.

OÄHOC y KojeM c e HA^a3e y paBHOTencn KCTOHCKH H eHOJiHH OÔAHK 33BHCH y BEFLHKOJ M e p a OÄ

n p n p o i e

p a c T B a p a n a ,

Kao UITO n o K a 3 y j e

OBa T a ô ^ H u a 3 a aueTCHpheTHH

pacTBapai

npou.

Boaa

0,4

eTH^ajiKoxo^ rjiauHjajma CHpheTHa KHce^HHa

eHo^a 12,0

.

.

.

5,7

6eH30fl

16,2

neTpo^eTap

46,4

ecrap:

208

OpraHCKO-npenapaTHBHH

H3Mel)y y n e u i h a

TayTOMepHHX M a i e p n j a

iiaTOM p a c T B a p a n y n o d o j H

aeo

y paBHOTe>KH h tbHXOBe

VI,

8

pacTB0pjbHB0CTH

y

( v a n ' t Hoff,

B a w a n OAHOC, KOJ'H c e H3pa>KaBa npocTOM je^HaMHHOM

Dlmroth):

C

c y KOHueHTpauHje,

Y

c-nyiajy

e c i a p J i a K i i i e p a c T B a p a y BOHH, Te^HH aueTCHpheTHH flecTH^OBaH,

Lg

Cb

L(,

L pacTB0p.i>HB0CTH 0 6 a H30Mepa,

BHCH o a p a c T B a p a ^ a .

CBOKe

Cg

aueTciipheTHor a enoJi-ccTap

eciap

cacrojn

3naTHo j e 6 o r a r n j n

a H b,

ecipa aaia

G j e KOHCTaHTa

Ta6;mua

y neipojieipy,

c e o.n 9 2 , 5 %

y eHOJiy,

K o j a He 3 a j i a c e KeTO-

noKa3yje,

IUTO H MIN>eHHue

KeTOHa

H 7,5%

noTBpijyjy.

eHo^a.

flpenapaT,

j e p eHOJiHH e c t a p 3 f i o r C B o j e HH>Ke Ta'iKe

J < j b y n a H j a H a j n p e H c n a p n H y TCIHOCTH c e IIOHOBO CTBapa. ORNEJJ:

n-coHe

oxjialjeHe ce

PacTBopH

ce

ox;ia,n,n c e

xiiapoKcufla,

HnaK

Beh

KOJ'H

jia3H

y

JiaKiue

Te>Ke

y

BO^H.

K.

je

H.

Terne

g ai}euicupheluHor

2,5 Jie^y

Kucejiune.

nocjie

enoji,

y

Ha

J\o6u')a

HeKOJiHKO

H

pacTBopJ£>HB

y

ce

pacTBop

ajin

M c i o i a "

TO

Ha

pa3flHiHTe HaiHHe, y

Keio-

no^eTKy

3axTeBa

ce

cMeuie

MoryhHOCT, TpHHHor

e c t a p

3aBHCH y

MOJKC

aa

ce

y

MHCTOM

ce

na

H3o;iyjy

npBOM p e a y

o a 6p3HHe TpaHccjjopMauHje jiaSHjiHHjer. npBH

nyT

flecMOTpdnHHX

CacBHM

(Clatsen,

1910).

Y

cayiajy

cyn-

HecHMe-

1896):

(C6H5CO)2 : C =

C OH

, j e 3 M o i p o n H j e "

CH3 y OHHM

cJiyqajeBHMa,

c e OHH p a 3 A B o j e .

MHoro6pojHH

c y n c T a H U H , K o j e j i a o e c a M o y H3pa3MTnjeM o 6 ^ H K y H c n o a a B a j y C B o j e

OTKpHBena c y y M e t j y B p e M e H y ;

CJIH^HH

(Knorr,

(Hantzsch,

c e y c n e j i o , a a c e H 3 0 a y j e KCTOHCKO, K a o h

H

r i o j a M T a y T O M e p H j e j e 3aMeH>eH nojMOM

TayTOMepHe o^Hoce,

npejiaMaH>a

H3pa>iyHa c a j i p w a j o 6 a o 6 ; i H K a

K o j H M a j e c a M o e K c n e p H M e n T a j i H a B e w T H H a o M o r y h n a a na

OAHOCH

nocToje

KOfl

O6JIHK y B e h o j KOAHIHHH. T e i H H n p e n a p a T OBa M a T e p w j a

H>HMa n p H n a a a

a i i e i H J i a u e i o B a ,

c e cacTOjH * o

6 E H 3 0 H J I - a u e T H J i a u e T 0 H a

3npaH>eM, « a

cjiywaje-

y C^O6OHHOM CTAAY o 6 a ofijiHKa HeKe TayTOMepHe

(C6H5CO)2 : CH • CO • CH3

Koa

paBHO-

(Knorr, K. H.

crafty

1 , 4 4 8 0 . 0,npeljHBaifceM n u a e K c a

HHTepnoJiaunjoM

A H S e u a o H J i a a e T o i i a

npi!Mepn

npe-

jeflWbeiba.

ao6Hjy

e n o J i H o jeflHHieHie y cTa6HjiHOM npHciajiHOM o 6 j M K y

y

H3_HBOJ'HO

no^oacaj

1 9 1 1 ) . T a K o l j e c e c OBHM c j i a w y p e a ^ f l T a T H Ao6HjeHH c n e K T p o c K o n c K H M n y i e M cTaHue,

ml

KOJ'H

norayHO

c e c n o p o y CBHM

na

20

MJieno,

c}>H3HHKe KOHCTaHTe c y cacBHM pa3JiHMHTe, TaKO Ha n p . HHjieKC n p e J i a M a a a

K e T O - e c T p a 3 a D 1 0 » H3HOCH 1 , 4 2 2 5 , 3a e H o j i - e c T a p paBHOTe>KHe

Kao

K o j e 0B,ne He MOweMo 6;iH>Ke a a yjia3HMO, y c n e j i o j e ; i a c e

H e n o j i a u e T C H p h e T H H

rt>nxoBe

Meyer).

n-pacuiBopa

Myhnaite

H TOTOBO

j03B0MBa

BHMa o n p e f l H c a n p i K a j eHOJia y p a c T B o p y TayTOMepHHX H

Y

ml

20 y3

3aMyheH

6p30

KaKO

y

zona

H36HCTPH.

BOAH,

KCTOH,

„6poMHa

ecuipa

HajeAHOM

ceKyH^H

pacTBopaH

Meyer-OBa1

0°

80%

H aueTCHpheTHH caMO

C6H5 • CO • C =

C -

OBfle

ecTap. eHOflHH

H3 eHOfla.

TOJIHKO j e j a n o H3paiKeHa

y o n u i T e n o c T o j a caMo K a o eHOJi.

je

KBTOHCKH

T e w f t a 3 a CHOJIHoSAHK j e

Heno3HaT,

CH3

I I H3C — CO OH H MepHjH. (J)aTCKHM peaKunjH 1

Koa

(JieHOJia,

eHo^

ce

eHO^HMa. ca

no

Kao

H y OBOM

cBOMe

noTceTHheMo

epHXJiopHflOM,

A. 380, 212

(1911).

caynajy,

XCMHCKOM caMO

3HTHM

j e ^ B A c e MOIKS

noHamafty na

y CBSKOM

noayaapHocT

Ha p e a K U H j e ,

Koje

TOBOPHTH o n p a B o j norjiejiy

y KHceaoM Ha c ^ H q a H

TayTO-

npHKayqyje

napaKTepy, y HaiHH

ann-

6ojeHoj

Teny H Koje

cy

209

eHOJIH H eHOflH

„aKTHBHoiuhy"

npoy3poKOBaHe

n B o c i p y K e Be3e,

ca xa^oreHHMa, ca A30TACT0M

KHCCJIHHOM

ca apoMaTCKHM ÄHa3o-je.nHH>eH)HMa (KynjioBafte). „EHOJiHa npHpofla" (jieHOJia je Jiena noTBpaa 3a Hauie c x B a i a f t e KOHCTHTyunje OHa H3pa)KaBa MauiHHje.

Te)Kn>y

Oßue

6eH30Jia y cMHCjiy

npcieHa, aa

oap»H

6H 6HJIO OÄ HHTepeca

KeKUAe-TuJie-oBt

„apoMaTcKo a

NO3HAßATH joiii

cTaH>e,

HeaoöHjeH

KojH 6H ce Morao ynopejjHTH ca KCTOHCKHM OÖJIHKQM (jjeHOM CO

A

II CH

(jiopMyjie, no KOJOJ

Kao eHepi^eTCKH ajiH(¡)aTCKH

Hajcnpo-

KCTOH

(B)'

(A).

CO

I CH

... CH 2 C H = CH 2

CH Ca TayT0Mepnj0M KeTOHa H ana.tXHjia je Bp.no ycKo noBe3aHa TayTOMepnja a JI H(jtaicjiHi HHTpo-jejiHHjeH.a. H OB«e jeAHOM HeyTpajwoM oö.iHKy oaroßapa KticejiH O6JIHK, T3B. OCI-O6JIHK

(Hanizsch)'.

—C=0 ¡ — C — H ! KeTOH

0=N=0 I —C—H I npaBo HHTpo-jeflHH>eH>e

-C —OH II — C

0=N —OH II — C

eHOJi

ocz-HHTpo-jeüHH>eH.e

¡

y norjiejiy ocoöHHa, nojaBe npeMeunafta h peaKUHOHHX OAHOca Mome ce jeAHOCTaBHo yKa3a-JH Ha OHO, UITO je Bell KOÄ KeT0-eH0.ua peqeHO. BpoMHa MCTO.ua H OBue ÄO3B0Ji,aBa jia eibe (yn>p) H Kao jiaßHJWO KpHCTajino acr'-HHTpo-je,HHH>eH>e (Hanizsch):

CgH5

CH„ • N0 2 H C 6 H 5 • CH = N O O H

O n i e , n : M y h K a ce 2 — 3 g (peHUJinumpoMemana

ca 15 m / 2 n - H a ü i p u j y M -

xuApoKcuaa y niHpoKoj enpyßeTH. HeyTpajiHo HHTpo-jeAHft>eit>e ycjieA CBoje HE3HATHE pacTBOpjbHBOCTH y B O A H JiaraHO he Aa ce TpaHctjjopMume Ha xjiaAHO, jj. Aa ce pacTBopn. (Y ajiK0X0JiH0M pacTBopy CTBapaity COAH HAe Bp^o 6p3o). 3arpeßajbeM he yjbe Aa ce pacTBopn 3a KpaTKO BpeMe. Kaj,a ce OBO A O R O A « , OHAa ce oxjiaAH, AOAa ce a./IK0X0JIH0M pacTBopy y MAJIOM nexapy HeK0^HK0 KOMaAnha JieAa, a n0T0M O A jeAHOM 20 ml 2ncyMüopne Kucemite. CJIOÖOAHH aci-cpemuiHumpoMemaH H3Aßaja ce y 6e3ÓOJ'HHM KpucTajiHHM naxyjbnuaMa, Koje ce OAMax oueAe, onepy B O A O M H npecyjy Ha IVIHHH. PaAehn 6p30, M O » e jeAaH A G O npenapaTa Aa ce npeKpncTaAnnie H3 jimor 6eH3una (y3 AOAaTaK HCKOJIMKO 3pHa KajinjyMxHApoKCHAa). M a ^ a npoöa ce pacTBopn y Majio amoxojia H AOAa Kan FeClx-pacUiBopa.

ü p y r o j Behoj ce

a.iKOxo^Hor pacTBopa ópoMa; OABHjajy ce HeraTHBHO K O A npenapaT. ripaKTHKyM opraHCKe xeMHje

AOAA

y3

XJIA^EFTE, H C K O ^ H K O K A N N XJIAAHOR

6poM he Aa ce o6e36ojn. Oße peaKijHje 4)EHH;IHHTP0ME'RAHa, Kojw CMO jxoöann Kao 14

210

VI, 8

OpraHCKo-npenapaTHBHH aeo OCT3T3K

HohH.

ac/-HHTpo-jeÄHffceH>a p a c T B o p n c e y

PacTBop

aKunjy

Hahn

Kao 36or Tora,

Tora

(pepuxjiopüaoM.

ca

craKJiy,

nocjie

uito uito

he

ce

HÄyher

h ocraBH

npeKo

Aa

cy

ce

npeTBopmin

y

yjbe.

tjieHHjiHHTpoMeTaHa MoiKe npHBpeMeHO a a c e a o ö n j e

caMo

My j e 6p3HHa n p e T B a p a a a M a j i a ; y p a B H O T e j K H H e n o c T o j n Kao K 0 M n 0 H e H T a .

y noipeöa aueicapt Cjio6oähh MajioHCKH e c T a p

HeMa 3HaKOBa

AaHa

bhäh aci-otmv.

ce

amoxony

hhth B e 3 y j e 6poM, hhth n o K a 3 y j e ö o j e H y p e A k o c e hckojihko 3 p H a u a oct3bh H a c a x a T H O M

3a

e c i p a

HMa KOHCTHTymijy Koja o a r o B a p a

chojihh o6.hhk

aa nocTojn

h MajioHCKor

i e i H o r

c

yoöHiajeHoj

h h t e 3 e. $opMyjiH;

/ O R ROOC — CH = ( Y

M n a K aejcTBOM

•

HaTpn-

\ O H jyMa Ha eTapcKH p a c T B o p CTBapa c e y 3 pa3BHjaH>e BoaoHHKa T3B. h a T*p h j y m-m a ji o h c k h xoaaTa. y

cnman

kojh

eHOJiaT r o p i f e e r T a y T O M e p n o r oö-iiHKa,

e_CTap,

TaKolje H a c T a j e Beh H3 e c T p a

h

aJiKO-

peaKUHjaMa o kojHMa h e ce OBae roBopHTH, HaTpHjyM-MajiOHCKH e c T a p j e n o r a y H o

HaTpujyM-aueTcupheTHOM e c T p y ,

koJh cmo

jih c e , a a ajiKHJixaaoreHHa

nycTH

obom

y

p a c M a T p a i t y y3eJiH Kao npHMep.

p e a r y j e ca HaTpnjyM-aueTCHpheTHHM e c T p o M ,

h e a a HacTaHe C-a.nKHJiaueTCHpheTHH e c T a p , a H e , K a o

uito 6h

a ß o r y ö a H3Mena. MoiKe a a c e

cyncTHTyHcaHH n p o a y K T . H e HacTaje aaKJie n p o c T a

to

c e oqeKHBaao, Ha K H c e o H H K y npeTiio-

CTaBH, a a h e y H a j n p e nacTajioM M0/ieKyjicK0M jeaHH>eH>y, a a c e x a j i o r e H j o H H 3 y j e h a a

ce

cjeÄHHH c a HaTpnjyMoM, aoK h e a.iKHJi-rpyna a a ce a a i i p a Ha a ß o c i p y K y BC3y. i l p o u e c n o w e a a c e y n o p e a n y H3BecH0M eMHeJiy ca a a H u n j o M H3C • C = CH • COOR 3 | O Na

Hcth tok

1,4:

H3C-C —CH II |

R Hai

>

O

COOR

+ Na Hai

R

y3Hiiia p e a K u n j a ca xjiopwaHMa KHcejiHHa.

