The Formulation and Preparation of Cosmetics, Fragrances and Flavors [2nd (Revised)] 9781870228107, 1870228103

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The Formulation and Preparation of

Cosmetics, Fragrances and Flavors

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The Formulation and Preparation of

Cosmetics, Fragrances and Flavors with an Introduction to the Physical Aspects of Odor

and Selected Syntheses of Aromatic Chemicals

Louis Appell Licencié és Sciences (Geneva)

Revised Edition

MICELLE

PRESS

Weymouth, Dorset, England

UNITED BOOKS & PERIODICALS Bombay, India

08.5

This edition of Cosmetics, Fragrances and Flavors is published by arrangement with Novox Incorporated, Whiting, New Jersey, United States of America. Copyright © 1982 Novox, Inc. Index copyright © 1994 Micelle Press

All rights reserved. Apart from any fair dealing for the purposes of research or private study, or criticism or review, as permitted under the UK Copyright Designs and Patents Act, 1988, no part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior permission in writing of the Publishers, or in the case of reprographic reproduction only in accordance with the terms of the licences issued by the Copyright Licensing Agency in the UK, orin accordance with the terms of licences issued by the appropriate reproduction rights organization outside the UK.

First edition published 1982 under the title Cosmetics, Fragrances and Flavors (ISBN: 0-9610056-1-0)

This revised edition published 1994

A catalogue record for this book is available from the British Library. ISBN: 1-870228-10-3

ESSEX COUNTY LIBRARY Published by Micelle Press, 12 Ullswater Crescent, Weymouth, Dorset DT3 5HE,

England

Distribution of this book in India is handled exclusively by United Books & Periodicals, 7 Vishwadham, Prabhat Colony Road, Santacruz (East), Bombay 400 055, India. Telephone 611 6909 and Fax (91) 22-610 5852.

Cover design by Slade Design & Marketing

Printed and bound in Great Britainby Antony Rowe Limited, Chippenham, Wiltshire

Publisher’s Preface to the Revised Edition This book is a revised version of Louis Appell’s Cosmetics, Fragrances and Flavors which was first published in the United States in 1982. Louis Appell was bom in Alsace-Lorraine in 1901 and died in New Jersey, United States, in 1987, at the age of 85. He left France at about the age of 30, and became head of the Department of Agriculture of Costa Rica. After several years in Costa Rica he moved to New York, where he was a founder of Don Juan

Cosmetics, serving as Chief Chemist. He was also the proprietor of Remsen Chemicals, a distributor of perfume chemicals, and towards the end of his life acted as a consultant. This book, which he wrote in his retirement, summarizes a

lifetime’s formulating experience in the cosmetics and fragrances industry. This revised edition is essentially the same as the original edition, but there are one or two changes. A general index has been added for greater ease of reference. The raw materials index has been completely revised to reflect changes in nomenclature in the cosmetics industry. Errors in formulations which the author himself discovered soon after publication have been corrected. The formulations in this classic book have thus been rendered more accessible to the many students of cosmetics and perfumery science, who will find it a valuable source of information.

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Preface to the First Edition This book deals with many aspects of the formulation of cosmetics, perfumes and flavors. It differs from other publications inasmuch as it reflects to a large extent the personal experience of the author. The objective was to present new material and reliable information. Chapter I deals with the formulation of cosmetics. The chemistry and manufacturing procedures are discussed, but the well-known generalities are omitted. The formulations are limited to quality products many of which are similar to trade prototypes. Several formulations are for entirely new products. Furthermore, over 200 manufacturers’ ingredient label declarations are reported under the various cosmetic classes. These declarations will be found particularly valuable in studying the present trend in formulation. Chapter II is an introduction to the physical aspects of odor. It sums up and expands the findings of the author that were published in a series of articles in the American Perfumer.' Chapter III deals with a practical method of creation in perfumery based on the principle of olfactory equilibrium and equivalent weight that is established in the preceding chapter. A formulary to assist in this work contains systematically arranged formulas for French style perfumes, colognes and floral compositions. Additional sections deal with imitation essential oils, perfume specialties and perfumes for cosmetics and soaps. Chapter IV deals with flavor compositions. The importance of olfactory equilibrium is again stressed. Furthermore, a sharp distinction is made between the highly volatile elements that impart freshness of odor and those of lower volatility that form the heart of the individual flavors. Chapter V deals with the stability of the aromatic products in various cosmetic media. Chapter VI is devoted to syntheses of selected aromatic chemicals. This chapter should be of interest to both perfumers and organic chemists who need information on the processes used today in the industry. As is well-known, many processes have been proposed but few are of practical and economical interest. Those selected were carefully checked. A short presentation has been used throughout the text. The perfume formulas are given in four columns which reduced considerably the size of the book. The cosmetic formulas are shown in two columns, again for economy of space without resorting to smaller, less legible type. Finally, a revised presentation of the aromatic syntheses shows all the reactants at a glance. This compendium of practical perfumery is meant to give useful information to supplement rather than duplicate other publications on the subject. New York, N.Y.

