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English Pages 204 Year 2019
Organic Reaction Mechanism : Through Problem Solving Approach
Nitin D. Gaikwad (M.Sc., Ph.D.) Assistant Professor Department of Chemistry, K.T.H.M. College, Nashik-422005 Maharashtra, India email :[email protected]
Organic Reaction Mechanism: Through Problem Solving Approach ISBN : 978-93-5267-423-7
All rights reserved. No part of this book may be reproduced in any form, byphotostat, microfilm, xerography or any other means or incorporated into any information retrieval system, electronic or mechanical, without the written permission of the copyright owner.
PREFACE
This book aims to teach students how to draw organic reaction mechanism for themselves. Almost all available books, on organic reaction mechanism describe reactions and their conversions. This book confronts the student with the organic reaction mechanism by showing how the reagent and starting molecule act together in the reaction. The reaction mechanism approach is learnt by students from this book who then teaches themselves how to use mechanism by solving a series of problems. It is not a conventional text book with detailed text explanation. In short this book understand quickly and giving information about reaction mechanism. Also the student has planned sequence of problems to demonstrate the use of each new mechanism and to test his understanding of it. Each problem is followed by possible reaction mechanism and short explanation, So that if the student fails to solve a problem he will still understand the answer better for having attempted the problem himself. The student therefore has the possibility of continuous self assessment through the use of large number of problems. There are some excellent books written about organic reaction mechanism but they mostly present complete synthesis not reaction mechanism. I have tried in this book to teach student to speak the language of reaction mechanism themselves. This book is originally written for the first year students. The programme aims to allow students to teach themselves but it shouldn’t mean any less work for them. Because students discover what they don’t know, they should have more sensible questions to ask when they were solving reaction mechanism. My aim is to give you more time for real teaching. The book should do the ground work and you should be able to set suitable programme and discuss then profitably. The book itself has plenty of problems of this sort.
Though the programme may introduce you reaction mechanism, its main aim is to suggest a mechanistic approach to the organic reactions. You therefore need to have a reasonable grounding in organic chemistry so that you are familiar with most basic organic reactions. If you are first year student with no much experience of organic chemistry or limited knowledge of organic reactions in practice you will probably be able to work straight through the book to learn the actual reaction mechanism. The point of book learning is that you learn at your own pace and that you yourself check on your own progress.
Contents 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24.
Nitration Reaction Nucleophilic Substitution by NGP Aromatic Nucleophilic Substitution Halo-hydroxylation Reaction and Aliphatic Nucleophilic Substitution Neighbouring Group Participation by sigma bond Aromatic Electrophilic Substitution and Diazotization Aromatic Nucleophilic Substitution Addition Reaction Nitration Reaction Aromatic Electrophilic Substitution Neighbouring Group Participation by sigma bond Elimination Reaction with Rearrangement Rearrangement Pyrolytic Elimination Reaction Gattermann Koch Reaction Pinacol Pinacolone Rearrangement Alkylation and Dehydration Reaction Neighbouring Group Participation by heteroatom Aromatic Nucleophilic Substitution and condensation Aromatic Electrophilic Substitution Addition Reaction Methylation and Vilsmeyer Haack Formylation Reaction Elimination and Addition Reaction Aromatic Nucleophilic Substitution
25. 26. 27. 28. 29.
Neighbouring Group Participation by sigma bond Diazotization Reaction with stereochemistry Friedel Craft Acylation and Condensation Reaction Addition Reaction: Bromination Rearrangement
30.
Aliphatic Nucleophilic Substitution and Chlorination by SNi mechanism Aliphatic Nucleophilic Substitution Jacobson’s Reaction NGP by Aryl ring
31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48.