HanpoTHB peaKunja aoBoan ao

aueTcnpheTiior

Q-a H H j i a e p H B a T a ,

aoK

ecTpa ca xJiopnaHMa KticeJiiiHa y

O-a j i K H J i a e p H B a T H

n n p h a h h y

Mory a a c e a o ö w j y caMo

HHanpeKTHo n p e K o a u e T a n a (cTp. 116) y 3 H3aßajaH>e a;iKoxojia ( C i a i s e n ) . HSC • C • CH2 / HsCO

\

COOR

OCH3

CH • COOR

M o r y a a c e TpaHCtfopMHuiy n o a

c e a o ß n j a j y C-H30MepH,

6 a p Koa

H3C • C =

+

HOCH3

I OCH3

h -auHJiaepHBaTH n e Kao uito j e

O-a^KHa-

>

O-auHJiaepHBaTa,

paHHje onwcaHO ( y n o p .

a e r n a ß a c e y 3 KaTajwTHiKo

VI,

ycjioBHMa, n o a KojHMa

2). HanpoTHB OBaJ n p e j i a 3 ,

aejcTBO „HBpcror Ka;iHjyMKap6oHaTa

y HHaH(f)epeHTHOM p a c T B a p a i y ( C i a i s e n ) , Ha n p . : HSC • C = CH • COOR

>

HgC • CO • CH • COOR

I O • CO • CH3

bhhh

AueTcnpheTHH ecTap

h

I CO • CH3

MaaoHCKH

ecTap,

koJh

cy jeaaHnyT

a-uKHJiOBaHH hjih

Ha y r j b e H H K y , n o u i T o c y jorn cnocoöHH 3a C T B a p a a e eHo^aTa, a 0 3 B 0 J b a ß a j y T a a a

aaKHJioBaH.e

hjih

a u H J i o B a f t e Ha

hctom

aunjioapyro

y r j b e H H K o ; o M aTOMy. T p y n e , Koje c e y B o a e M o r y

aa

6 y a y B p a o pa3JiHiHTe 3a o 6 a c T y n a a ; cHHTe3a Möwe a a c e H3Beae ca CBHMa c y n c r a H u a M a , K o j e c a a p a t e peaKTHBaH x a j i o r e H , aaKJie He caMo ca xajioreHOBaHHM yrjbOBoaoHHUHMa pnaHMa

KHcejiHHa.

yBotjeae

aHxajioreHOBaHHx

napac})HHa

CHHTe3y n p o c T H x yrjbeHHKOBnx npcTeHa (IV. H. Perhin), ROOC — CH =

/OR C< \ONa

+ B r C H 2 • C H 2 • C H 2 Br

y peaKunjy

je

noroaHo

h xjioh

3a

Ha n p . : ROOC — CH COOR | +NaBr C H 2 — CH2 • CH2Br

eHOJIH

H

211

eHOJIH

/ O R > R O O C — C=C( I \ONa C H 2 — C H 2 — CH 2 Br

> ROOC

COOR I c — CH2 I I CH2 — CH2

+

NaBr

UHK^oöyTaHÄHKapöoHCKa KHcejiHHa M o r y h H O C T , a a ce TaKO narpaljeHH n p o a y K T H M o r y jiaKO npeBecTH y npocTHja je.unH>etba, aaje joui

jeaHO aajbe B3>KHO npenMyhcTBO

cHHTe3H n o M o h y

àueTCHpheTHor H Ma-

jiOHCKor ecTpa. OcoôHHy MajioHCKe KHcejiHHe, aa npH Tonjbefcy HcnyuiTa C 0 2 H npejia3H y c n p h e T H y KHcejiHHy, npwnHcyjeMO TOMe, aa yrjbeHHK HHje y CTaity m BeiKe Äße KapôoKCHJiHe r p y n e . O ß y ocoöHHy HMajy H CBe cyncTyncaHe canoHHtJïHKauHjoM ripHMep : K H C

e il

KHceJiHHe, Koje M o r y aa ce a o ô n j y

M a JI o U c K e

o a r o B a p a j y h n x ecTapa. Thmc ce CHHTe3a MHorwx n p o a y n a T a ynpomhaßa. CHHTe3a

ca

a3onponH»6poMHioM

aaje

H30BajiepHjaHCKy

y.

H H

JeÄHO aajbe KapöoKCHJiHe

ynpoinhaBafte

rpyne

(aoôHjafte

peaKiiHonor npoayKTa cacTojn ce y H3aßajaH>y

UHKJioóyiaHa

apyre

H3 ecTpa ÄHKapöOHCKe KHcenHHe, KOJH

CMO paHHje opMy.iiHcaJiH). MeTHfleHCKa rpyna y aueTcnpheTHOM ecrpy CTojH y Be3H ca — C O • C H 3 H — C O O R . aueTCHpheTHa

CjioßoÄHa jiHHe

H

pacna.ua

ce Beh

OBa, HaiiMe Ha a i i e i o H CHHTC30M,

H C02.

HCTO noHamajy,

MHHepajiHHM C02,

KHcejiHHa

join je

nafte nocTojaHa oa MajioHCKe KHce-

pa3ÖJia)KeHHM

Hamie,

nacíale

KHce/iHHaMa

pa3jiarajfaa, Koje ce 03HaHaBa

HCTH

H a i H H Kao

H

flouiTo ce CBH aepuBaTH àueTCHpheTHor ecTpa, aoÖHjeHH

Kao

aueTCHphenie KHce^Hiie canoi&icjHiKauHjoM ca

pas-naacy

MOMy y pacTBopy, Ha npHHUHnnjejiHO

ao

ce

cnoHTaHo,

pacnaaatte, na np.:

KCTOHCKO

H3C • C = CH COOR + HoCCl COOR I

ano ce 3arpeßajy, ryöehn

M o r y h n x aepHBaTa aueTOHa, n o M o h y OBor

CBHX

>- HSC • CO • CH • COOR

"

I

ONa

CH2 • COOR >-

CH3 • CO • CH2

CH2 • C O O H +

C0

2

+2

ROH

JieByjiHHCKa KHccjiHHa JaKHM ajiKajiHjaMa, MOJieKyji aueTCHpheTHe KHcejinne, KOJ'H HacTaje canoHH e H > a . Tano ce H M a 33MHCJIHTH, Aa ce y pacTBopy eiapa y KOHBaaoH

ueHTp0B3H0j c y M n o p H o j KHCCJIHHH Ha;ia3e OKCOHHjyMcyji(}>aTH, KOJ'H ce AejcTBOM BOAe XHApo-

JIHTH^KH PASJIAWY. Baeyer je 3a n H p o K c 0 H H j y M-COJIH Ha Taj HAMHH ymiHHo BepcBaTHOM HaBeAeHy cfopMyjiy, uiTo je TepunjapHy co, Koja Hacxaje aAHixnjoM MeTHjijoAHA"a Ha AHMeTHJinnpoH, Morao Aa npeBeAe ca aMOHHjaKOM y IIHPHAHHOB AepHBaT ca MeT0KCH-rpyn0M y p-no;io>Kajy.

-

u H

c —CH3

-

3

C—C

C —CH3

/

+2NH3H3C—C

N

\C

- C H

3

+ NH4J HC

CH

HC

\ C OfH

n H p O K c 0 H H j y MX JI O p H A

CH

\ C OfC H

HC

CH

\ C O C/H

3

jojiMeTH jai

3

2,6-AHiieTHJi4-MeTOKCHnHpHAHH

M a H T O U H j a H H , upBeHe H ruiaBe 6oje MHorHX UBeTOBa H nflOAOBa jecy TepuHjapHe oKCHHHjyM-cojiH, Koje ce H3BOAe H3 6 e H 3 o n i i p a H O J i a ( x p o M a n o i ) (/?. Will-

siatier, P. Korrcr, R. Robinson). CI / \ / I

0

\

C

H

HC. "

\/\C/ /

C H

/ V ° \ |

\/\

\

|

C

H + H2O

/

CH

CH

H OH 6eH3onHpaHoa 6eH3onnpH;iHjyMXJiopHA AHTOUHjaHH cy n y K 0 3 H i n BHiiieBajieHTHHX (JieHO^a H (JieHOJiHHX eTapa KojH y nnpaHOBOM npcTeHy Kao cyncTHTyeHTe HMajy XHApOKCHJiHy H $eHHJiHy rpyny. OHH Mory Aa ce cBeAy na Tpn THna a H T o u n j a H H A H H a . OH V

> / OH CH neJiaprOHHflHHXJIOpHA

HO . OH CH UHjaHHAHHXJIOpHA

VII Ae^(j)HHHjiHHtxjiopHfl H e s a ce n p o y i e B a w H H THHa,

KaiexHHa

caflp>KH

joui

h

HajBaiKHHja

uHjaHHflHHa,

BOA

a30T0B0ji0HHqHHX

peaKimja

MHorocTpyKe

rjiejiHMTa.

k b e p u e-

ftHaBoje,nHH>eH>a

je^Híteita,

Tj. aMOHHjaKa

koj'h j o u i HMajy boaohhk Be3aH 3a a30T, jecTe peanunja

ceiHHOM. Taque

O H - r p y n y y 03HaqeHOM n o j i o w a j y .

H3Met)y

jyieojiHHa.

Y flepHBaia,

jeAHy

6HJbH0-H3H0Ji0iiiKH oíihoch

VII.

koa

213

flHa3ojeaHH.eiba

ílopea

nojaBe

KOje

ripn

TOMe

Hacrajy,

3a

Tpeóa

h cbhx H>eroBHX

a30T3CT0M

nocMaTpa™

,k h-

ca onuiTe

CTBapan>a cojih, Koje 3eh HcpMajiHO Teqe koa caMor aMOHHjaKa h

ajiiiíjiaTCKHX aMHHa,

peaKTHBHa

flBOCTpyKa

Be3a

y

N = O

a30TacT0j KHcejiHHH n r p a

Bpjio BaiKHy y j i o r y .

HajnpocTHjn cnyiaj AHMeTH^aMHH

h m 3 m o koa

cenynjapnax

aMHHa.

rpaAH Hajnpe iiHMeTHJiaMOHHjyMHHTpHT, npn noBHineHoj TeMnepaiypn

HinpaMOJieKyjiCKH ce ajmpa AHMeTHJiaMHH Ha ABocTpyKy Be3y íiBajafte sojie Haciaje

a u h n o b a h> e

Tj. CTBapaH>e

a30TacTe KHcejiHHe h y3

+

—

(CH 3 ) 2 N H + H N 0 2

» (CH3)2NH2 • N O 2

> (CH 3 ),N - N - O H I oh

• (CH3)2N • N O

OBaj npouec n0TnyH0

m-

h h t p o 3 a m a h a.

oaroBapa jeflHOM ApyroM

+

H2O

auHJioBafty, Ha n p . ohom, koa Kojer

ce CTBapa aueTH^-j.epHBaT H3 aMOHHjyMaueTaTa. CaMO OBfle peaKiuija 3axTeBa BHiuy TeMi;epaTypy, 3 6 o r HeflOBOJbHe peaKUHOHe

enocoóHOCTH C =

O

— ¿iBocTpyKe Be3e y

cwpheTHOj

KHCejIHHH.

OH (CH 3 ) 2 N H

+

_

OH

I C —

O =

I - ->. (CH 3 ) 2 N — C — I OH

CH3

— • (CH 3 ) 2 N - c - c h 3 + II o AHMeTHJiaueTaMHA

CH3 •

h2o

BejiHKa 6p3HHa ecTepnijjHKauHje a30TacTe KHcejiiiHe, Koja y tom n o r j i e a y co6om CBe apyre KHcejiHHe, o6jauiH>aBa ce 6 a m Ha hcth HaqHH ( c T p . CHS • CH„OH

-(- O = N — O H

C H

3

ocraBJha 3a

122).

CH3 • C H „ -

0 \ >N — H O /

- C H

2

— 0 - N

=

OH

0

eTHJIHHTpHT

IlpeHeceMO na ony npeTCTaBy Ha peaKUHjy ca a m o h h j a k o m, 6nhe jacno aa aiiHJinpoayKT kojh ce CTBapa Ha Toruio, Mopa na ce pacnaaHe Ha a30T h BOiiy. HO\ H3N

+

O = N —

OH

> h

2

>N n /

+ N =

— O H

N

+

2 H

2

0

floTnyHO to hcto Ba>KH 3a n p H m a p h e ajiHíjiaTCKe aMHHe H3C

NH2

+

O =

N — OH

OH -> ( H 3 C • N H — N - O H ) > N = N

+

H„C

OH

(HSC • N =

NOH)

214

OpraácKO-npenapaTHBHH .neo

VII, 1

O ApyroM MetjynponyKTy, KOJ'H j e CTaBJbeH y 3arpaay, i H j e cy COJIH no3HaTe, 3 H 3 M O , «a noA ycflOBHMa cBora nocTojaH>a Mopa Aa ce pacnajme Ha a30T H aJiKoxon. KOA npocTHx npHMapHHX aMHHa ajimjiaTCKor pena He Ao.na3H AaKae no cTBapaH>a flHa3o-jeflHH>eH)a, jep p e a K i w j a , KojoM OHH nocTajy, T e i e Te« Ha OHOJ TCMnepaiypH Ha Kojoj ce OHH pa3apajy. A J I H peaKUHOHa CIIOCOÔHOCT N H 2 - r p y n e Mowe Aa ce noBeha npncycTBOM je^He cyceAHe KapSoHHJiHe rpyne. Zl0Jia3HM0 Ha c j i y n a j e c T a p a a - a M H H 0 K a p 6 0 H C K H X K H c e j i H H a H cc-a M H H o K e T o H a. R^HKOKoaecTap naje ce Beh Ha X M A H O na AHa3 0 T y j e ; AHa30jeAHH>eH>e, noje ce He pacnaaa no« OBHM y c j i o B H M a , cTa6H.nH3yje ce, y 3 H3ABajaH>e H 2 0 H npejia3H y i H a s o c H p h e r H H eciap: RO • C • C H 2 • N H „ + II O -H,0

RO • C • C H 2 N H \ II >N — OH O H O/

O = N — OH

RO • C • C H 2 • N O

u

„

j

RO • C • C H — N

« \N

HON

f

O

AHa30CHpheTHH

ecTap

K O A peaKijHje npHMapHHX a p o M a T C K H X aMHHa c a a30TacT0M KHCCJIHHOM HeoieKHBaHO je TO, Ra npn HHJKOj TeMnepaTypH AHa30-jeAHH>eH>e, H a c í a l o 6e3 cyMH>e npeiia Beh noKa3aHoj cxeMH, n p e j i a 3 H y 6a3y noA ACJ'CTBOM KHcejiHHe, Koja je npHcyTHa y peaKUHOHOM pacTBopy, i H j a ce co, A H a 3 o H H j y M-C O Aoówja nao npoAyKT AHa30T0BaH>a.

C6H5 NH2 + O = N • O H

> CgH5 • N = N O H

HCI

+ -> C 6 H 5 • N = N +

H20

C! OBAe ce cpeheMO ca jeAHOM HaponmoM OCOÓHHOM apoMaTCKHX jeAHH>eH>a. flna30HHjyM-cojin HHcy no3Haio y aaH(J)aTCKOM peay, jep THII aHHJiHHa - C = C - lie Mowe na nocTojH. NH2 Hwje HCKJbyneHO, Aa ce FJiHKOKOJieciap TaKO Jiano AHa30Tyje Ha 0CH0By TayioMepHor npeMeiiiTafta ROC — C H „ ROC = C H II I " "» I I O NH2 OH NH2 A J I H H Taaa n o TOMe IHTO KOA aJiHtfiaTCKHX AHa3o-jeAHH>eita ce ÓHTHa pa3JiHKa H3Mefjy o6a peAa. 3a

caaa

He ajiKHfl — HHX

ocoÓHHa.

MaTCKHX j e 3 r p a Tpe6a

c e Mopa

ÜPHMHTH K a o

MO)Ke Aa 3 a a e r a CnniaH pa

.asoT

Bpme, K a o

jeAHe A H a 3 o - r p y n e

UITO h e

n o T c e T H T H , na KOA c a M H x aMHHa a p o M a T C K o OA

A Hanízsch-a,

Die

ce

aTOM, K o j H j e 3 a a e r a

n o B e h a B a AejcTBOM a j i K H J i - r p y n a . Aejio

KacHHje ( I X ,

H 30

noKa3ara

BHuie

apo-

COJIH). 3 a T H M

ce

j e 3 r p o j a K o CMaH>yje 6 a 3 H q H o c T , AOK c e OHa Leipzig,

g

1921,

Koje j e npepaAHo

Reddelien.

flMA30JEflMHbEHbA flHaaoMeTaH1

HHTp030MeTHJiKap6aMKfl. 126)

7)

ajin 6a3-

3 a C T y A H j y x e M H j e AHa3o-jeAHH>eH>a n p e n o p y i y j e c e H 3 B p c H o

Diazoverbindungen,

1.