1982 'Now Cosmetics and Toiletries.

Louis APPELL

Contents

Chapter I The Formulation of Cosmetics

1. Aerosols . Bath preparations . Creams and hand lotions . Dentifrices . Deodorants and antiperspirants . Depilatories . Gels . Hair bleaches and related preparations OoNNMN WN 9. Hair conditioners 10. Hair dyes 11. Hair grooming preparations 12. Hair waving preparations 13. Lipstick 14. Make-up preparations 15. Perfumes and fragrance products 16. Shampoos 17. Shaving preparations 18. Molded glycerin and transparent soaps 19, Suntanning preparations 20. Miscellaneous cosmetics

Chapter II Physical Aspects of Odor

1. . . . .

Volatility and vapor pressure Physical laws in odorimetry Measurement of vapor pressure Minimum perceptible Odor intensity Olfactory equilibrium

HAWN ADM . Odor

classification

Chapte r II] The Formulation of Perfumes

1 . Formula presentation . Coding system . Volatility sequence . Composition styles . Raw materials . Compounds and specialties ANA WW NP . Method of creation in perfumery

Contents co.

Symbols and codes . Perfume formulations 9-1. Perfumes (French style) 9-2. Cologne fragrances 9-3. Floral fragrances 9.4. Perfumes for cosmetics and soap

9.5. Specialty bases 9.6. Essential oil imitations Chapter IV The Formulation of Flavors Chapter V Stability of Perfumes and Cosmetics

Chapter VI Selected Aromatic Syntheses . . . . .

Acetophenone and methyl acetophenone Amylcinnamic aldehyde Anisic aldehyde and p-cresyl methyl ether Benzophenone Cinnamic aldehyde Citral

. Citronellyl oxyacetaldehyde . Cuminic aldehyde . Cyclamen aldehyde . Esters: —SOW ANNMNHRWN Allyl hexanoate (Caproate) Amyl hexanoate (Caproate) Cinnamy]l isobutyrate Geranyl acetate Geranyl phenylacetate Linalyl acetate Menthyl acetate Phenylethyl acetate Phenylethyl formate Vetiveryl acetate . Ethyl methyl phenyl glycidate . Eugenol . Isoeugenol . Geraniol and citronellal . Hydratropic aldehyde . Hydroxycitronellal . Ionone . Methyl ionone . Jasmyl acetate (Nonanediol acetate)

ix

265 278 219

x

Contents

20. vAe eles ZS; 24. vane

Phenylacetaldehyde dimethylacetal Menthol Musk ambrette Cyclic musks. Ethylene glycol brassylate Phenylethyl alcohol Pinene and camphene derivatives: Terpineol Terpinyl acetate Isobornyl acetate Bornyl acetate

Chapter VII Outline of Aromatic Syntheses . Carvone . Cinnamy]l alcohol . Coumarin . Dimethylbenzylcarbinyl acetate . Heliotropin . Isocyclocitral . Methyl nonyl acetaldehyde . Undecalactone . Vanillin from eugenol —SOO ANAINMNRWN . Total syntheses of linalool, linalyl acetate and citral

425

Appendix

427

Concluding Notes

439

Chapter I The Formulation of Cosmetics The cosmetic formulations developed for this text comprise the following groups: 1. Aerosols 2. Bath preparations

3. Creams and lotions 4. Dentifrices 5. Deodorants and antiperspirants 6. Depilatories 7. Gels 8. Hair bleaches 9. Hair conditioners 10. Hair dyes