Elimination Reaction by E2 Mechanism Cyclisation by protonation Cyclisation by using PTSA Aromatic Nucleophilic Substitution by Elimination –Addition Mechanism Diazotization Reaction with stereochemistry Neighbouring Group Participation by heteroatom and Aliphatic Nucleophilic Substitution Friedel Craft Alkylation Reaction and Aromatization Reaction Riemann Tiemann Reaction SN2 Mechanism N-Acylation and Nitration Reaction Addition Reaction Aromatic Nucleophilic Substitution by Elimination –Addition Mechanism and Diazo coupling reaction Grignard Reaction Halogenation Reaction and amide formation Elimination and Addition Reaction
49.
Dehydration and Epoxidation Reaction
50.
Aliphatic Nucleophilic Substitution and Chlorination by SNi
51. 52. 53. 54. 55. 56. 57. 58. 59. 60. 61. 62. 63. 64. 65. 66. 67. 68. 69. 70. 71. 72.
mechanism and SN2 Mechanism Friedel Craft Acylation and Clemmensons Reduction Nitration ans N-Acylation Reaction Chlorination with stereochemistry and Elimination Reaction by Saytzeff rule Diazotization Reaction with stereochemistry and oxime formation Hydroboration – Oxidation Reaction SNi Mechanism Nitration and Aromatic Nucleophilic Substitution Halogenation and Nitration Reaction Aromatic Electrophilic Substitution Vilsmeyer Haack Formylation Reaction Friedel Craft Acylation Reaction Hunds Dicker Reaction Oxidation and Nitration Reaction Aldol Condensation Reaction Epoxidation and Hydrolysis Vilsmeyer Haack Formylation Reaction Halogenation Reaction and Neighbouring Group Participation by Pi bond Halogenation: Aromatic Electrophilic Substitution Halogenation: Aromatic Electrophilic Substitution Methylation and Nitration Reaction Rearrangement Diazotisation and Diazo coupling Reaction Rearrangement
73. 74. 75. 76. 77. 78. 79. 80. 81. 82. 83. 84.
Pyrolytic Elimination Reaction Vilsmeyer Haack Formylation Reaction Dehydration: Elimination Reaction Aliphatic Nucleophilic substitution: Chlorination Cyclisation Aliphatic Nucleophilic substitution Aromatic Electrophilic Substitution Phase Transfer Catalyst Addition and Elimination Reaction Methylation , Oxidation and Hydrolysis Aliphatic Nucleophilic substitution and Reduction Halogenation: addition Reaction with Stereochemistry
85. 86. 87. 88. 89. 90. 91. 92. 93. 94. 95. 96. 97. 98. 99. 100.
Elimination Reaction (E2) Alkylation Reaction Iodination Reaction Addition Reaction Through Rearrangement Friedel Craft Alkylation Reaction Aromatic Electrophilic Substitution Friedel Craft Acylation Reaction and Bromination reaction Pyrolytic Elimination Reaction Sulphonation and Nitration Reaction Aromatic Nucleophilic Substitution Nitration and Oxidation Reaction Sandmeyer Reaction Pyrolytic Elimination Reaction Diazotization and Neighbouring Group Participation Dehydration: Elimination Reaction Neighbouring Group Participation with Stereochemistry
109. 110. 111. 112. 113. 114. 115. 116. 117. 118. 119.
Benzyne Formation Ortho Nitration reaction Grignard Reaction Friedel Craft Acylation Reaction and Clemmensons Reduction Elimination Reaction Addition Reaction Neighbouring Group Participation by Hetero atom and Grignard Reagent Elimination Reaction and Neighbouring Group Participation by Aryl ring Cyclisation Nitration Reaction Dehydration and Elimination Reaction Elimination Reaction with Stereochemistry Methylation and o-Nitration Bromination and Elimination Reaction Elimination and Epoxidation Reaction Addition and Cyclisation Reaction Neighbouring Group Participation by Aryl ring Pyrolytic Elimination Reaction Acid Hydrolysis reaction
120. 121. 122. 123. 124. 125. 126.