(cTp.

ywHHH HOCHOueM j a K o

Be3aH (Kap60HHjyM0Be

A. A J l H f c A T C K A

xjiopuaa2

6a3HHX ocofiHHa cacrojH

H e o 6 j a u i H > H B a iHH>eHHua, A a a p o M a T C K o j e 3 r p o —

Be3aHH

yTHuaj

yrjheHHKOB

neMa

PacTBop

KajiujyMqujaHama-

20

(crp.

g 110)

MemujiaMOHujyMy

1 2 0 mi

BOfle

1 E. A. Werner Chem. Soc. 115, 1098 (1919); F. Arndi H ]. Amende, Z. A n g . 43, 444 (1930). 2 3 a AoôHjafte Behe KOJiHMHHe M e T H J i a M O H H j y M x a o p H f l a cjiywH OBaj jeBTHH noctynaK ( B r o c h e t H Cambter, Bl, (3) 13, 5 3 3 (1895)): 2 5 0 g aMOHujyMXAopufiti ca 570 g

VII, 1 3arpeBa

ce

pacTBOp XOAHO y

40

1/4

caia

oxjiaflH

Ha

Ha

CNPEMJBEHH Böse;

ml

MEXAHHIKO

y

nocjie

empoM.

narube

Koje

xohe

ce

H3flBaja y

JL[a 6u

ce

HSKOH

na

ce

H3ÖerHe

20°.

pacTBop

Tana

ce

2

y3

xjiaijeite

BOÄOM

;ie,neHOM

OTNPNJIHKE

m

JICÄOM

H

y H e c e ce y

npHHoc o x j i a ^ H c e p a c T B o p y C M e i u H KpaTKor CTajaita N P O I X E A H H Tajior o n e p e Tone

ce

ce

na

caTa

Ha

124°.

Ha

ILPHHOC

20

g.

MeTHJiaMHHa, p a n « c e Ha cjienehH Hamm:

Kanjbe 100

g nuMemujicyjupama

TeMnepaiypa

BoneHOM

p a n « najbe Kao LUTO j e Beh paHHje onHcaHO. iieTHJiaMOHHjyMXJiopHnH ( F .

Pa^H

npeBOljeiba

MeWujiicapffaMUMa y

M3JIHM

y

KOJIHQHHE

npH

KynaTHJiy,

TOMe

ílpiiHoc 20—22 g

y

y 3 xnaljeibe ca

He Tpeöa na n p e l j e

KyBa joui 15 MHHyra, nona

nona pacTBop on 40

ynorpeöH

oiieī

nocjie cyiueita

Ä B O C T P Y K E

H

mcemne.

g KamjyMì^ijaHama y 80 ml Bone H KyBa FIOHOBO 2 0 MHHyTa. Tana c e g HampujyMHumpuma y 70 ml Bone H oHna oxjianw. XaanaH MajiHM oöpomiMa y cMeiuy on 40 g Kom{. cymnopne Kucenune u 170 g

50

H

npeT-

g HaïïipujyMHtinipuwa

20

2 5 % - H e cyMüopne

XJIA^HE

cnpaBJbaH>e

nycTH

3arpeBa

OÄ

ce

oue^H

ÄO^a

KpHCTajiHHHHHHM n a x y j b n u a M a ,

CMeuiOM jiena H COJIH H y 3 CH3)KHO M y h n a a e ; npeKO

npoKyBa,

noBehao

KpncT3JiH

ml kohVJ. aMOHiijoKa

BpeMe

MemujinapâaMum

pacTBop

onepe

NPEKPACTAJIHIUE

—15°,

KpaTKo

nyc™

ml

100

onepaunje,

CßeTJio-jKyTH

AKO 135

Ha

ce

pacTBopy

cMeuiy

3aBpiiieHe

H COJIH

ce

OXJIAIJEHH

MENIATE,

Mewujiamoxojia.

Ta^a

Ta^a

TAKO^E

BAKYYIUEKCHKATOPY,

JIEßA

60—80°,

0°,

oxjialjeHy

Huwp030-jeAUH}eH>e, ce

215

AjiH({)aTCKa ÄHa3ojeaHH>eH>a

oneT pacTBop Jiena H

3H3tho j e MaftH Hero npw

Arndt).

y

flna30M6T3H

oópouHMa y

100

yHOce

ml

ce

10

g

eWpa,

HHCTOT

ce noÄ^iHje 30 ml jano oxJiaijeHor 4 0 % - H o r pacTBopa

HUüip030-

ncnoA KOFa

icajiujyMxuapoKCuaa.

r i p o u e c pa3JiaraK>a ce H3BOÄH y ep^eHMajepy i i m p o K o r rpjia nofl KanejioM. HenpecraHo rioc^e

Mopa aa ce Myhrca H Äa ce TeMriepaTypa

5—10

eTapcKH 35°/0-nor

MHHyTa

pacTBop,

peaKijHja

cya

ce

ce

Hcnepe

3aBpmaBa; ca

HewTO

OAP^aBa Ha

o^Jinje

ce

TaiwHO

eTpa, a eulapcm

+5°. >KyTH

pacMBop

pacmBopa eHie

g.

penyKyje

BHuiKOM (JjopMannexHna: OH H

2

C:0 +

HNH2

->

H2C — NH2

->.H

3

C

—NH

2

r i p u TOMe ce (JjopMannexHn (Kao xnnpaT) n e x n n p o r e H y j e y MpaBJby KHcejiHHy H C 0 2 . noBehanH

ce

KOJiHiHHa

HHjyMXJIOpHna.

annexana, TO c e Ha c n a ï a H HAQHH noJia3H n o

TPHMETHNAMO-

216

OpraHCKo-npenapaTJiBHH aeo

Aua30MewaHa

cyiiiH

xuapoKcuaa.

y

VII, 1

oko 3 qaca ca hêko^hko Maanx

mjiujyM-

KOMa^nha

npenapaT Hehe o.HMax &a ce ynoTpeÔH, pacTBop

caynajy

ce CT3BH y Majiy cTanaeHy 6 o u y y3aHor rpjia y Kojy ce yHece HaTpHjyM, KaKo

je

to

PacTBop

onHcaHo

Ana30MeTaHa

koä

eTpa

(cTp.

77)

ce äpjkh

bhlug

Äana,

h

nyBa am

Ha xJia^HOM

MecTy.

ce HnaK orammo,

nano

jiaraHO, pa3^a»e y3 H3,n,BajaH>e a30Ta. C T o r a He CMe n,a ce HBpcTO 3anyuiH 6oua y Kojoj ce qyßa pacTBop. HHTp030MeTH^Kap6aMHÄ, MeHa, ana

je Hajôojbe « a

HyBaH Ha x/iajHO,

ce ^Ha30MeTaH

nocTojaH je ayme Bpe-

npwnpeMH caMO y ohoj kojih-

i h h h , Koja je TpeHyTHO nOTpeßpa. A H a 3 0 M e i a n je Bpjio OTpoBaH rac, HtyTe 6oje, Taine KJBynaH>a -24°; 3a npenapaTHBHe CBpxe cnpaBjba ce caino y pacrBopy. Y cjioöoähom CTaity je eKcn;io3HBaH. Beh npw jiecTHflauHjH xohe KgTKaÄ aa eKcnaoimpa; dora 6yan onpe3aH! Kao HHamjiepeHTHH pacTBapaHH Mory ochm eTpa TaKolje za ce ynoTpeöe a j i K o x o j i H , 6 e h 30 ji h n e i p o j e i a p , 3a KpaTKO BpeMe h a u e t o h. OApe^HBafte [Marshall Memana

h Aeree,

KOHueHTpaunje

pacTBopa

(1/20) pa3ÔJiaaceH' ancoJiyTHHM eïïipoM,

Kait>e h xJiaijeifee JießOM y n/5 ewapcicu ce AOÖHje

TaKO uiTO ce y MepHH

ÄHasoMeTaHa

A j i h k b o t 3 h _a.ee> pacwBopa

B . 43, 2524 (1910)].

aua3o-

nycTH ce aa Tene y3 Myh-

pacmßop

öeH3oeße

Kucemm.

ôajioH oä 50 ml pacTBOpH

Oßaj

1,22 g Haj-

HHcraje 6eH3oeBe KHceJiHHe y ancoayTHOM e T p y ; OHa M o p a 6 h t h y BHuiKy npeMa ,HHa30MeTaHy, i i i t o ce iio3Haje no TOMe, aaBafta

Mopa na

pa3BHja N 2 h u i t o

pacTBop

l u t o ce CBe äo Kpaja äooeraHe

6e36ojaH.

BHiuaK

6eH3oeBe KHce^HHe THTpuine ce ca n/10 N a O H . ripenapaT cnpaBjbeH Ha noroaaH HaiHH, nano je oB^e onwcaHO, MHoro ce yncrrpeóibaaa 3a HayqHe pajiOBe, jep oh OMoryhaßa eaeraHTHo, rjiaTKo MeTHJioBaH>e cKynwx KHcejiHHa h (fceHOJia. A j i K o i o j i a e OH-r p y n e nao h a m h h h npaKTHWHo ce He MeTHjiyjy. O MeTOÄH MeTH^oBaaa a j i K o x o J i a ca ana30MeTaH0M bhäh H. Meerwein h G. Hinz, A. 484, 1 (1930). OnieflH:

PacTBopH

ce ^ 2 — 3 g

(e raca h äok ce pacTBop He

oôojH cjiaôo acyTo. fla MeTaHa

6h ce BH^e^o a a y cHna

ce hcko^hko

o 6 o j e h o m pacTBopy KanH

y

HMa BHinaK

enpyBeTy h y H>y yHece

uiTajinh, 3aMyqeH npeTXOAHO y rjiaifujamy

cupheïïiHy

Kucemny;

ma30-

eraKJieHH ofliuax Ha-

CTaje pa3BHjaft>e raca. PeaKUHOHH ce npoayKTH, noerce HcnapaBant>a pacTBapaqa^npeiHiiihaBajy öhjio AecTH^auHjoM, HJiH ano cy ^BpcTH KpHCTajiH3auHjoM. H3BpiiiH or^e^ ca HeKHM (J) e h o Ji o M, KojH nocTojH y jia6opaTopnjH h HcnwTaj npapò^y HacTa^ior

MeraaeTpa.

Ha hcth

HaqnH ypa^H ca K a p ô o u c K H M

khcë-

n. h h a m a (p-TOJiyHJiHOM KHceauHOM, (jjeHH^cnpheTHOM, uhmcthom, oKca^HOM, Tepe4)TajiHOM, cajimiHjiHOM HT^.).

AjiH(t)aTCKa

VII, 1

n o c r o j e (j)eHOJiH,

Kojn ;iaraHO

217

flHa30jeÄHH>eiba

p e a r y j y ca

flHa30Meiaii0M.

Y

TOM c j i y i a j y

noMeiuajy

ce OHH ca BHUIKOM AHa30MeiaHa H OCIABE ce na c r o j e BHIIIC natia y 6OUH Ha KOjy c e craBH KANW^APHA ueB. ÄHa30MeiaH,

HajjeAHOCTaBHHje

ajiHcJjaTCKO nna3o-jeiiIIFT.eifce,

Hajnpe

ÄOÖHO

je

Ha cJie,nehH Ha'imi;

Pechmann1,

/OC2H3

/OC2H,

0 = C (

+ \C1

H.,N • C H 3 "

HO.NO

/OC„H5 0 = C< O N \ N - CH3

->0--=C< \NH

ecTap xnopMpaBJbe

CH.

MetiuiypeTaii

Hmp030Me-

x

KHCEJIHHE

THJIYPEIAH

/ N H 2 C ( ^ || +

KOH

c CI 2 + H „ N • N H 2 /

H

Kupfers.

Jia n p u M e i t y j y h H H30HHTpnjiiiy peaKUHjy npHMapHHX aMHHa Ha XH,npa-

~

N —NH,

H C ,'

2

N — N =

C =

||

"

aeh

j H a 3 0 M e i a H '

N - N H

"

-

HCC1

ÄHa30MeTaH j e nyxce BpeMeHa

C,

H C

/ N

L

->

~

H„C
eroBHM

MHoro-

ßpojHHM peaKUHjama (ca uHjaHOBöÄOHH'MOM KHCCJIHHOM, a n e m i e u o M , XHHOHOM HTÄ.) BHÄH y cneuwjajiHoj Beh

.nHTepaTypH.

noMeHyTO,

Kao

BastHy

cpeÄdBo

npenapaTHBHy

Ļa3oMcxaH Ha;ia3ii, nao UITO j e

npiiMeHy

3a MeTHJioBaibe, H a p o i m o 3a c|ieHOfle.

TaKo, Äa ce o6a aTOMa a30Ta H3ü.Bajajy nao n o c i a j i e cnoöoÄHe, B e 3 y j e ce H

eJieMemapHH

a3or, a na

h OR.

N H

2

11 +

cr

O H ca H>HMa p e a r y j e o 6 e Bajienue, Koje c y

H H O • C0H5

>

HJCF

+

\ O

N2

• CGHS

a II H 3 O A A JI H ej) a i c K a BafteM

jma30-jeÄHH>eH>a

xHÄpa30Ha

HOBAH>eM y

(Curtius,

(ca H g O )

Siaudinger)

I

CTora,

a

H

H3 pa3jiMqnTnx

Ä p y r a oTBopeHa (JjopMyjia (Angeli, A30MeiaH (Ha

CH3 • N =

- 2 H

|

/ N

+2H

|

\ N

N — NHO

I

rac,

H OÖPATHO npejia3e OHH XHjipore-

XH.npa30He: C =

3HBaH

Mory Äa ce a o C n j y naiKJbHBHM iiexHAporeHo-

||

ÄpyrHx

pa3jiora

Thiele),

Hanine ^ . C =

N • CH3,

Kojn

ftHMa

ce N =

n p H n n c y j e y HOBHje BpeMe N.

ojiroßapa a306eH30Jiy, 6e36ojaH j e eiccnjio-

HHJKOJ* TeMneparypw CBETJIO - w y i a TCHHOCT),

UHjoM 0 Ä r 0 B a p a j y h e r xnjpa3HHa ( x a i p a ä O M e i a H )

Thiele,

noja ce ÄOÖHja a e x n a p o r e H a B. 42, 2575 (1909).

O c t a j i e peaKUHje ajiHiJiaTCKHX ;INA3O-JE.AHIFCEH>a BHHH KOÄ a n a 3 o c H p h e T H o r 1

B. 28, 855 (1895).

2

Hanizsch

H Lehmann,

B. 35, 897

MeTHJiH30ÄHa30taTa n o c i a j e npeMa Thiele-Y 3

B. 45, 505 (1912).

4

y

(1902).

TaKoije H3

(Äoayme

ecTpa.

CTepe0H30MepH0r)

( A . 376, 253 ( 1 9 1 0 ) ) ÄHa30MeTan.

paHHjHM H3MH.HMa j e onHcano npenapaiHBHO H3BohjeH>e LLluiayaumepOBe

MeToae.