11. Hair grooming preparations 12. Hair waving products

13. Lipsticks 14. Make-up 15. Perfumes and fragrance products 16. Shampoos 17. Shaving preparations 18. Soaps 19. Suntanning preparations 20. Miscellaneous cosmetics

In each group, the product or composition forms such as liquids, gels, creams, etc, are enumerated together with references to the corresponding formulations in the text. Formulation characteristics are discussed, but generally known facts and references to the literature are omitted since this information can be found in several encyclopedic works. Manufacturers’ ingredient label declarations are reported in the various groups. The formulations are based on raw materials listed in a special index. In order to arrive at a uniform presentation and nomenclature, common and generic names were preferred. This also includes CTFA! adopted names for the ethoxylated products and the quaternary compounds designated as “quaterniums” under the CTFA codes. However, trade names were retained for a limited number of chemicals that are widely known in the industry. These have the advantage of short names that readily identify the supplier. In any case, the source of the ingredients used in the formulary is always given. This is of course essential since many products are not interchangeable although they are classified under the same CTFA name. In the selection of raw materials preference has been given to well-defined chemicals for proper label declaration as required by law. Furthermore, a comparatively limited number of materials are recommended to avoid excessive stock items as much as possible. An attempt has also been made to give a satisfactory description of the end products which are often similar to well-known prototypes. Of course, in most cases this reflects only similarity in physical appearance and use. However, 1The Cosmetic, Toiletry and Fragrance Association, Washington, D.C.

2

The formulation of cosmetics

since label ingredient declarations are now mandatory, the duplication of cosmetics is greatly simplified and similarity in chemical composition can also be achieved to a certain extent. The formulas show the ingredients in two columns for economy of space. In order to list integral quantities as much as possible, the formula total is not always exactly 100. If for some reason this total is requested, a simple proportion gives the desired result, but of course decimal parts are introduced which are undesirable in manufacturing operations. Preservatives

Not all the formulations given in this book show the preservative explicitly. However, all cosmetics must be preserved, including anhydrous preparations that are used with aqueous application such as mascara and cake make-up. In view of this, the usual annotation “q.s. preservative” is omitted since it is of little use unless the preservative is mentioned specifically. Anionic emulsions are often preserved with 0.15% methylparaben in the — water phase and 0.15% propylparaben in the oil phase. This assumes preservation of both phases, although methylparaben may partially migrate into the oil phase since it is more soluble in oil than in water. The preservation of non-ionic emulsions is particularly critical. For this purpose, imidazolidinyl urea in the presence of both methyl and propylparaben is now frequently recommended. Quaternium-15 is also increasingly used. As mentioned above, preservatives are not always specified in the formulas. In this case the manufacturers’ ingredient label declarations for similar cosmetics should be consulted as guidance on the preservatives to be used. Antioxidants are also frequently added. This seems unnecssary in most cases since many raw materials already contain antioxidants, particularly the aromatic chemicals used in compounding perfumes. Perfume Concentration

The perfume is often omitted in the formulas. Its concentration generally varies from 0.1 to 0.5% and depends on the strength of the perfume oil, the nature of the basic cosmetic and the desired volume of odor. The perfume is usually added to the emulsions at 65°C or lower, but it can also be added to the oil phase before emulsification. However this is not recommended for perfumes high in citrus oils since the main component, limonene, is volatile, although no more so than propylene glycol. These factors rarely present problems. The stability of perfumes in cosmetics is another question which is treated in Chapter V. Ingredient Label Declarations

About 200 examples of ingredient label declarations of leading cosmetic firms have been added to the text. These are of great interest in many respects

The formulation of cosmetics

3

since they reveal the present trend in cosmetic formulation and preservation. The ingredients, as requested by law, are shown in the order of decreasing predominance. This however can be misleading since dilutions are usually not reported. For instance sodium lauryl sulfate is sometimes not listed in the correct order for the 100% material. A frequent ingredient reported is glyceryl stearate. This could be glyceryl monostearate, but often refers to widely used specialties. Since the label ingredient declarations can involve materials that are not used in this text, alternate materials are sometimes suggested to substantiate the interpretation as much as possible. Manufacturing Adjustments Manufacturing adjustments are often required when passing from the laboratory scale to the production scale. This may involve changes in the agitation system or the filling operation in order to reproduce exactly a cosmetic that was approved on a laboratory scale. These mechanical adjustments are made on preliminary or pilot plant runs. Occasionally an adjustment in the formulation may also be necessary. Particular attention should be given to make-up and other preparations that must be kept at fairly high temperature prior to filling since this may cause unwanted changes in color, transparency, consistency, or other factors. Although this is not a common occurrence it can be spotted in the laboratory by heating samples at the same temperature and for the same length of time as during processing in the plant. This operational stability test should not be confused with cosmetic and perfume stabiliity tests which are treated in Chapter V.