Elimination Reaction: E2 Aliphatic Nucleophilic substitution and Catalytic Reduction N-Acylation and Nitration Reaction Friedel Craft Alkylation, Oxidation and Halogenation Addition and Rearrangement Reaction Dehydration and Hydroxylation Reaction Grignard Reagent and Dehydration
101. 102. 103. 104. 105. 106. 107. 108.
127. 128. 129. 130. 131. 132. 133. 134. 135. 136. 137. 138. 139. 140. 141. 142. 143. 144. 145. 146. 147. 148. 149. 150. 151. 152. 153.
Dehydration and Epoxidation Reaction Elimination and Addition Reaction Aromatic Nucleophilic Substitution Friedel Craft Acylation Reaction Dehalogenation Reaction Aromatic Electrophilic Substitution Aliphatic Nucleophilic Substitution Cyclisation Neighbouring Group Participation by heteroatom Aromatic Electrophilic Substitution Aromatic Nucleophilic Substitution: Elimination Addition Mechanism Gattermann Koch Reaction Benzyne Formation and [4+2] Cyclisation Reaction Aromatic Electrophilic Substitution Diazotization and Diazo coupling reaction Aromatic Electrophilic Substitution Vilsmeyer Haack Formylation Reaction Benzyne Formation and Aromatic Nucleophilic Substitution Alkylation and selective Reduction Catalytic Reduction and Elimination Reaction Aromatic Electrophilic Substitution Wolf Kishner Reduction and Halogenation Reaction Elimination and Ozonolysis Reaction Neighbouring Group Participation by heteroatom Esterification Aliphatic Nucleophilic Substitution and Reduction Neighbouring Group Participation by Pi bond
154. 155. 156. 157. 158. 159. 160. 161. 162. 163. 164. 165. 166. 167. 168. 169. 170. 171. 172. 173. 174. 175. 176. 177. 178. 179. 180. 181.
Nitration Reaction Nitration, Reduction and N-Acylation Reaction Dehydration, Epoxidation and Grignard reagent Addition Reaction and Cyclisation Dehydrohalogenation Reaction O-Acylation Reaction and Cyclisation Reduction and Sandmeyer Reaction Chlorination and Aliphatic Nucleophilic Substitution Reaction Michael Addition and Hydrolysis Nitration Reaction Friedel Craft Acylation Reaction Halogenation and Amide Formation Reaction Elimiantion and Epoxidation with Stereochemistry Dehydrohalogenation and Bromination Reaction Higher Alkyne Formation and Selective Reduction N-Acylation, Bromination and Deprotection Cyclisation Reduction, Diazotisation and Sandmeyer Reaction Aromatic Electrophilic Substitution Elimination Reaction Halogenation, Alkylation and Elimination Reaction Hydration Reaction and o- alkylation reaction Iodination and Cyclisation Friedel Craft Alkylation Reaction Friedel Craft Acylation Reaction Nitarion Reaction Aldol Condensation Crossed Aldol Condensation
181. 1. Nitration Reaction
2. Nucleophilic Substitution by NGP
3. Aromatic Nucleophilic Substitution
4. Halo-hydroxylation Substitution
Reaction
and
Aliphatic
Nucleophilic
5. Neighbouring Group Participation by sigma bond
6. Aromatic Electrophilic Substitution and Diazotization
7. Aromatic Nucleophilic Substitution
8. Addition Reaction
9. Nitration Reaction
10. Aromatic Electrophilic Substitution
11. Neighbouring Group Participation by sigma bond
12. Elimination Reaction with Rearrangement
13. Rearrangement
14. Pyrolytic Elimination Reaction
15. Gattermann Koch Reaction
16. Pinacol Pinacolone Rearrangement
17. Alkylation and Dehydration Reaction
18. Neighbouring Group Participation by heteroatom
19. Aromatic Nucleophilic Substitution and condensation
20. Aromatic Electrophilic Substitution
21. Addition Reaction