218 2. a)

OpraHCKO-npenapaTHBHH

fleo

flHaBocHpiïeTHH

ecTap

VII,

2

rjiHKOKOJiecTap-xflopxHflpaT1, H 5 C 2 0 0 C • CHS • NH 2 • HCl

94 g xnopcuphemne Kucemne ( 1 M O J Í ) pacTBopn ce y 50 ml BORG H nycTH ce A3 T e i e y3 MyhKan>e Ha 15° y 1 JiHTap KOHaeHTpoBaHor aMOHujam ( D , 0,913). BajiOH ce O C T 3 B H aa CTojH 3anyiiieH 24 naca. I I O T O M ce y 3AejiH HcnapH B C ^ H K H BHiuaK aMOHHjaK3 Ha n^aMeHy (p3An noA KanejiOM), H K3A ce fteroB Mnpnc CKopo BHiue He oceha, 3 3 C H T H ce ca 100 ml KOHueHTpoBaHe cone tcucemne, M jacHO KHcejio 3arpeje Ha KOHro H Ta^a HcnapaBa — npeA Kpaj C T a j i H O M e i i i a j y h H — Ha oTBopeHOM nasMeHy CBe AOTJie, AOK jeAH3 npo6a, Koja je. Beh Ha Tormo n o ^ y i B p c T a CBeivioHcyTa Maca, nomyHO He OHBpCHe npw oxjia^enby. PeryjiHcaaeM n;iaMeHa H HHTCH3HBHHM MemaibeM Mopa Aa ce H36erHe nperpeBaibe y OBOM CTaÄHjyMy. Bpejia Maca ce 3a BpeMe xjial]eH>a Aoöpo HCHTHH T p ^ a a e M y nopiieJiaHCKOM aßaHy H joui npncyTHa Bo^a npe ecTepH(j)HK0Ban>3 yAajbH Ha Taj HaqHH, UJTO ce cnpamena CMema aMOHujyMXJiopu^a H rnimoKOJi-xjiopxuApaïïia 3arpeBa noA CMa&eHHM npHTHCKOM y óa^oHy npaTKor BpaTa, KOJ'H ce CT3BH y KJbyuaJio B O A 6 H O KynaTHJio. flocjie 4 caTa Maca ce joui jeAHOM cnpaiiiH H HacTaBH 3arpeBaft.e noA CMaiteHHM Ü P H T H C K O M jorn 3 caTa y yjbaHOM KynaTH^y Ha 1 1 5 ° . T A A A ce cacBHM cyBH npax coHe CMeiue2 npoKyßa ca 3 5 0 ml aücojiyíüHor amoxojia y öa.iOHy 3a ecTepH4)HKOBAFT,e (CJI. 4 6 . C T p . 8 8 ) ca öpymeHHM rpjiOM N ycnpaßjbeHHM K O H A C H 3aTopoM. (IlpcTeH BOACHor KynaTH^a Ha KOMe J I O K H öa^ioH, Tpeóa Aa ce O Ö J I O Ä H TK3HHH0M 3Öor yAap3ib3 np« Kjbyqsfty); y KJbyqsJiy CMeiuy Y B O A H ce jaKa CTpyja cyBor BOAOHUKXJIOPUAO. CBe A O K H 3 K0HAeH33T0pa He no^He Aa H3^a3H rycTa Mawa. IlpeKHHe ce caAa A O B O A HCl, O C T 3 B H joui HCKOJIHKO C 3 T H A3 KyB3 y Bpeo pacTBop oÁBojn ueljeHjeM Kpo3 Hyq O A aMonujyMxjiopum; Hcnepe ce Asa nyTa BpejiHM ancojiyTHHM a;iK0X0;i0M. H3 TpaTa npH oxjialjeiby HCKpHCT3JiHiue rjiuKoicojiecïïiap-xjiopxuapaïïi, KOJ'H ce H3KOH 12-q3C0BH0r crajaft>3 oABOjH ueijeibeM. npeKpHCTSJiHCSBaibeM H3 U J T O j e Moryhe Maii>e sncojiyTHor ajiK0X0/ia, — Herró HeuiTO aMOHHjyMx^opHA3 ocTaje Hep3CTB0peH0, CTora He Tpeöa y3eTn cyBHiiie 3 J I K O X O J I 3 — AOÔHj'a ce noTnyHO qncTa co. Tame Ana30C H P H E T H O R ecrpa MOJKÊ A3 ce ynoTpeön C H P O B H npoAyKT Aoópo ocymeH. RIPHHOC

je

5 0 — 6 0

OBÄE

OCHM umx

KOHUEHTPHCAIBEM

g.

MARAQHE

JIYACHHE

HJIH

AOA3TKOM

npHHoc Moxce A3 ce noBeha.

eïïipa

xoMoaora

HUNIER

onHcane

Hjie

aMexH.ua

HajjeÄHOCTaBHHje

MaH>e rjiaTKO,

( V , 7),

Sirecker-ona,

1

Hantzsch a Silberkad,

2

3a

CMerne

HÄYHH

COJIH.

ORNEA

cHHTe3e

n o c T o j e j o u i ÄBe; Kojy

B. 3 3 , 7 0

ÄOÖHJAITA

CC-aMHHOKHceJiHHe,

Koja

KOA

jeflHa Koja nojia3H OÄ n p B o r

CMO MH OB«e

nam

Kao

npenapaT

BH-

HÄyher (aamiHja

(1900).

XHíiypHe

KHCCJIHHC

ocTaBti

HCKOJIHKO

rpaMa

A^HiJ)aTCKa ÄHa3o]eÄHH>eH.a

219

aMOHHjyMunjaHaTa Ha h h t p h j i ) h MeTo^a MJiatjer Erlenmeyer-a,

koä Koje ce ajutexnn h h j k h

VII, 2

3a ÄBa C-aTOMa K0HÄeH3yje ca

xnnypHOM

khcgjihhom.

ripw TÖMe nodaje a, ß-He3acnheHa a-6 eH30HjiaMHH0 k ii c e ji n n a, Kojav ce aoöwja ce a-aMHHOKHce^HHa.

XHÄporeHyje; xhäpojihthmkhm pa3aaraH>eM 6eH30HJi-rpyne R • CO + H 2 C • C O O H H | N H COC6H5 >

• R

R • C H = C • COOH | N H • COC6H5

CH„ • CH • COOH + |

R • CH2 • CH COOH | N H • COC6H5

C6H5 • C O O H

nh2 Kanaß je 3Haiaj aMHHOKHcejiHHa 3a H3rpaÄH>y npoTeHHa? K o j e cy aMHHOKHceviHHe .no cajia n30Ji0BaHe npn Bapeay h KHcenoj xhäpojih3h öejiaHqeBHHa? OaBajaibe nojeÄHHHx a-aMHHOKHcejiHHa n o c m H i e ce ÄOHeKJie KBaHTHTaTHBHO no mctojih

E. Fischer-a

TaKo u i t o ce Kao r o p e

ecTepH(}>HKyjy h l u t o ce e c i p n

aMHHOKHcejiHHa

jejiaH

oä Ä p y r o r oaBoje cJipaKUHOHOM .necTHJiauHjoM noa CMäaeHUM uphthckom. CMaipa ce, aa c y nojeÄHHe aMHHOKHcejiHHe y MOJieKyjiy 6e;iaH>ieBHHa Be3aHe Ha aMHÄHH HanHH. 3a cHHTe3y T3B. nenTH,na E. Fischer je K0HaeH30Ba0 1 moji XJiopHÄa aMHHOKHcejiHHe ca 1 mojiom aMHHOKHce.iHHe, na np.: H 2 N • C H „ • COC1 +

H„N • CH • COOH I ch3

H 2 N • C H 2 • CO

NH • CH • COOH I ch3 r^HUHA-a^anHH

n o obom npHHUHny cy taKolje H3rpaljeHH BHCOKOMOJieKy^iCKH nojmnenTH.nH. KBaHTHTaTHBHO o,npetjHBaH>e aMHHOKHcejiHHa y pacTBopy: 1. n o pacTBopy. 2.

no

Van Slyke-y.

MepeaeM

Soerensen-y.

a30Ta, koJh

ce

pa3BHja

ca h h t p h t o m

y

khccjiom

KoHÄeH3auHja ca (jJopMajiaexHjioM h 3aTHM THTpaunja caaa ao-

BOJbHO jaKHX KHCeJIHHa 3. n o

Wlllstätler-Waldschmidt-y.

flnpeKTHOM

THtpauHjoM y ajiKajiHOM pacTBopy ca

n/10 pacTBopoM xHÄpoKCHAa h (JieHo^cjiTa^eHHa. AMHHOKHce;iHHe no CBojHM ocoöHHaMa h no paeTBopjbHBoeTH noKa3yjy Kapaiaep y H y TpamHjHx

ycneji

cojih;

HiHxoBor

y

boachom

aM xjiaAaH 3acnheH b o a c h h pacTBop o a , . 2 6 g T e x H . naüipiijyMHunipuiüa, a 3 8 t h m K a n a j y h n (ca nnneTOM) 4n-cyMüopHa mcemna, y a ä h b o MyhKan>e. H3AbojeHH wa3ocupheüiHu ecülap M y h K a i t e M ce pacTBopn y ropiteM e T a p c K O M jihhhhh

caojy.

flouiTO

cyMnopHe cyBHiue KHce^HHe

ce

y

He c y B H u i e

KHcejiHHe,

HcnycTH

KOHueHTpoBaHH h 33THM c e

ce

cnopoM

Ana30CHpheTHH

npoAy>KH

TeMny

ca

yHeJio

pacTBop,

b o a c h h

ecrap

KanaaeM

Aa

h3jiomcho

cyMnopHe

Kan 6h ce

no

20

ml

cTBopeHH

nan

He

AejcTBy

c a o ö o a h c

KHce^HHe y

jieBKy

3a OÄBajaH>e, nouiTO ce npeTxoAHO n0H0B0 AOAa e i a p . Oßa ce o n e p a n n j a o a B a j a f t a h n0H0BH0r AOAaßaita eTpa n0H0BH 5—6 nyTa. Ka^a Haj3aÄ pacTBop npecTaHe Aa ce 3aMyhyje, h a30TacTa k h C 6 j i h h 3 noqHs>e Aa ce pacTBapa y eTpy ca 3ejieHOM öojoM, npecTaHe ce ca KanaHbeM k h c c j i h h c h cjeAHfoeHH eTapcKH pacTBopn ce caAa MyhKajy ca Majio pacüiBOpa coae ( a o crajiHo upBeHor oöojeifca) a n0T0M jom ABa nyTa ca Majio BO^e. 3aTHM ce cyiun oko 1 / 2 caTa neiuhe MyhKajyhn ca Majio KajiiiujyMxjiopum, h HajßehH Aeo eTpa npeAecTHJiHiue H3 6anom 3a (JjpaKunOHHcafte 3anpeMHHe 2 5 0 ml ca b h c o k o nocTaBJbeHOM o a b o a h o m aeBH, Ha B O A e H O M KynaTH^y Koje He C M e Aa 6yAe 3arpejaHo B H i u e o a 40° h t o y n o ^ e T K y noA o ö h ^ h h m ü p k t h c k o m , a nocJieAita T p e h H H a noA CMaft>eHHM 1

Curilus,

J. pr. 38,

396, (1888);

IV.

Frankel,

Ztschr. physik. Chemie, 60,

202

(1907).

VII, 2

NPHTHCKOM1

HA

ecTap

y

öa^oHa.

ijHJby

npHKa3aH

je

je

ca Ä ß e

pyne,

Kao

Ha

ö a j i O H , KOJH c e

CJIHUH

xaaijeifee,

Koja

cyBHiue

Mopa

a AECTHJIANHOHH

Kao

Aoöpo

ce A3

nape

6ajiOH

B a K y y M y

H3

HCTOT

BOACHOM

napoM

pa3BHjaa>e

3a

qnjH

BOAOM,

Koja

Kannjiapy

ca

CBe AO r o p n > e

nape

ce

pery^Hiue

HBHue

yßyqe

ca^a

CT3BH

3arpeBa y

3Aejiy

BOAOM

H

OAPATABA

flua30cuphemHu

c a BOAOM y

45

60

mm.

33Top, 45°/l2

BpeMeHS

KynaTHJiy

an»

nocTojsH,

y g

CMeuiH

3a

(TeopncKH

ce

He T p e ö s

Aa

ce

iyB3

H aäoioBojioBHiHe

ETap

Ha K p a j y Ha 4 0 °

HHCT

npeAecTH-

H HAJ3AA

ce

( K p 3 T 3 K . KOHAeH-

xjia^eite!).

TaiKa

KJbyqaita

npenapaT

xepMeTHHKH

/I,Ha30CHpheTHH ecTap, KOJ'H j e 1888 ro,iHHe oTKpno Th. xnapa3HHa

cyrne

BaKyyMy

3 8 g).

eT-

CKH e K C T p a K T H

3arpejaHOM

AeCTHJiaUHj'OM y

HHCTH

20—25

ca

etap-

ce

X^SAHTH

ripimoc

H3MyhKa

p o M , a cjeAHH>eHH

icajiifujyM.xjiopuaoM.

Ha BOACHOM

peuHnneiiT, mm.

peuanH-

eKCTpaxyje

B O A e H a .

3a

OA

óapujyMxaapoKcuxa

qHiuheita

Ypeljaj

25°, OCTATKY ce A O A A 20 ml h npeAecTHjmuie AHa30CHpheTHH

HajBHiiie

TEMNEPATYPW

BOfle h 2 g qßpcTor

H

221

Ajin(})aTCKa ÄHa3oJejiHH>eH.a

je

Ay>Ke

3aTBOpeH. 6HO j e npeixoflHHK

Curtius,

KHCCJIHHC.

Xiiapa3HH je Hajnpe aoönjeH XHflpoJiimmKHM pa3JiaranbeM . 6 H c-A > i a 3 0 c n p h e i H e KHceiHHe",

Oßa,

Kao

Teipa3HH-aepHBaT,

nocTaje

H3 ÄHasocHpheTifor

ecTpa HCTOBpe-

MeHOM canoHHfjjHKamijoM ecTapcKe r p y n e noa (KaiajiHTHHKHM) aejcTBOM j a n i i x a^Ka^Hja, Kao aJiKa-ima co, n p i i qeMy ce Äßa- MOJieKy;ia jejiHOCTaBHO 3ajeÄH0 B e » y . ¿N = N KOOC -

CH N =

,N — N H CH

COOK

->• K O O C •

W

\ c HN -

• COOK

W

KyBaibeM ca KiicejiHHaMa ce 6nc-aHa30cnpheTHa KiicejiHHa pa3./ia5Ke Ha ii

oKcajiHy 1

K n c e JI H i i y .

A o m i u j e onncana onepaunja q m i i h e f t a aaje Bpjio MHCT npenapaT, KanaB j e noTpeöaH

3a oflpetjHBafte H-KOHueHTpauHje no Bredig-y neuiTo

XHjpa3HH

O TOMe ce öJiHwe MOJKe aa Halje y B. 41^ 3161 (1908).

cjiaÖHjii OÄ OHOT Kojn ce nocTHMce

H Fränkel-y

(BHÄH cTp. 222). OpHHoc je unaK

naa ce BaKyyM-aecTH;iauHja

oAMax

npeay3Me.

222

OpraHCKO-npenapatHBHH a e o

TaKo^e

XHÄpa3HCHpheTHH

ecTap,

XHapa30H

VII, 1

ecipa

nwoKCHjme

KHCCJIHHC

ROOC • C = N • N H 2 , KOJ'H nocTaje XHaporeHOBaiteM aHasocHpheraor ecipa, XHapoflittoM, H ÄejCTBOM KHceJiHHa aaje X H a p a ä H H , r j i i i o K c H j i a y

K H c e j m H y H ajiKoxoji.

BeoMa pa3HOBpcHe peaKunje ÄHa3ocHpheTHor ecTpa, Kao H CBHX npocTHx ajim{>aTCKHX ÄHa30-jeÄHH.eH>a pa36naiKeHHM

oaJMKyjy ce aaöHflHOM Be30M a30Ta. Pa3JiaraH>e ce KaTa^HTHHKH

KHcejiHHaMa H TO TaKO, aa je 6p3HHa

pa3Jiarati>a anpeKTHO

y6p3aoa

nponopuHOHajiHa

KOHueHtpauHjii BOÄOHHIHHX joHa, Koja Mo>Ke Ha Taj HaqHH aa ce Mepw Koa KHcejiHHa

3Haior auHflmcTa ( B r e d i g , Frankel, flocjie

H3ÄBajaH.a a30Ta

Heno-

Ztschr. physik. Chemie, 60, 202 (1907)).

octaje

HesacHheHH

ociataK

/

ROOC CH, KOJH ce y pa3.iH-

HHTHM npaömiMa aajbe Metta. Y npHcycTBy Boae aanpajy ce H>eHe KOMnoHeHTe y ecrap r n h-

KOJiHe K H C G J I H H C , HCl ce aanpa y e c i a p x j i o p c u p h e T H e K H c e j i H E e , joa y e c T a p a n j o a c H p h e T H e K H c e a H H e , Ha aHajior HSHHH KapßoncKe KHcejiHHe, anKOXOJIH, ajiaexHan, aMHtin, N 0 2 H TpHcJjeHHjiMeTHji. AKO Heaociaje aaeHa, Kao IHTO je a i y i a j Koa TepMHCKor pa3JiaraH>a, oHaa ce aßa paaHKajia cjeaHH>yjy y e c T a p i j ) y m a p H e K H c e JI H

,H,a 6 h c e yTHijaj

R O O C • CH = CH

COOR

H-joHa

KOHueHTpauHje

Ha

6p3nHy

j i a r a i t a 6 a p KBajiHTaTHBHO y n o 3 H a o , p a c T B o p n c e o k o 0 , 5 ml ecwpa

y Maao 5 0 % - H o r

ajiuoxojia,

h y o 6 a ÄOAa no 1 ml n/10

coue

p a c T B o p c e n o ^ e ^ H Ha Äßa Maaa n e x a p a mcemne

h n//0 cuphemne

c e y MeH3ypn cnpaBH H3 rjiauHjajiHe C H p h e r a e

tcucemne

(Koja

khcs.thhc).