4

The formulation of cosmetics

CTFA Abbreviations' BHA BHT DEA DMDM EDTA GMS He MEA MIPA

Butylated hydroxyanisole Butylated hydroxytoluene Diethanolamine _Dimethylol dimethyl Ethylene diamine tetra acetic acid Glyceryl monostearate Hair color Monoethanolamine Monoisopropanolamine

PABA

Paraaminobenzoic acid _

PEG POE PPG PVP SD TEA VA

Polyethylene glycol Polyoxyethylene Polypropylene glycol Polyvinylpyrrolidone Specially denatured (Alcohol) Triethanolamine Vinyl acetate

Other Abbreviations

CRMCS D&C Ext. D&C FDA

FD&C NF USP

Cosmetic Raw Material Composition Statement? Drug & Cosmetic (Color) D&C color for external use Food & Drug Administration Food, Drug & Cosmetic (Color) National Formulary United States Phamacopoeia

'The Cosmetic Toiletry and Fragrance Association, Washington, D.C. The initials also refer to the CTFA Cosmetic Ingredient Dictionary. 2CTFA Dictionary, Section IX. Compositions under these numbers have adopted chemical names for label declarations.

The formulation of cosmetics

5

INDEX OF RAW MATERIALS Trade Chemicals Used in the Formulary Note: The suppliers of the raw materials listed below and the lexicographical status of these materials have been brought up to date for this new edition. Except where otherwise indicated in the notes atthe end of this index, the nonproprietary names appear in the fifth edition of the CTFA International Cosmetic Ingredient Dictionary.

Adol 85

Oleyl Alcohol (cosmetic grade) [Witco

Adol 158 Amerlate P Ammonyx 4 Arlacel 60 Arlacel 165

C15-18 Glycol!

Chemical]

Brij 30 Brij 35

Brij 56 Brij 58 Brij 76 Brij 78

Isopropyl Lanolate [Amerchol] Stearalkonium Chloride 20% active [Stepan] Sorbitan Stearate [ICT] Glyceryl Stearate (and) PEG-100 Stearate, (self-emulsifying, acid stable) [ICT] Laureth-4 [ICI] Laureth-23 [ICI] Ceteth-10 [ICT]

Ceteth-20 [ICI] Steareth-10 [ICI] Steareth-20 [ICI]

Brij 99

Oleth-20?

Calgon Carbopol 940

Sodium Hexametaphosphate [Calgon] Carbomer [B.F. Goodrich] PEG-32

Carbowax 1500° Carnation oil

Cellosize QP 520004 Cetyl alcohol Chloracel 40%

Chlorhydrol 50% Coconut Oil, hydrogenated Crodafos N3 neutral Dicrylan 325 WA-50 Dowicil 200 Duponol ou Ethylene glycol monostearate Ethylene glycol distearate Germall 115 Giv-Tan F” GMS

Igepal CO-730 Igepon AC-78 (now called

Mineral Oil (white, cosmetic grade) [Witco

Chemical, Sonneborn]} Hydroxyethylcellulose [Amerchol] Cetyl Alcohol (NF grade) [various suppliers] Sodium Aluminum Chlorohydroxy Lactate [Reheis] Aluminum Chlorohydrate [Reheis] [various suppliers] DEA Oleth-3 Phosphate [Croda] Acrylate/Acrylamide Copolymer® Quaternium-15 [Dow Chemical] Sodium Lauryl Sulfate [DuPont] Glycol Stearate® Glycol Distearate (Kessco grade)[Stepan] Imidazolidinyl Urea [Sutton] Cinoxate [Givaudan] Glycery1 Stearate (glyceryl monostearate) [Henkel/Organic Products] Nonoxynol-15 [Rhéne-Poulenc] Sodium Cocoy] Isethionate [Rhéne-Poulenc]

Geropon AC-780)

Kaydol

Mineral Oil (white) [Witco Chemical, Sonneborn]

6

The formulation of cosmetics

Lantrol

.