22. Methylation and Vilsmeyer Haack Formylation Reaction
23. Elimination and Addition Reaction
24. Aromatic Nucleophilic Substitution
25. Neighbouring Group Participation by sigma bond
26. Diazotization Reaction with stereochemistry
27. Friedel Craft Acylation and Condensation Reaction
28. Addition Reaction: Bromination
29. Rearrangement
30. Aliphatic Nucleophilic Substitution and Chlorination by SNi mechanism
31. Aliphatic Nucleophilic Substitution
32. Jacobson’s Reaction
33. NGP by Aryl ring
34. Elimination Reaction by E2 Mechanism
35. Cyclisation by protonation
36. Cyclisation by using PTSA
37. Aromatic Nucleophilic Substitution by Elimination –Addition Mechanism
38. Diazotization Reaction with stereochemistry
39. Neighbouring Group Participation by heteroatom and Aliphatic Nucleophilic Substitution
40. Friedel Craft Alkylation Reaction and Aromatization Reaction
41. Riemann Tiemann Reaction
42. SN2 Mechanism
43. N-Acylation and Nitration Reaction
44. Addition Reaction
45. Aromatic Nucleophilic Substitution by Elimination –Addition Mechanism and Diazo coupling reaction
46. Grignard Reaction
47. Halogenation Reaction and amide formation
48. Elimination and Addition Reaction
49. Dehydration and Epoxidation Reaction
50. Aliphatic Nucleophilic Substitution and Chlorination by SNi mechanism and SN2 Mechanism
51. Friedel Craft Acylation and Clemmensons Reduction
52. Nitration ans N-Acylation Reaction
53. Chlorination with stereochemistry and Elimination Reaction by Saytzeff rule
54. Diazotization Reaction with stereochemistry and oxime formation
55. Hydroboration – Oxidation Reaction
56. SNi Mechanism
57. Nitration and Aromatic Nucleophilic Substitution
58. Halogenation and Nitration Reaction Aromatic Electrophilic Substitution
59. Vilsmeyer Haack Formylation Reaction
60. Friedel Craft Acylation Reaction
61. Hunds Dicker Reaction
62. Oxidation and Nitration Reaction
63. Aldol Condensation Reaction
64. Epoxidation and Hydrolysis
65. Vilsmeyer Haack Formylation Reaction
66. Halogenation Reaction and Neighbouring Group Participation by Pi bond
67. Halogenation: Aromatic Electrophilic Substitution
68. Halogenation: Aromatic Electrophilic Substitution
69. Rearrangement
70. Methylation and Nitration Reaction
71. Diazotisation and Diazo coupling Reaction
72. Rearrangement
73. Pyrolytic Elimination Reaction
74. Vilsmeyer Haack Formylation Reaction
75. Dehydration: Elimination Reaction
76. Aliphatic Nucleophilic substitution: Chlorination
77. Cyclisation
78. Aliphatic Nucleophilic substitution
79. Aromatic Electrophilic Substitution
80. Phase Transfer Catalyst
81. Addition and Elimination Reaction
82. Methylation , Oxidation and Hydrolysis
83. Aliphatic Nucleophilic substitution and Reduction
84. Halogenation: addition Reaction with Stereochemistry
85. Elimination Reaction (E2)
86. Alkylation Reaction
87. Iodination Reaction
88. Addition Reaction Through Rearrangement
89. Friedel Craft Alkylation Reaction
90. Aromatic Electrophilic Substitution
91. Friedel Craft Acylation Reaction and Bromination reaction
92. Pyrolytic Elimination Reaction
93. Sulphonation and Nitration Reaction
94. Aromatic Nucleophilic Substitution
95. Nitration and Oxidation Reaction
96. Sandmeyer Reaction
97. Pyrolytic Elimination Reaction
98. Diazotization and Neighbouring Group Participation
99. Dehydration: Elimination Reaction
100. Stereochemistry
Neighbouring Group Participation with
101. Benzyne Formation
102.