3aTHM ce eTapcKOM p a c T B o p y ecTpa Ao^a HeuiTO ewapcicor joaa.

pa3-

wasocupheüiHor

paciüBopa

P a c T B o p ce o6e36ojH TCK riocne. n3BecHor BpeMeHa y 3 pa3Bujan>e

a3oma.

riopea HaBeaeHHx peaKiwja aHa30CHpheTHH e c i a p urpa yjiory jorn Koa MHoroöpojHHx KOHji.eH3auHja, KOÄ KOJ'HX a30T ocTaje y McuieKyjiy, Kao UITO je aaminja HG aueTHaeHCKe H eTHJieHCKe aepHBaie. TaKO nocxaje Ha np. ca ecTpoM 4>yMapHe KHcejiHHe e c i a p n n p a H i p i i n p ö o E C K e Kucejimie: 3o CH

/

COOR

+

ROOC•CH

\

N

/N = N ROOC • CH R O O C ^ C — C — COOR H H

CH • COOR

Y pacnaaaay oBor Ha noBHmeHoj TeMnepaiypn cacTojw ce 3HaiajHa cHHie3a UHKJIQnponaHCKHX

aepHBaia

(Büchner)-.

H ROOC — C — N,

I

ROOC — C H +

>

ROOC — C - C — COOR H H

ROOC — CH

\ — CH — COOR

N2

Kojn Mory aa ce nojaBe y pa3JiHMHTHM cTepe0H30MepHHM oöjimiHMa, Koje ycjioßjbaBa paBaH npcTeHa. ripeMa

HCTOM npHHUHny

cnpheTHHM ecTpoM

(Buchner).

p e a r y j e Ha noBHmeHoj

TeMnepaiypn

6 e H 3 o n ca ana3o-

ApoMatcKa flna30jeflmbeika

VII, 3

I

+ || >CH • COOR

\/ Kofl

-» I

^>CH • COOR + N2

\ /

N /

223

H /

ecTap

nceyaotjjeHMCHpheTHe khccjihhc

0B0r HHTepecaHTHor peaKUwoHor npoayKTa Mowe noA

H3BecHHW ycJioBHMa npcTeH

UHKJionponana aa ce H30MepH3yje y jiBa npaBua:

CH, • COOR

f\H\

V

CH • COOR

>

f

\H2 ^ • COOR.

'ecTap ({)eHHJiCHpherae Knee^HHe

/

ecTap u H K J i o x e n i a TpHeHKapCoHCKe KHCeJIHHO iI.iia30cnpheTHH rinpasojia

eciap

ce

KOHaeH3yje

ca

R02C CHN„ + H2C(C02C2H=)2 O peauuHjama drazine oa

MajioucKitM

ecipovi

y

(Bertho u Mussel, A . 4 5 7 , ' 2 7 8 (1927,):

>

ajimjjaTCKHX flHa3oje,nHHJeH>a

/y

aepHBaT

4-o

k c h-

.N-NH 2

1

ROX C3 4 5 \ c = c • co 2 c 2 h 5 . OH aeTa:Minje ce HaJia3H y kh>h3h D i e

Hy-

H. Wieland-a, S t u t t g a r t 1913, c i p 97 h ziajbe.

5. APOMATCKA AHA30-JEAHft>EH>A 3. 3na30T0Banbe aHHJiHHa. OeHoji, jo^6eH3on, deHBOJi H3 aHHJiHHa. HsoMepHja ,HHa3o-je,HHffeeH>a a) H a h h h a o 6 h j a it a p a c T B o p a j H a 3 0 H H j y M O B e c o j h , y 150 ml BOfle, noja ce Ha;ia3H y oShihom nexapy oa jeAHor JiHTpa h;ih y cxaKJieHOM nexapy AeSejmx 3HA0Ba, y-nnje ce, y3 Ao6po Meuiaite, 30 ml KOHijeHTpoBaHe cyMuopne

mcejiane

h y Bpe^y pa36jia)KeHy KHceJiHHy 30 g

floiuTO ce 3aTHM Majio no Majio yHece 250 g Jie^a, n y c ™ ce, Aa y TaKoije h cnojba aeAOM (a;iH He KaKBOM CMeuiOM 3a xflaijefbe!) xJiaijeHH pacTBop aHUJiuiicyjicpauia, H3 Kojer ce a^jihmhhho CBeme

^ecTHJioBaHor

anujiuna.

H3flBojH^a TeuiKO pacTBopJbHBa co, nocreneHo Hcreqe H3 jieBKa 3a Kanaite

pacTBop oa 22 g wulpujyM-HUMpunia y 90 ml BOAe; npn TOMe ce Mopa Ao6po MernaTH. KaAa n/iaBHa kojihhhh3 HHTpHTa oyAe AOAana, OH.ua ce ca xaprajoM H3T0n^beH0M CKpo6oBaHHM Ka^HjyM-joAHAOM1 HcnHTyje, a s HMa

BHLUKa asouiacuie

mcejiune.

flpn

Towe

ce

Mopa HMaTH Ha yMy, Aa

KoMaawh CKpo6a, BejiHHHHe rpaxa, ,no6po cnpauueH, y H e c e ce y 200 ml KJbyqaae h y3 Ao6po Meuiaite KpaTKO BpeMe nponyBa. n o xjiai)eH>y flo^a ce KOMaaHh KajmjyMjoflHAa B e . n H m i e c o i H B a pacTBopeH y Ma.no Boae h tom cMernoM Harone a y r a i K e , orapHjiHKe 3 cm u m p o K e TpaKe oji xapTHje 3a ueljeH>e, n o j e ce 33THM Ha 3aTerHyTOM noHonuy o c i a B e 1

BOjie

a a ce o c y m e y npocTopnjaMa, y KojHMa HeMa y B a 3 j y x y KHceanx napa. n o cymeH>y HceKy

ce

ayraiKe

Tpaxe h lyBajy

y

3aiB0peH0M cyay.

OpraHCKo-npenapaTHBHH aeo

224 ripea

peanunje

npaj

CMaifcH —

— Aaiuie

KaA

n p o u e c Teqe c n o p o ;

MHHyTa, npe Hero neT MHHyTa

ce

VII, 3

KOHueHTpauHja

c e npeAy3Me HcnHTHBaite.

LUTO

MOHíe jom y B e n

peaKTHBa

3aTO c e Mopa yBeic npHieKaTH AOKa3aTH

A K O

cjiodoAHa

c e Haj3aA

a30TacTa

MHOTO

HCKOJIHKO

noaie

H

KHcejiHHa y

He3HaTHHM KOflH^HHaMa, ,nna30T0BaHie je 3aBpiueHo; aHmiHH-cyjicJjaT Mopao je, pa3yMe c e , npehH n o m y H O y y3Me ce

aifemaffia;

Mana.

KojH ce,

KaKBe

c e AOAa

CTBopn y KOHaeHTpoBaHoj conoj HeKOJiHKO

PHTH

J\op.a na joj

HacTajie

ycneA

OBor

H

mcenmu.

COJIU.

COJIH,

R-mcemne

HJIH

Mua3o-aMuno-

^e^a, y

AOAaTH

HHTCHSHBHO

,,KyiuioBaH>a u ,

3HBaHje AHa30HHjyM0Be

c e c a ^ a HeK0JiHK0 n0H0B0

3 a ApyrH oivieA T p e ó a

pacTBopy

OBOM

KOMa^nha

HCKOJIHKO

p-Ha

na npeiaa TOMe

ua;iOM

Ma;io

pa-

pacTBoBHiiiKy

AOÓHJEHOR

oprancm

6oje

cpeACTBO 3a AOKa-

3a AOKa3HBait>e npHMapHor

apoMaTCKor aMHHa, OA Kojer c e npH paAy H noui;io. 6) C T B a p a i b e jyMOBe

(JieHOJia n p n K y ' B a i t y

pacTBopa

cnpaB^eHor

pacüiBopa

3a p e a K u w j e

B ) H r). B e h n p n

am30HujyMcyji(paüia,

a A p y r e A s e TpehHHe caqyBaTH

caMOM CTajan>y

He xjiaAH, pa3BHja ce nojiano ASOFFI.

pacTBopa, ano ce

BOAeHOM KynaTH^y, Koje ce OAp3KaBa y

BHjaK>e raca Majio napoM.

HcriHTa ce ÓPOMHOM

Aecra^aT ce 33CHTH

npeAecTH^Hiue

HS

KyxuwcKOM COJIU, BHiue icajiifujyMXJiopum Majior

AS

BOROM,

pacTBop ocyiiiH noMohy

(JjpaKUHOHor

M3JIOM

a i a 6 o M Kjbyiafby.

HCTepa ce CTBopeHH

CMHPHJIO,

HapciHHTO

j e 6ojbe H3BecTH p a ^ a r a ^ e Ha

AJIH

HeuiTO noBHiiieHÓj TeMnepaTypH ( 4 0 — 5 0 ° ) y craKJieHOM

AeHOM

A H a 3 0HH-

y n o T p e S a T H 3a OBy p e a K u a j y caMO je^Hy TpehHHy CBejKe

coJIh.

ipenon

óa^OHy Ha

FIOIIITO

ce pa3-

AHpeKTHO ca

BO-

-NH je caB eH)a cjioóoAHa MHHepajiHa KncenHHa, HeyTpajincaTH HaipHjyMaueTaTOM H TaKO C T B O P H T H caa6o KHce^a cpeflHHa, yc^oB, noA K O J H M ce CTBapa AHa30aMHH0jeAHH>eH>e. MHHepaaHe KHcejiHHe pa3Jia)Ky OBO jeaHH>eH>e Ha A H 8 3 0 H H j y M 0 B y c o H £ o a M H H a, Ha np.; C6H5 • N = N — N H

C0H5

2

^ ^

C 6 H 5 • N = N + HCI • H 2 N

CSH5

C1

flocTojH yocTaaoM H m3jih 6poj AHa30HHjyM0BHX coíh, KojH ce Beh y KHCejiOM pacTsopy Kynayjy ca ccncTBeHOM 6a30M, tano na np. /7!-4>eHHjieH.nHaMHH (B«3MapK0B0 MpKO).

VII, 3

ApoMaTCKa

225

Äna3ojeflHH>eH.a

ÄoAaBaH>e h h t p h t s n p « nHa30T0BaH>y KOHTpojinme c e xapTwjoM HaioriJbeHOM CKpoöoBaHHM KajiHjyM-jOÄHflOM; p.a 6 y j i e

iiito

je

xapTHja

Moryhe

Mopa

Mann.

Ha Kpajy

na nonjiaBH, ana BHiuaK HHTpma Tpeßa

T p e ó a HMaTH Ha yMy xia ÄHa30T0ßaH>e HHje joHCKa

peaKUHja, a a j e 3a H>y noipeöHo BpeMeHa h na c e , H a p o i m o npejt Kpäj, Mopa n p e HcnHTHBaita nenaTH HeKOJiHKO MHHyTa. TernKO pacTBopjbHBe cojih npHMapHHX apoMaTCKHx aMHHa Ä n a 3 o i y j y c e Ha i a j Haimi, IIITO c e CH3JKH0M MeuiajinuoM jipHœ y cycneH3HjH. B p j i o cjiaöe 6 a 3 e , jiHuu,

HHTpaHHjiHHH,

c e y TUM cJiyiajeBHMa BaHe

coHe

3axTeBajy

pacTBapa

KHcejiHHe,

33thm

3a

Hajnpe

CTBapaH.e

y

pa3ÖJia)KH

cojih

Kao

.na

ce

paciBa"paH>e

roBan

cyjitjiaT

H3jiB0jeH

cjioöoähh

y3

JieaoM ÄHpeKTHo ÄHa30Tyje.

aMHHH y KHceJioj

3aio

XJiafjefte neuom cnojba h Ha Taj

HCTOBpeMeHO

MecTO j e 3a n p e n o -

BpiriH y KOHueHTpoBaHoj cyMnopHoj KHce^HHH cycne.H3HjH,

c e yßeK 6 h t h cwrypaH, na ce npeTXOAHO

KHCejiHHe.

TaMaH Ä0B0JbH0j KOJiïmHHH Bpejie, KOHueHTpo-

HaqHH BehHHOM TemKO pacTBopjbHBy c o M3ÄBojn Äoöpo Ä H c n e p r o a a n y . pyny,

xajioreHaHH-

Behw BHuiaK

Ann

h Äo6po ÄHcnep-

c e HHKaa He cMejy ÄHa30T0BaTH

j e p o h h p e a r y j y h cyBHUie c n o p o ;

CTBopmia

Mopa

co.

HenocTojaHOCT ÄHa30HHjyM0BHX cojih HHje y -cbhm cjiyiajeBHMa HCTa; n o c T o j e Ha npkoä

B)

j 0 A Ö e H 3 0 J I

jyMcyjKpaiïia, y

ôa^OHy

OCT3BH Ha

OA

A3

6a;iOH

THJiy, ce

aepHBaTa

aHTpaxHHOHCKHx

Koja 1

CMeiija

craBH

Koje

(penoji

peHH JieBKa

3a

paiiHje BprHe

3a na npeKO

Be3ao

eTpa

Haj3aA

papTBop

noMohy

y3

xJiaijeifae

xaa^eifce

h

3arpeBa

y

224)

ml

20

BOAOM.

aoas

ce

BOAe H

Ca^a

ce

Ha BOACHOM

Kyna-

KOA o i i i T p e

cena-

C B e AOK

H

h3abojh

ce

joA6eH3oa

cyma

ca

hcko^hko

Ta^na

j oä h a

aaHUHOHHX

(V.

Ys

j e a h h. e a a

BOAeHor

BOAC

—

KcvmujyMXJiopiißa

189—190°.

BpejiHa

je

IlpHHOC

noMeHa

H>nxoBa

npeljy y opraHcne joÄHe aepHBaie

Meyer, Willgerodt).

xjiai)eK>e

ancopimnja.

oa

3pHua

KJbyqait>a

npoaynaTa

í e H H A j o A H A X J i o p H A .

npecTaHe

(cTp.

g icamjyMjomao.

15

He n p e c T a H e pasBujawe a3owa; j a n o HawpujyMxunpoKCuaoM — A a 6 H c e CTBO\oa6eH3on. c e H C T e p a BOACHOM n a p o M . r i o M o h y

Kjbyia,

—

jojoM

xjiopotpopMa.

paCWBOpa aUÜ30HU-

TpehHHH

OBOM n p e n a p a T y

HCKOAHKO n a c o B a

ACCTHJiauHjH.

xjiopHHX

oa

Ba3AyuiHO

—

apoMiTCKa

BajieHTHHM

3a

OhOJ'

HaMeiteHa

KOHueHrpoBaHHM

OABajatbe

6e3

a H H JI H H a .