Maprofix NH Methocel EAM

Miranol C2M Multiwax 180M

Natrosol Neo-Fat Neo-Fat Neo-Fat Neo-Fat Neo-Fat

250 12-43 14 18 18-55 255

Ozokerite!°

Paraffin wax, m.pt. 53°C (128°F)

Polyethylene glycol 400 distearate Polymer JR 125 (now called UCARE Polymer JR-125) Polymer JR 400 (now called UCARE Polymer JR-400) Potassium stearate Propylene glycol PG monostearate

Protol Protopet 1E

Protopet 1S PVP, NP-K30 Shell Sol 71 Silicone L-43!! Silicone L-45 Sodium stearate Solulan 16 Solulan-C24 (Solulan 24 in the first edition of this work)

Standamid Standapol Standapol Standapol Standapol

LD A ES-2 ES-40 T

Standapol WAQ Special!”

Lanolin Oil [Henkel/Organic Products] Ammonium Laury] Sulfate [Onyx] Hydroxypropy! Methylcellulose [Dow Chemical] Disodium Cocoamphodiacetate [RhdnePoulenc] Microcrystalline Wax [Witco Chemical, Sonneborn] Hydroxyethylcellulose Lecualon| Lauric Acid [Akzo] Myristic Acid [Akzo] Stearic Acid [Akzo]

Stearic Acid [Akzo] Coconut Acid [Akzo] [various suppliers] Paraffin [various suppliers] PEG-8 Distearate (not self-emulsifying, Kessco grade) [Stepan] Polyquaternium-10 [Amerchol] Polyquaternium-10 [Amerchol]

[Witco Chemical] [Union Carbide] Propylene Glycol Stearate (propylene glycol monostearate pure, Kessco grade) [Stepan] Mineral Oil (white) [Witco Chemical, Sonneborn] Petrolatum (yellow, NF) [Witco Chemical, Sonneborn] Petrolatum (white, USP) [Witco Chemical, Sonneborn] PVP (polyvinylpyrrolidone) [ISP] Petroleum Distillates [Shell] Dimethicone [Union Carbide] Dimethicone [Union Carbide] Sodium Stearate C-1 [Witco Chemical] Laneth-16 (and) Ceteth-16 (and) Oleth-16 (and) Steareth-16 [Amerchol] Choleth-24 (and) Ceteth-24 [Amerchol] Lauramide DEA [Henkel] Ammonium Laury1 Sulfate [Henkel}

Sodium Laureth Sulfate [Henkel] Sodium Myreth Sulfate [Henkel] TEA-Lauryl Sulfate [Henkel] Sodium Lauryl Sulfate [Henkel]

The formulation of cosmetics

Stearic acid

7

Stearyl alcohol Super Hartolan

Stearic Acid (cosmetic grade, triple-pressed) [various suppliers] Stearyl Alcohol (USP) [various suppliers] Lanolin Alcohol [Croda]

TEA

Triethanolamine (commercial)!* [Union

'

i

Carbide]

Triton X-400 Tween 20 Tween 60 Ucon Fluid LB-1715

Stearalkonium Chloride [Rohm & Haas] Polysorbate 20 [ICT] Polysorbate 60 [ICT] PPG-40 Butyl Ether [Union Carbide]

Veegum HV ,

Magnesium Aluminum Silicate

Varion CADG Tech.!*

Cocamidopropyl Betaine, 35% [Witco]

Vegetable oil 1400!4

[R.T. Vanderbilt] Caprylic/Capric Triglyceride [PVO]

Victory wax Volpo 3

Microcrystalline Wax [Petrolite] Oleth-3 [Croda]

Volpo 5

Oleth-5 [Croda]

1. Deleted after the second edition of the CTFA Cosmetic Ingredient Dictionary, in which it is described as cetyl stearyl vicinal glycol, supplied by Ashland. This range is now supplied by Witco Chemical, although this particular item may no longer be available.