Ortho Nitration reaction
103.
Grignard Reaction
104. Reduction
Friedel Craft Acylation Reaction and Clemmensons
105.
Elimination Reaction
106.
Addition Reaction
107. Neighbouring Group Participation by Hetero atom and Grignard Reagent
108. Elimination Reaction and Neighbouring Group Participation by Aryl ring
109.
Cyclisation
110. Nitration Reaction
111. Dehydration and Elimination Reaction
112. Elimination Reaction with Stereochemistry
113. Methylation and o-Nitration
114. Bromination and Elimination Reaction
115. Elimination and Epoxidation Reaction
116. Addition and Cyclisation Reaction
117. Neighbouring Group Participation by Aryl ring
118. Pyrolytic Elimination Reaction
119. Acid Hydrolysis reaction
120.
Elimination Reaction: E2
121. Aliphatic Nucleophilic substitution and Catalytic Reduction
122.
N-Acylation and Nitration Reaction
123.
Friedel Craft Alkylation, Oxidation and Halogenation
124.
Addition and Rearrangement Reaction
125.
Dehydration and Hydroxylation Reaction
126.
Grignard Reagent and Dehydration
127.
Dehydration and Epoxidation Reaction
128.
Elimination and Addition Reaction
129.
Aromatic Nucleophilic Substitution
130.
Friedel Craft Acylation Reaction
131. Dehalogenation Reaction
132.
Aromatic Electrophilic Substitution
133.
Aliphatic Nucleophilic Substitution
134.
Cyclisation
135.
Neighbouring Group Participation by heteroatom
136.
Aromatic Electrophilic Substitution
137. Aromatic Nucleophilic Substitution: Elimination Addition Mechanism
138.
Gattermann Koch Reaction
139.
Benzyne Formation and [4+2] Cyclisation Reaction
140.
Aromatic Electrophilic Substitution
141. Diazotization and Diazo coupling reaction
142.
Aromatic Electrophilic Substitution
143.
Vilsmeyer Haack Formylation Reaction
144. Substitution
Benzyne Formation and Aromatic Nucleophilic
145.
Alkylation and selective Reduction
146.
Catalytic Reduction and Elimination Reaction
147.
Aromatic Electrophilic Substitution
148.
Wolf Kishner Reduction and Halogenation Reaction
149.
Elimination and Ozonolysis Reaction
150.
Neighbouring Group Participation by heteroatom
151. Esterification
152.
Aliphatic Nucleophilic Substitution and Reduction
153.
Neighbouring Group Participation by Pi bond
154.
Nitration Reaction
155.
Nitration, Reduction and N-Acylation Reaction
156.
Dehydration, Epoxidation and Grignard reagent
157.
Addition Reaction and Cyclisation
158.
Dehydrohalogenation Reaction
159.
O-Acylation Reaction and Cyclisation
160.
Reduction and Sandmeyer Reaction
161. Chlorination and Aliphatic Nucleophilic Substitution Reaction
162.
Michael Addition and Hydrolysis
163.
Nitration Reaction
164.
Friedel Craft Acylation Reaction
165.
Halogenation and Amide Formation Reaction
166.
Elimiantion and Epoxidation with Stereochemistry
167.
Dehydrohalogenation and Bromination Reaction
168.
Higher Alkyne Formation and Selective Reduction
169.
N-Acylation, Bromination and Deprotection
170.
Cyclisation
171. Reduction, Diazotisation and Sandmeyer Reaction
172.
Aromatic Electrophilic Substitution
173.
Elimination Reaction
174.
Halogenation, Alkylation and Elimination Reaction
175. Hydration Reaction and o- alkylation reaction
176.
Iodination and Cyclisation
177.
Friedel Craft Alkylation Reaction
178.
Friedel Craft Acylation Reaction
179.
Nitration Reaction
180.
Aldol Condensation
181. Crossed Aldol Condensation