ÔHJia

CTOJ'h

ijeB

yMepeHO

3aajiKa^Huie

H3

je

nmpa

/2

TaKBe cojih, Koje c e a a j y npeKpHCTaaHcaTH H3 Bpejie BOiie.

jieAOM

JlenH

uiMpna,

PacTBope

ce

yBOAH

kphcthjih

3

ce

h3

xjiopotpopMOM

onepy

b h ui e -

\on6eH3ona 6 o M Ô e xjiop, C B e «cyTe

6oje

noAg.

cnocoöHocT ca

rpaMa

oTBOpeHo

H

14—16

15

ml

AOK

He

y

oueAe

H Ha x a p T H j H

3a

ce ueljefee

o c y u i e na B a 3 A y x y . CI TaKO ÄoöHjeHH

ijieüHijojiHASJiopHA

C 6 H 5 JeH>a y

npii-

OKCHja c p e 6 p a ; o6a MOJieKy.na, K o j e c a A p w e j o ñ a ,

c j e f l H H > y j y ce y 3 H3flBajatt>e j o a a T a , < \

CgH5 • J = O + j0fl06eH30Ji nope«

NaOH

\ J — C6H5 QY

C6H5 • J • C0H5 • + NaJ0 3 . OH

>

nocTaJe H3 j0A0306eH30Jia HHTepMOJieKyjiciuiM AHcnponopunoHHcaH>eM

j0,a6eH30Jia:

JO + OJ • C 6 H 5

—•

C6H5 • J < f

C6H5J ,

^O CJIHIHO nao HITO ce a30TacTa KHcejiHHa AHCNPONOPUHOHMUE Ha a30THy KHceJiHHy H a30TM0HOKCHA.

OBa

ce

peaKuwja

y

MajiOM

OÓHMY AeiuaBa Beh Ha x j i a j i n o H Taiy

j0A0306eH30Jia.

Jofl030jeflHH>eH>a a HapcmHTO joAojeAHH>eH>a n p a c n a j y npw 3arpeBaa.y, n o r m o

caApwe

KHceoHHK y HaneToj Be3H. M3 3aKHuieJbeHor pacTBopa KajiHjyMjoAHAa ocJio6a(jajy ona enBHBaaeHTHe KOJIHWHHC j o ñ a ,

npH neiuy ce n0H0B0 npeTBapajy y j0A6eH30J].

HajHHTepecaHTHHja j e 6a3Ha yHKiiHja j o A a y j0A0HHjyM6a3aMa, Bapa

aMOHHjyMOBHM,

j y M j o A H A

je

CyjItjjOHHjyMOBHM

AHMep j 0 n 6 e H 3 0 J i a

npyrHM jiHcouHjauHjaMa nao

H OKCOHHjyMOBHM

LIITO j é " c a y i a j KOA N 2 0 4 ,

jeAHH>eH>a

flH^eHHJljOAOHH-

H n p n 3arpeBaH>y p a c n a j i a ce ER30TEPMHIH0

O r j i e A e BPUIHTH ca MBJIHM KOJiHHHHaMa y ApoMaTCKa

Koja n o i n y H o OAPO-

6a3aMa.

(cynp0TH0

N H 4 C 1 , P C I 5 ) Ha ABa MOJia C G H R> J.

enpyBeT«!

BHIUEBAJIEHTHOR

joAa,

Koja

V. Meyer

cy

H C.

Willgerodt

HCTOBPEIUEHO H HE3ABHCHO jenaH OA A p y r o r OTKPHJIH, CMAIPAHA c y A y r o BpeMeHa,

Kao IUTO

ce jorn AAHAC C M a i p a j y AHa30HHjyM je,¡iHH>eH>a, nao MOHONOJITICAHA KJiaca a p o M a i c n e xeMHje, Thiele

CBE AOK

HajnpocTHjH HiicKHM

HHje

(1909)

npHMep

npoHauiao

u e o HH3 JEAHM>EK>A H KOA 0JieKe H TO

Aa

Ha METHJIXAOPHA H XJiopjOA

(3AMEHA jOAa XJIOPOM). FLEPHBATH BHuueBaJieHTHor

joAa ÓHBajy

T.EK ouna nocTojaHH, KAAA j e j o A Be3=>H Ha yrjbeHHKOB BTOM KOJ'H j e Be3aH ABory6OM b£30M. r)

E e H 3 0 J i

Meiuajyhn pacTBopoM ra

OAMax.

Majio

no

CBanor

» 3

MyTHH OA Y3

Majio

a H H ^ H H a .

pacTBop

50

g

A0A3BaH>a

HaqHHH

40

g

x;ia^ett.e

noc^eAity yBen

ce

nena

y

JICAOM

TpehHHy Aa

ce

60

yHece

pacüiBOpa

npecTaae

pacTBop

a^KajiHH

tcajiaj-2-xjiopiiaa

Hampu'¡yMxuapoKcu¡i,a

Aoópo y

OA

mi ce

y BOAe OBaj

200 H

mi

ca

pacxJialiyjyhH

pacüiBop

aua30HiijyM0Be pa3Bu'¡awe

cTaHHTa, BOAe

a3on¡a.

cmamuia COJIU; n o

npe

CBp-

ApoMaxcKa AHa3ojeAHH>eH>a

VII, 3

meTKy

peaKunje

npeaecTHJiHiue

K0H^eH3aT0pa; o h y

B o ^ e h XBaTa c e ce

npelje

ce

ctbopchh

227

npeno

6en30Ji

JlHÖnroBor

caB, n p e Hero u i t o n p e ^ e c r a j i n i i i y Behe

enpyBeiy.

cyuies>y

no

c a Majio

CaCl2

kojihhhhc

peKTH^HKyje

6eH30Ji H3 M a j i o r ^ e c T H J i a i i H O H o r ö a j i o H a c a HaByneHHM K 0 H ^ e H 3 a T 0 p 0 M ;

6eH30Ji n p e ^ a 3 H

cnopo

6e3

ocTaTana

Ha 8 1 ° .

ilpHHOc

6

g.

3aMeHa rpyne N H 2 boaohhkom npeno Ana3ojeAHH>eH>a y HaBeaeHOM n p H M e p y HeMa pa3yMe ce HHKaKBor npaKTHiHor 3Hanaja, aJiH y apyrHM c^yqajeBHMa oßa 3aMeHa Möwe 6 h t h 3HaiajHa. Tano 'ce Ha np. m-HHTpoTo^yo^ (a H3 H>era /72-TOJiynnHH) Aoßnja H3 p-TOJiyHAHHa Ha Taj HanHH, uito ce (aueTHJiOBaHa) 6a3a HHTpHiue h rpyna N H 2 (no OTCTpaiteity aueTHJia) 33MeHH BOÄOHDKOM H3 MaflO npe OIlHCaHH HaiHH. CHS I

CHS

CH3

NO„

I N H'22

Tok peaKunje je Bpjio nyAHOBaT. M o p a ce npeTnociaBHTH Aa ce ÄHa3oiaT peayKyje y HenocTojaH ( ^ c h h j i a h h m h h , koj'h ce pacnaAa Ha 6en30.rc h a30T. CGH3 • N = N O N a

,

2 H

C 6 H 5 - N = NH +

NaOH

> Q H G - f . N2.

Ha MecTO ajiKajwor pacTBopa CTannia MOixe ce y UHjby 3aMeHe AHa3orpyne boaohhkom ynoTpeßHTM h a j i K 0 x o j i , KojH ce npn tom OTnyaiTajyhH ABa aTOMa BOAOHHKa AeXHAporeHHiue y aJiAexHA. y obom cjiyiajy Tpeöa AHa30HHjyM0By co KyßaTH HeKO BpeMe y ajiKoxojiy. Kao npoAyKi cnopeane peaKunje nocraje HCTOBpeMeHo ycjiea 3aweHe AH330HnjyM0Be rpyne annoKCHnoM (jjeHojieiap. O ß A e je jacHa napa.ne.ria H3Metjy oBe peaKunje h npeJia3a AHja30HnjyM0Be cojih y (jieHOJi npH 3arpeBaH>y. / N - N ^ h N I | -

ä)

M b p c t

+

cone

y

2 0 ml h

mcenune

h j i h 4 g u3oaMUJiHumpuUla.

xom

ce

noMohy 1:1,

u eüipa

aücojiyülHor OH^a

y3

xjialjefce

BoaeHor

Äa

y^apoM BJiaacaH ißpcTHM Ca pacTBop

hjih oa

+

h

3aTHM c e r p o M .

imaMeHOM

eTpa

AOBeae

crojn

onepe

Co

ao

HCl.

PacTBope

5 ao

3,5 ^

ce

33thm

JieAOM 3 g

1/2

iiOTnyHO

co

ml

emujiHuwpunia

1 0 MHHyTa h

Hajnpe ca

nocTe-

H3ÄB0jH.

Majio CMeuie

amo-

Bjia^Ha

Tpeöa

&&

ocymn

Ha x a p T H j H 3 a i i e ^ e i t e ,

ocTaHe Hh

eKcrui03Hje.

He CMe c e Ä O ^ H p u B a T H

N2 +

AO^a

c e ma30HujyM0Ba

mMpica

h caMO c e j e ^ H a M a a a k o j i h h h h 3

eTpa

f/Nx;OC2H3 | [

amoxom,

OcTaBH ce a a yqHHH

neHHM ^ O Ä a B a H j e M eüipa Oue^H

->

4)eHHJi-Äna30HHjyMXJi0pHÄ.

aHüJiuHXJiopxuapama amoxome

HO • C2H3

cnaTy^oM

npenapaT

hjih

k3kbhm

kojh

o ä h je

ApyrHM

npe^MeTOM. xapTHje c e ÄHa30HHjyM0Ba c o ynoTpeÖH

H (J)eHHJia3Haa

3a

AOÖHjaibe

(bhäh

pacTBopn

y

JieAeHy

BO^y h OBaj c e

4>eHH^ÄHa30HHjyMnep6p0MHaa

^a^be). 15*

228

OpraHCKO-npenapaTHBHH

< 5 e H H J i Ä H a 3 0 H H j y M H H T p a T

aeo

ao6nja

VII,

ce

y

KpHCTa^HOM

3

oöJiHKy,

ano ce y Aoöpo o x j i a l j e H y c y c n e H 3 H j y aHünaH-mmpama y boäh yBO^e y3 xjiaijeft>e HüUlpo3Hu racoBH (h3 apcenma h a30Mne mcenme 1,35) äok ce CBe He p a c T B o p H , a 3 8 t h m no^iaKo ^OÄaje amoxon h emap. O ß a j ce oivieA h3boah ca HajBHiue 2 g aHHJiHHa h oä AoönjeHe COJIH cyiua ce caMo BpxoM h o h o y3eTa k o j i h h h h 3 nocjie a e i j e i b a h H c n H p a i t a ca C M e r n o M amoxojia u eüipa (1:1) Ha nopo3Hoj neneHoj IVIHHH. HaTpaT ÄeTOHnpa npH 3arpeBaK>y Ha cnaTyjiH h ica^a ce y^apw *ieC a

khHcm.

ce

m3h>om

5KecTHHOM

pacnaAa

cyBa qyBaTH, Kao i i i t o ce yoniiiTe ca Mopa Bpjio onpe3Ho pyROBara. J l H a 3 0 H H j y M 0 B e COJIH n p o c T H X

npHMapHHX aMHHa

HOCTH H3C>JIOBaTH H3 BOÄeHHX p a C T B O p a . C T a j i H c a r a ÄOÄaTKOM e i p a . TO c e y

OBOM

c^yiajy

He M o r y

COJIH

cy

h OBa c o

c e 3 6 o r BeJiHKe

HOMTO COJIH a 3 0 T a c T e K H c e j i H H e H H c y

can0HH(j)HK0BaHH KHcejiHHOM H d o r a

ce

He

ana30HHjyM0BHM

cMe

cojiHMa HenocToja-

H a n p O T H B H3 aJIKOXOJIHHX p a C T B O p a M o r y OHH H C K p H -

Ä H a 3 0 T y j e c H>eHHM ecTpHMa,

Äna30HHjyM0Be

a m

x^opHÄ,

cybhm

ce noHamajy

6e36ojHe,

nouiTO

cnopo

H>HXOBH

y

OHH

ajiKoxojiy pacTBopjbHBe, ÖHBajy H3ßaHpeAHO

K a o COJIH (BHÄH c T p .

BoaeHH

pacTBopH

6p3o

122).

pearyjy

HeyTpajmo.

Oiiy3Me JIH ce coJiHMa KHceJiHHa noMohy ajiKajiHja, oHÄa ce y npBOM MOMerny CTBapajy Bpjio HenodojaHH

Ä H a 3 o H H j y M-X H Ä P O K C H Ä H ,

BpeMe « a j y

ÄOKasaTH H KOjn n p e j i a 3 e y +

CeH5

N =

N

NaOH

— C1

3aKHcejiHj:H ÄHa30HHjyM0Ba

C6H5 • N = *

ÄH330HHjyM0Ba

CO

ce

KOJH c e c a M o y

N

C6Hs

N a O H )

— OH

oßaKo

H r o caMO K p a i K O

aoÖHjeHH

N =

ÄHa30iaie.

NONa

H.O

-

ÄHa30HHjyM-XHÄpOKCHil

n0H0B0

pacTBopy

COJIH K H c e j i o r ÄHa3oxH,apoKCH.na, y T3B. +

HaTpHjyM({)eHHJIÄHa30TaT

pacTBop aHa30Taia, o h m

ce n0H0B0

cTBapa

co: 2 HCl N =

NONa

[C

»

6

H

• N =

5

L

N O H ]

C1

+

NaCl

J

+ - H , o

C

>•

6

H

5

-N = —

N

C1 Mh h THna

o B i i e HMaMo ÄaKJie BaacaH n o ß p a r a H

ÄHa3oxHÄpoKCHÄ, Kao

kojh

nodaje

Ä a j e c a KHcejiHHaMa Ä H a 3 0 H H j y M 0 B y npe

Hero

iiito

ÄejcTBOM

jaKHX

n o c T a j e jeÄHH>eH.e

THna

Ä H a 3 O H H j y M 0 B 0 r

THna

aiiKajiHja 4>eHHJiAHa30TaT H 3 0 Ä H a 3 0 T a T a

yuijia H y

ndopnjy.

XaniOBOi

o6jauiH>eH>a,

Behima

aTOMH.

HcTO

cyncTHTyncaHHX UHCTpaHC

xeMHiapa

Kojn C6H5

T3KBO

o k c h m a

H3 ÄHa30HHjyMXHÄp0KCHÄa, 0 3 n a q a B a

caMa H H j e 6a3a (uiTa BHiiie oHa j e

p e a K U H j e ÄHa3oje,HHibeH>a

BOÄHjia c e H3MeIjy Bamberger-a

nojio>«aj rpyna

Ma«a

je

OBy

h OH CXBaTaH>e

npejia3H y

(Schraube

cMaTpajy

aaHac,

H30Mepnjy cxBarao paBHH y

MOrjIO Oho

A c p H B a i a

je

c o jejiHe H30MepHe O

ÄyroroÄHuiH>a «a

je nHTaite peuieno y

Kao n p o c T o p n y

h CBeo j e

je

eMHejiy Ha p a 3 -

Be3aHH

a3o-

HeCHMeTpHIHO

cjiaiKe ca T e o p n j o M

((JjyMapHe h MajieHHCKe

H30-

ÄHCKycnja, K o j a

K o j o j c e Hajia3H Ä ß o c T p y K o

npHHUHny

KHcejiHHe;

KOHCTHTymijH

p a H H j e OÖjaCHHTH H 3 0 M e p n j y

ce y

oöpatjy-

KJiace je,aHH>eH>a. E H e p -

h Schmidt).

h Hantzsch-a

npeMa

(b. I X , 3).

eTHJieHCKHx

ce

KHcejiHHa)

aajbe npenaparaBHo

o j o u i j e A H o M o 6 j i H K y OBe H H T e p e c a H T H e

flHa30T3Ta

TOBH

H3Meljy

co.

n p o j i y j K H M O na

jeMo, MopaMo nporoBopHTH rHiHHM

H30MepauHj0M

( H a n t z s c h ) , iioiiito

n c e y Ä o 6 a 3 a

jihiht

oähoc

i H a s o x H f l p o K C H j a .

KHcejiHHe).

H30MepHje

VII,

229

ApoMatcKa ÄHa3oje,aHH>eH>a

3

npeMa OBOJ TeopnjH jiaöHjwn HopwaJiHn AH330TaTH HMajy ce ( = une-), nocTojaHH aiiasoTaTH uao anil- ( = TpaHc-) jeÄHH>eH>a. QHS

ONa I

N =

C6H5 I

N

N =

HOpMajIHH AHa30TaT

nao syn-

CXB3THTH

N

I ONa H30HH330TaT

ÄOK ce npe.na3 npocTor ^eHn^-^n-ÄHasoiaia y H30Mep BpuiH noA ¿xejcTBOM jaKHx ajiKajiHja, iioTJie je syn-o6nmt ÄpyrHX ÄHa30TaTa Taito jiaöwjiaH aa ce OHH CKopo TpeHymo nocjie H>HX0B0r CTBapaita H3 ÄHa30HHjyM0Be CO;IH npeTBapajy y anti-o6nnK H 3ôor Tora ce He Mory >jaK HH y pacTBepy KOHCTaTOBara. BawaH npmiep OBe BpcTe je p-H H i p o i j i e H H J i Ä H a 3 0 T a T , onHcaH noÄ i]) inj« nynjioBaHH npojiyKT ß-Ha(})f0;i0M npeTCTaBjha MHOTO ynoTpeßjbaBaHy 6ojy „n a p a u p B e H O". i>eHH^AHa30HHjyMnep6p0MHÄpacTBopy

I^EHOM

paHHj'e onHcaHe q e p c r e

ßoÖHjeHOM h3 2 g aniuiuna

paclüBopy,

pacTBopeHor y

âpoMa

r o A ce H3Äßaja

ÄOÄaje ce y3

15 ml 2 5 % - H o r pacïïiBopa

MpKO yjbe,

Koje ce

OABOJ'H

AeHOM B o a o M , npH qeiuy üepöpOMun

J\a 6H ce n p e ß e o y y

3 — 4 oöpoKa

ciMOHujaica. MHpHca, HaqHH

y

MOtfie

AAJE

10 ml

y

H

pacxjia-

HJIH

,.aua30-

xjiaijeibe Jie,a,OM 1,5 ml

KanujyMÔpoMuna onepe

CBe AOKJie

HCKOJIHKO

(„AHA30ÓEN30./IHMHA")J

Aoôpo

oxjiaijeHòr

cTBapa ce C 6 H 5 • /NN< \N

NH 4 OBr

H20

|| + NH 4 Br +

H,0

eHHjia3H,n ce MOUCQ Bpjio o6a3pnBHM xHaporeHOBaiteM (ca Sn CI 2 y eiapcKoj coHoj KHcejiHHH) npeBecTH y H3BaHpeAHo oceubUBH 4 ) e H H J ' T P n a 3 e H (Dimroih), Kojw, Kao HITO je Beh noMeHyTo, .nexHÄporeHOBafoeM noHoBo npeJia3H y a3HÄ. Kao H ajin^aTCKHM ana3ojeÄHH>eH>HMa, Tano ce H a a o ï o B o j o B H i H o j K H C C J I H H H H aeHHM ecTpHMa npHnwcyje auHKJiHmia cTpyKTypHa (jjopiuyjia, ca KojoM ce noMeHyie peanunje Mory oBaKo (JJOPMY^HCATH : + 2 H

CgHs . N = N s N

(

— 2

H

C 6 H 5 • N = N — NH 2 .

OpraHCKO-npenapaTHBHH

2 3 0

y

npHJior

anHKJiHMHe

npenapaTHBHo

opMyjie r o B o p w

Hajóojba

neo

VII,

H peHflreHCKH

Me-ro.ua 3a « o ó H j a f t e

aswna.

«HjarpaM

4)eHHjia3H.na

3

nojia3H

on

4)eHH,nxH,apa-

3HH3 ( V I I , 6 ) . A p H J i a 3 H S i i H3flBajajy

iiBa

cy

Kpajtta

XCMHCKH B p j i o a K T H B H a

a30T0Ba

aroMa

a p H J I X H f l p O K C H J i a M H H , cjiyqajy

y

ajiKajiwja — a3HA

0

HeraTHBHor

HCTO O H a K O

ajmajiHja

N

rpHftapoBHM

2

+

3

N a 0 H

peareHCOM

• N

S

Ce O f l M a X

MajioHCKe

+

3

H

0

5

h, Ha n p H M e p , ca N


2

N

npHMajyhn

y

—

6

H

N

3

+

3

ONa

nociajy

2

npejia3H y

ce

aejCTBOM

pacnaaa

C npeno

6

H

• N =

5

cBojax

• (COOC

H

2

+

NsNa

+

H

;iHa3oaMHHo-je,HHH>en>a,

Dimroth),

H

MgBr

3

KHcejiHHe aaje

CH

a3H/iorpyna

XHAPOJIHTHHKH

Ha

np.:

N —

N H

Ha

0

2

Tj,

1,3-an-

TayTOMepHHx

o^Hoca

• CH

HHTepecaHTHnx

S

(Dimroihy. / N

C

KHcenHHaMa

Boay

aMHHO(j>eHOJI.

npcieHy

/

a3Hjia

Wlslicenus

(IV.

T p H a 3 o JI o H-A e p H B a T e

3HAWAJHE

C

ijieHoi,

T p H a 3 e H H C0H

EcTap

jeflHfbeHia

ociaiaK

IUTO c e TO . n e m a B a C x a j i o r e H O M

H oaroBapajyhH

cyncTHTyHcaHH

N2;

cyncTHTyema y

Kao

N

2

Ca

KOjH

nao

5

)

-> C 6 H

2

-

5

N < \

=

N | C —

C =

C02C2Hr,

uo/ OBa Kao

KOHAeH3auHja

LUTO a 3 M i i n

yonuiTe

jia c a B e 3 a c n h e H H M IHlia,

je n o T n y H o

aHaJiorná KOHaeH3auHjH ecTpa HHa30CHpheTHe

H noKa3yjy

ynajUfeHBy

jciiHH>eH>HMa

nao

ca

CJIHMHOCT C ajiH(f)a TCKHM

a u e T i u i e u H t i a ,

K H C e j I H H O M

UHJAHOBOJIOHHHHOM

HJip.

KHcejiHHe

;iHa3oje.nHH>eH>HMa j e p n B a-

OJIC^IIHCKHM

flajy

XeTepOUHKflHWHe

npCTeHOBe. N O N a

T1, O

1)) H A T P H J Y M - P - H H T P O ^ E H H n - a n t i - A H A 3 O T A 1 4 g p-Humpamuiima (1/10 MOJia) icucejiune ( 3 0 mi K o m j e H T p o B a H e Ha

80

g

ce

Ha

5 — 1 0 °

jieAa,

ce

y 3

CH3HCHO

ce

KOJ'H ca

Hajia3H

p a c T B o p o M

M e r n a a e

pacTBope

y

o a

ce

KHcejiHHe Majiy 8

o a j c a h o m

h

y 3

q a m y

BOAe);

AeSejiHx

h,

•

n o m T O

y

60

y ce

mi

cone

ce

cmia

pacTBOp

3HAOBa.

g HaüipujyMHunipunia AOAa,

N /

3arpeBaH>e

mi

30

2

,Z3,Ha30Tyje

mi

20

BOAe,

y B e p H M O

Koj«

je

pe-

3aBpmeHa, pacülBop aua30nujyM0Be COJIU cnnaMO y 3 MeiiiaH>e y mi 4n-HampujyMxunpoKCuda, KOJ'H j e npe'rxoAHO 3arpejaH H a 4 0 — 5 0 ° . x ^ a ^ e a y anti-atia30ülani ce H3ABaja y jienHM, 3JiarHO j K y r a M jbycnH-

anuHja 400 r i p n

uaMa. H

n o c a e

Hcnepe

BHiueq&coBHor

3acnh€HHM

ne^eHoj

noerojaH

TJIHHH

CTBapafteM

pacTBopa

y

R

—

OCJIO6OAHTH

c e JIOSHTH HO H>eroB

npoueaH aso-óoja.

npejia3

1

Schraube

2

O

y

H

OA

on

co

KyxuwcKe

3AOCTA^E

He

Ha

KYXHITCKE

naxyjbHixa

HacTanor

BOAeHor

cyiueita

BpeMeHa

COJIH.

IlpHHoc

HaipHjyMOBOM

Ha

COJIH —

uiMpKa

n o p o 3 H o j

Moace

H

HcnapaBaH>eM

H

27, 7.

518

H c a H>HM

s.Y«-aHa30TaTa

anti-o6mK. B.

n o M o h y

ílocjie

A y r o 60°

KynJiyje ce ca

HepacTBopeHHx

Cje,NHH>aBaH>e

Schmidt,

oijeAH

COJIU.

ce

(1894).

H3Beae

18

g.

[3-Ha(f>T0.na

KynjioBafte,

c a (JDCHOTOM

pa-

n p o u e ^ e H o r

y B e p H T H . A J I H a n o ce pa36jiajKeHH p a c T B o p 3aKHceJiH

ce Tpe6a

¿ ? - C O J l H M a BHFLH V I I ,

ce

np0H3B0^>H0

3arpejaHOM

flHa30-C0^H

COJIU 2 , o n e M y

KHcejiHHOM,

je

amoxony

BojieHH pacTBop ca

CTajaita

pacüiBopoM

aemaBa

nnv¡

COHOM

OHAS ce

he

ópwe,

VII, 4

ÄpoMaTCKa Ana3ojeÄHH>eH)a

4.

p-TojiyHHTpH;i

na

p-TOJiyn^HHa

231

(Sandmeyer-oBa

peaKijHja1)

öajiOH OÄ 2 jiHTpa pacTBopH ce y3 3arpeBaii>e Ha BOACHOM THJiy 50 g cyji(pawa öaicpa y 200 ml BOAe H }'3 HenpeKHAHO nocTeneHO A O A a p a c T B O p OÄ 55 g KamjyMiiujaHum y l O O m / B O A e . ce npH TOMe pa3BHja racoBHTH iiujan, TO OBy peaKixnjy Tpeöa y Kane^iH.

Kyna3arpeBaH>e

Y

IIOIUTO H3BOÄHTH

XI,OK ce pacüiBop KOMüJieicctior KyüpoiiujaHuaa AAJBE ö . a a r o 3arpeßa Ha 6 0 — 7 0 ° Ha BOÄeHOM Kynara^y, Tpeöa cnpeMHTH pacTBop p-T0JiHJiAHa30HHjyM-xjiopHAa Ha OBaj H3hhh: 20 g mojiyunuHa 3arpeBajy ce y CMeuiH 0Ä 50 g KOHixeHTpncaHe cone Kucemne H 150 ml Bo^e AOK ce He pacTBope, noc;ie

qera

ca

ce c y A

TCHHOCTH 33MOHH y

JieAeHy

BOAy

h TCHHOCT

>KHBO

ÖH ce UiojiyuauHXJiopua H3ÄBOJHO y KpHCTajiHMa. 3 a T H M ce OBOM x-rcopHAy a-MHHa y3 x J i a t j e i t e ./ieAOM A O A a j e p a c T B o p OÄ lö g HaJHpujyMHuUipum.a y 80 ml B o ^ e

cTaKJieHHM

npoMeiua

IUTO" j e

CBe

Moryhe

AOivie,

niTannheM,

CHTHHJ'HM

AOK c e c a

H3 ö a ^ o n a

ycyTH

UnjaHHÄa,, n p a meHOM BOAeHOM

neiuy

yjbe;

OHO

ce

Ha

qecro jom

öa^oH

OH^a

na c e (Känejia,

ce

10 MHHyTa y Tpeöa

Tonao

eKCTpaxyje

TpajHa

pacTBop

1/4 q a c a

CTBBH u e B ,

HHTPHJI

eTpoM,

^oönje

npoMyhna™.

je^HO

AecTHJiauHjoM

HCN!).

H e

aua30HujyMXJi0pua

AOÖnjeHH

CMeuia

n p H qeiviy c e

K0HÄeH33T0p,

jKyhKacTO

Tony

OBaj p a c T B o p

wojiymiMpuji

H3ABOJH

y

peanuHOHa

KynaTH^y,

Ba3AymHH

KHce^iHHy. T a K O

nocTeneHo

ÄOJiHBafcy

Ka./injyMjOÄHAOM

ckpoöob3hhm

peaKuwja Ha a 3 ( m c T y

FIo

3aBp-

3arpeBa

Ha

Koja c^y^KH K a o

napoM

ca BOAeHOM

npH

Tpeöa

Kynpo-

TOMe

npejia3H

emapcm pacüiBop

ABa

Kao nyT

n p o M y h K a ca 2n-HaüipujyMXUApoiccuaoM, A a ÖH c e O T C T p a H H O p-tcpe30Ji KOJ'H TaKol^e nocTaje npH OBOJ p e a K U H j n ; 33THM c e e T a p HcnapH H a3oUiojiyoji, 3öor

Kojer

n p e n a p a T HMa > K y T y ö o j y ,

ca p a c r B o p o M

icucejiuHe2. BOAeHor yjbacT,

OÄ

4

3aTHM

ujMpKa OHAa c e

OTCTpaHH M y h n a i b e M T o r u i o r

g nana) (H)-xjiopuaa

y

0CTaTi K H BOAOM, o q B p c ; m T O J i y H H T p H J i o u e A H

H cyiuw

Ha n 0 p 0 3 H 0 M

pacTBopH

y

elüpy;

Tas>npy. erapcKH

A K O je n p e n a p a T

pacTBop,

paAH

com

noMohy

Majio

OTCTpait>eH>a

j o m jeAHOM H3Myhica c HawpuiyMxuApoicciiaoM, cyiiin H AecTH^aunja. T a q n a K j b y q a i t a 218°, T a q n a T o n jbes.a 29°. H p H H O C 1 2 — 1 4 g. 3aocTajior SnCl 2

Huüipuji

Haj3aA noABprHe

B e H 3 0 H H T p H J I . H a HCTH HaHHH MOHCe ce y OTnpHJIHKe HCTOM npHHoey pacTBop Ana30HHjyMXJi0pHAa H3 18,6 g aHHJiHHa npeBecTH y 0en30HHTpH.fi. TenHOCT, Koja lobyqa Ha 186°.

p-Tojiyuflna mcejiuna. KauHjy

HHTpHJia y

KHcejiHHy

jiHHa, CTp. 116) Moa (J)eHHJicHpheTHa

B. 17, 2850 (1884); 18, 1490 (1885); 2 2 , 2178 (1889). f l o Henle-y, O r g a n , e h e m . P r a k t i k u m , 3 , H3Äaite, CTp. 149.

232

OpraHCKO-npenapaTHBHH

g mojiymülpujia

5,5

K0HuéHTp0BaHe

yHecy

cyMüopm

6a./iOHy

ca

Hait>y

1

caT,

ijeity

pa3ÓaajKH

y

3arpeBajyhH

mi

neumaHOM

KpwcTajiacTa

y

BO,a,e, K o j a

CMerny

ce

K0H,zi;eH3aT0p0M

Ha M p e > K H ujm

BOAOM,

VII, 4

oópouHMa

MSJIHM

H 10

JIhSHFOBHM

ycnpaBJbeHHM

ce

ce

rncemne

aeo

h

o a 20

Hajia3H y y

KJby-

Fio

oxjia-

OApacaBa

KynaTHJiy.

(peHUJicupñeüiHa

mi

MajiOM

Kucejiuna

oue,a,n

n o M o h y B o a e H o r niMpKa, eBeHTyajmo nocTajm aMH,a, oTCTpaHH pacTBapatteM CHpoBor

npoAyKTa

(JiHJiTpaTa AOÓHja

ce

ano Pajw

npeTXOAHO,

y

ca

ce

je

ce

Moryhe

npH Tonu

177°.

ripenapaTHBHO p-To^yH^He

BpuiH

pacTBop

nyT

4

He

ce

MucTujH

^acoBa ce

150°

ajiiwxojia,

(y

He

yuiTpua

CMe

yHOCHTH

y

HCKpHeTaflHeaBa

ra

caMO

MHHYTA

KjbyiaflH KHcejiHHa

g. KHCJIHHC

icpeijiiajHe

HaipHjyMOBe

a OKCHnauHja o - i o n H n c y n t y a M H a a y y

Mep 3a oBaj m n

yjbaHOM

cyuuehH

COJIH

noJia3H on

OKCHAHiue ca nepMaHraHaTOM Ha

TeMnepaTypw BojieHor KynaTHJia. H a HCTH iiamiH MOHte ce Tojiyon n p e B e c i H y KHcejinay,

npo^yKT

K y B a HCKOJIHKO

h

He

pacTBopa

Ha

npenapaT,

33MyTH

rniaK

3a ,no6HjaH>e

ii>eHe

5

kjbyqajior

npouei^eHor

HajóojbH

KHce^HHe;

KOJ'H

IlpHHoc

nucejiune.

pacTBopH

ynpaBO

yjba,

xjiatjeity Ha

cone

Maite

pacTBop

5KHB0THft>CK0r

pacTBop. Koja

canoHH(})HKauHja

IIITO

npou.e,n,n H H3

HaüipujyMxuApOKCUfly,

noMohy

npe^HiuhaBaifea

BO^e,

Majio

pa36jia>KeHOM

KHcejiHHa

ce

KynaTHJiy).

TOJIHKO

y

K3ABojH

6eii3oeBy

j e c i e TCXHHMKH Bawan npH-

caxapHH

peaKUHje:

S O , • NH2

xSO„NH.

NH COOH .HyncH ÓOHHH aarniH c a r o p e B a j y y KapóocnjiHy

rpyny

Be3aHy nenocpeAHO 3a npcTeii.

JIOUIKO

flemaBa

ce

caropeBafte

co-apH.uMacHHx

KHceaHHa

no

npiiHunny

BHO-

p-o K C H A a u i i j e

(F. Knopp). p e a K u H j a.

CaiiAMajeposa

JlaKOha c KOJ'OM nocTaje

o6jauiH>aBa ce cnomaHHM pacna«aH>eM jiHja30HHjyM j o .n H a a C6H5.N =

BpoMHfl „ynpaiKfteHO eM 0CH0BH0r jeambeiba

nao

je

mro

no3HaTo,

VBeK

IIOCTHHH. T a n o

npH

6p0M0BaH>y

He u o x e

Tojiyojia y npcTeHy n o c i a j y

HCTOBpeMeHO o- H p-6poMTojiyoji Koje j e TéuiKO n o t n y H o OABOJHTH jeaaH OÜ a p y r o r .

floMohy

VII, 5

ApoMaTCKa ÄHa30jeflHH>eH>a

CaHAMajepOBe

233

o-

peaKUHje o6a TOJiyH,nHHa jiajy Mcf)yTHM HCKJbyqHBO

h p-6poMTOJiyon äok

ce /n-6p0MT0Jiy0Ji Monee ä o ö h t h caMo H3 m-TOJiyHÄHHa. CnHTe3a

apoMaTCKHx

h h t p h ji a

no

CandMdjepy

je MHoro ejieraHTHHjH Ha- 3 h h j i h h ,

b h ä h CTp. 125).

5.

ApcaHHJIHa

KHCejIHHa

/7-H H T p O ( j ) 6 H H J i a p C H H C K 3 Äna30Tyjy

ce

oHaKO,

(cTp. 2.30).

3aTHM c e

KSKO

je

TO

pa3ÔJia)KH

H3

p-HHTpaHHJIHHa1

KHCCJIHH3.

onncaHO

KOA

1 3 , 8 gr

p-HUMpaHUJlUHa

Ao6njan>a

BOAOM H jieAOM AO j e ^ H e

a/¿ffiü-Ana3oraTa JiHTpe,

KHceJiHHa

ca 4n-HampujyMxuapoKctißa TOJIHKO, A a Kouro xapTHja TaMaH BHiue He non^aBH, na ce OHAa pacTBop P,UA30HUJYM0BE COJIU y3 y

Meuiafte

T3HKOM

HeyTpajimue

M^a3y

apcemiUia2, Kojn AeöejiHx

yjiwje

je

3HAOBa.

y

8 0 0 ml

npeTxoAHO PeaKunjs

ce

5%

pacUiBOpa

cetcyunapnor

HawpujyM-

c n p e M j b e H H KOJH c e H a j i a 3 H y B e ^ i H K o j npn

Memaity

craKJieHHM

uiTannheM

laiun

aeiuaßa

CKopo TpeHyTHO y3 6ypHO pasBujawe a3owa. Ca^a ce y nopue.'iaHc«OM HaHKy KOHueHTpHiue na OTnpnjiHKe 4 0 0 ml h h 3 T3MHO oôojeHor pacTBopa COHOM KUCeJIUHOM H3ABOje CJiaÖO KHCeJIH CMO^aCTH CnopeAHH n p O Ä y K T H . f i o 3aBpiueHOM H3ÄBajaiby npoueA« ce Kpo3 HaöpaHo ueAn-flo'pacTBop Kojn je nocTao CBeranje 6oje H KojH je caAa Knceo npeMa KOHTO xapTujw, h TOJ1HKO Hcnapn, Aa KpwcTajiH n o i H y Aa ce H3ABajajy. Tío ox^aljeity hckphcrajimne 8 — 1 0 gr p-HiiIüpo +

6 H

ce Moate aoôhth 3arpeBaH>eM

KHceJiHHe,

HHTpHiiie

H CTBopeHa

2

0

BOAeHor HHTpo-

O H A a c e A a j b O M p e A y n i u i j o M MOJKe a o ô h t h

apceHO-jeAHH>ett>e,

c a j i B a p 3 a H .

i>opMyjiHcaTH

oae

peanuHje! Be3HBaHje

rpyne

npeMa -noMeHyToj jeAHH>eKja, rpaijeHor J133H

6ub&

pa3BHjaft>e

5

6p30

i

C

6

H

5

• N = N

• A s f - O N a

\ O H C

O H

6

H

5

• A s f - O N a \ O H

+ N

2

.

ce

Ana3o-

- f N a C l

canpey3

ApoMaTCKa Äna3ojeÄHH>eH>a

VII, 6

235

6. ^eHH^XHflpaBHH 1 47 g anujima ( 1 / 2 MOJia) pacTBópe ce y 100 ml KomjeHTpHcaHe com Kucemne, Koja je pa36jia>KeHa ca HCTOM 3anpeMHHOM BOAe, H Ana30xyje ce, Kao iiiTO je Beh BHuie nyTa onHcaHO, ca pacTBopoM OA 38 g HawpujyMHuwpuwa y 100 ml BOAe y3 Aoöpo xjiaijeibe. ripe Tora ce npanpeMH IUTO je Moryhe 3acHheHHj°H BOACHH pacTBop IV4 MOJia — 158 g HeyTpajiHor, aHXH^poBaHor

HJIH 3 1 5 g

KpHCTajiHor ( 7 H „ 0 )

HampujyMcyjikh

ce

COHOM

H a T o n j b e H e KomienmpuccmoM

HekopacTon

BOAeHOM

nocjie

npenapaTa

nap^e

mcenuHOM.

o 6 o j e it> e.

H H3HeHaI)yjyha CHHTe3a H H Ä O J I H H X

flena

o6jauiH>eHa

Kyna.THJiy,

H CMerna 3 a r p e ß a y 3 Meinaft>e

3 a r p e j a H O M Ha 1 8 0 ° . T a M H O o ö o j e H

CTBopeHH

o^BpcHe

Tamca

P e a K U H j a KyBa&eM

ce

/ 4 ^ a c a y K j b y q a ^ O M BOACHOM

ifuwca

JIHKO M H H y T a y y j b a H O M K y n a T H ^ y onepe

3

OCT3BH c e Aa c r o j H

VII, 7

ÄeiajbHMa

noja je onurrer Ka-

NEPUBAIA,

tck npe KpaTKor B p e M e H a

MopaMO

( R . Robinson).

npeinocTaBHTH na KeT0-— — N N< /

S

CH 3

>Kyia HaipujyMOBa co h3boah ce h3 OBor „a30"-06jiHKa, aoK ce jiejcTBOM KHcejiHHe CTBapa upBeHO oöojeHa XHHonana co.

M o w a a cJioöoaHa, TaKolje upBeHO oöojeHa KHcejiHHa HMa cTpyKTypy jeaHe yHyTpaiiiH>e xiiHoimHe

co/ih,

jeaiior

6cTanna:

HN

N

i OoS — O — 36or OB3M

ii3BaHpeaHor

npHHUHny

TexHHuxor

KynjioBafba,

anajiHcatbe, B p e a n a je noMeiia. rpHjyMXHnocyjiíjjHTa p a c n a a a j y Ha ABa

h

(koä

jejiHa

il / C H 3 N < + \ch3

3nawaja onuiTa

ÄejcTBOM

6e36pojHHX

npHMeaeHa

Ka ji a j (li) -

a3o6oja, peawiHja

xji o

p

h a a hjih

cpeacTBHMa,

y OBoj peaKUHjH n o c x a j y , flHHa

h

HjHxobo hü-

TaKolje aejcTBOM

cBe c e a 3 o 6 o j e npiiMajyhH i e T n p n BoaoHumia aTOMa peayKUHOHO

no;iH-a3o6oja Ha BHiue) MOJieKyjia

npmiapHor

0KCH-xHApa30-jeÄH[ieHja c y , 3a pa3JiHKy o a npocTHX a e p H B a ì a

pejiyKUHOHHM

Koje c y carpatjeHe no Koja c;iy)KH 3a

a a c e H>nxoBa XHapa30HCKa Kao

uito

toahko

Be3a o a M a x Kiiaa.

c e H3 cjjopMyjie Mowe BHaeTH,

/7-ÄHMeTHJi-tj)enHJieHÄHaMHH.

aimua,

Mh bhähmo

aanjie,

H3 xejinjaHTHHa

cyjiifiaHMJiia aa

Amhho-

HenocTojaHH npeMa Kiice-

c e a30T, Kojn je npH

ÄHa30T0ßaH>y CTynHO y MOJieKyji, nojaBJbyje Koa „a30-K0Mn0HeHTe" (OBae aHMeTHJiaiiH;iHHa) Kao N H „ - r p y n a , a o k c e aHa30T0BanH aMHH (cy;i(})aHHjiHa KHcejiHHa) noiioBo Kao TaKaB aoöHja.

O n i e f l : 3 gr xejiujanmuHa pacTBope ce y i i i t o j e Moryhe MaK>e Bpejie 33THM ce o a pacTBopa o a 8 gr icajiaj(U)-xjiopuMa y 2 0 ml kohuchTpoBaHe cone tcucemne a o a s Ha Tonalo t o j i h k o , Aa ce n p B H p a c T B o p o ó e 3 0 o j n . n p H x^aijeiby h Tpjbaiby CTaKJieHHM lUTanwheM HCKpHCTajimne cyjKpanujiHa Kucejiuna, Koja ce nocJie Heia

COHOM

enpyBeTH

He p a 3 B n j a

ca

y3

Aua30dMUH06eH30Jia

ÄOÄaBa&e

eM

6a3a.

A n c o p n u n j a y BHÄAMBOM jiejiy cneKTpa T]. cyôjeKTHBHa 6 o j a ,

ycjioBJbeHa j e KOÄ yrjbeHHKOBHX jeÄHH>eH>a npHcycTBOM T3K03BaHe MOJieKyay. Kao j a s xpoMoijjop

Äejiyje HHTpo3o-rpyna,

aajieKo

xpoMotjjope

cJiaôHje

rpyne y

HHTpo-rpyna, Bpjio

jaKo a3orpyna ajiH OBa caMo'KOÄ apoMaTCKHX jeÄHH>eH>a. A30MeTaH j e 6e36ojaH. MetjyTHM, HHTeH3jjBHO HapaHyacTo upBeHo oôojeH HHje HH HHTpo3o6eH30Ji. npHpoÄOM H3a3HBa

3aTo j e noTpeöHa j o m

a306eH30fl HHje 6 o j a Kao UITO TO

jeuHa « a ^ a r p y n a Koja

CBojoM XCMHCKOM

aijjHHHTeT npeMa. BjiaKHy H Koja y HCTO BpeMe Äaje

TaMHwjy HHjaHcy

6 o j e . HajBa>KHHje OBe r p y n e , Koje c e 30By

ayKcoxpoMe,

j e c y O H « N H 2 , Ga H>HXOBHM

ayKcoxpoMHHM yTHuajeM yno3HaaH CMO c e KOÄ o-HHTpoi}>eHOjia H KOÄ HHTpaHHJiHHa Kao c a npocTHM npHMepHMa. ilpaKTHKyM opraHCKe xeMHje

16

42

OpraHCKo-npenapaTHBHH aeo

ByHa

H CBHJia

VII, 7

cy 6ejiaHqeBHH3CTe MaTepnje H Kao TaKBe aMtfioTepHor KapaKTepa.

OHe ce M o r y npeMa TOMe cjeAHfbaBara KaKO ca KHceJiHHaMa Tano H ca 6a3aMa. VI3 Tor pa3jiora 6ojeHe Maxepnje 3 a x B a j b y j y h H CBojHM a y K c o x p o M H H M r p y n a M a M o r y

AHPEKTHO

ÖOJ'HTH

B y H y H CBHJiy. ÄpyKqwje j e 6ojaÄHcaH>a

T o j e CKopo

naMyna.

KOA

iHCTa uejiy;i03a

XCMHCKH

CTora y CMHCJiy

H

HHAHijiepeHTHa. O ß a e ce cjeAHH>aBaH>e c 60j0M Bpuin noMohy

XCMHCKH

Koje ce npe 6oj3AHC3H>3 HaHece Ha

BMKHO

H

Koje caA M o » e

M 0 4 H JI

aa Bewe 6 o j y ,

XCMHCKH

H

KOMiuieKCHO. MoHHJia 3a B a w H y r p y n y KHcejiwx 6oja (VIII, 6) j e c y yrjiaBHOM

XHAPOKCHAH

Taaa,

BEHHHOM

H TO

xpoMa, ajiyMHHHjyMa, rßowlja, aHTHMOHa, KaJiaja

KOA CBHX 6ojaÄHcaH>a

nopeA

HTA.,

3a 6a3He 6 o j e

a

TO

Me-

Tamm.

Be3HB3H>a oA H3BaHpeaHor 3 H a i a j a je H

XCMHCKOT

(j) H 3 H q K o, npeKO noßpuiHHCKe aTcopnunje. OHa T H B H H M OA

OBHX

j e Ta Koja

0M0ryhyje jeAHOM

cpa3MepH0

MajioM 6 p o j y

6ojaMa 3a naMyK, Aa ce HenocpeAHO Bewe 3a 6oja cy

K0Hr0-upBeH0

H

AHC-a30-60je,

6oja,

HeMoneHa

T3B.

cyncia-

BJiaKHa* HsjßawHHje

Koje ce H3BOAe H3 AßocTpyKO AH330T0B3H0r öeHSHAHHa,

H>eroBH AepHBaTH. OHe c e y

BOACHOM

pacTBöpy Ha;ia3e y o6;iHKy cö;ia

H

6HBajy OA cTpaHe BJiaKaHa Ko.noHAajiHo aicop6oBaHH Kao HpeBepcHBHH rejin. O

K y n j i o ß a i b y

ÄHa3ojeAHH>eiha

Oßa peaKUHja, K0j0M ce Aoönja H3BaHpeAHO ce, CBeAeHa Ha HajnpocTHjy cxeMy, y TOMe, c cjieHOJiHMa

HJIH

apoMaTCKHM

6poj TexHHMKHX a30-6oja, cacTojw

BCJIHKH

ce apoMaTCKa AH33ojeAHH>eH>a KOHAeH3yjy

IUTO

HMHHHMa y a30-jeAHH>eH>3. M3 Jia6HJjHor AHa30-CHCTeMa

no-

CTaje Bpjio n o d o j a H 330-K0MiuieKC. A s o - ö o j e cy npeMa TOMe ycTBapn jiepHBaTH 3306eH30.ua HJIH

H A30HACJ>TAJIHIIA

H

Ap.

nocTojH npsBHJio, Aa ce K0HAeH3auHja ca i j i e u o j i H M a HeyTpaJinoM

HJIH

pacTBöpy,

ce

AOK

apouaicKH

a

BpuiH caMO y

aiKainou

KynJiyjy y cjia6o

M H H H

K H-

C e JI 0 M pacTBöpy, BehHHOM y pacTBöpy cHpheTHe KHcejiHHe. HajnpocTHja AHa30TaTa

a30-60ja,

H (jieHOja;

ajiH Koja

HeMa

ana30 rpyna

TexHHiKor

3Haiaja,

nocTaje

H3