2. Deleted after the fourth edition of the CTFA International Cosmetic Ingredient Dictionary, in which it is described as Oleth-20. Subject to confirmation by ICL, it can probably be replaced by the similar Brij 98. 3. Deleted after the second edition of the CTF'A Cosmetic Ingredient Dictionary, in which it is described as PEG-6-32. Subject to confirmation by Union Carbide, it can probably be replaced by the similar Carbowax PEG 1450. 4. Now called Cellosize HEC QP. 5. In the first edition of Cosmetics, Fragrances and Flavors, the author suggests Cobee 92 [PVO], although this material is deleted after the fourth edition of the CTFA International Cosmetic Ingredient Dictionary. 6. Deleted after the second edition of the CTFA Cosmetic Ingredient Dictionary. Since it may no longer be available, Ciba-Geigy should be consulted regarding a replacement. 7. Deleted after the third edition of the CTFA Cosmetic Ingredient Dictionary. This material is a standard item and available from many suppliers. 8. In the first edition of the present work, the author suggests Kessco 70 [Stepan], although this material is not listed in any edition of the CTFA Cosmetic Ingredient Dictionary, Stepan should be consulted conceming the correct grade. 9. Deleted after the third edition of the CTFA Cosmetic Ingredient Dictionary. Since it may no longer be available, Givaudan should be consulted regarding a replacement. 10. In the first edition of the present work, the author suggests Ozokerite No. 4, m.pt. 85°C

[International Wax Refining] although this material is not listed in any editions of the CTFA Cosmetic Ingredient Dictionary. The following footnote appears in the first edition: Ozokerite is a natural wax that used to be imported from Czechoslovakia and the Ukraine. Today it is produced synthetically from microcrystalline wax with additives for hardness. These products are therefore not always interchangeable. Ozokerite is available from many suppliers. 11. Not listed in any edition of the CTFA Cosmetic Ingredient Dictionary. Union Carbide should be consulted regarding the correct grade to use. 12. Deleted after the second edition of the CTFA Cosmetic Ingredient Dictionary. Henkel should be consulted regarding a replacement. 13. In the first edition of the present work, the author suggests 85% purity, although higher grades,

with lower diethanolamine levels, are now preferred. 14. Deleted after the second edition of the CTFA Cosmetic Ingredient Dictionary. This material is a standard item and available from many suppliers. 15. Deleted after the fourth edition of the CTFA International Cosmetic Ingredient Dictionary. Witco Chemical should be consulted regarding a replacement.

8

The formulation of cosmetics

COLOR INDEX Cosmetic Lakes and Pigments Color index

D&C name

Sun code! C C C C C C C C C

19-012 19-025 19-003 15-007 15-010 21-003 23-009 69-002 70-5270

D&C Red No. D&C Red No. D&C Red No. D&C Red No. D&C Red No. D&C Red No. D&C Red No. FD&C Yellow FD&C Yellow

6, Barium Lake 7, Calcium Lake 7, Calcium Lake 8, Sodium Lake 9, Barium Lake 19, Aluminum Lake 36, Barium Lake No. 5, Aluminum Lake No. 6, Aluminum Lake

Common name

no.

Light Rubine Lake Rubine Lake 1 Rubine Lake 2 Toning Orange Desert Red Geranium Lake Flaming Red Yellow Lake Persian Orange

15850 15850 15850 15585 15585 45170 12085 19140 15985

Inorganic Colors Color index

Sun code C C C C C

33-007 33-115 33-120 33-123 33-128

Sun name Cosmetic Cosmetic Cosmetic Cosmetic Cosmetic

Tan Brown Oxide M, Yellow Red Oxide M, Blue Red Russet

Common name

no.

Dark Ochre Brown Umber Sienna Dark Sienna Russet

77491/2 77491/9 77491/2 77491/2 77491

C 33-134

Cosmetic Black

Cosmetic Black

77499

C 43-1810 C 61-1245

Cosmetic Blue U Cosmetic Green

Ultramarine Blue Chromium Oxide Green

77007 77288

'Code letter C refers to colors manufactured by Sun Chemical Corporation, Rosebank, Staten

Island, N.Y. 1030S.

Make-up formulations given in the text are based on the color codes. The D&C names cannot be used for this purpose since these do not fully specify the type of color. For instance, D&C Red 7 Calcium Lake is available as four different colors depending on the manufacturing procedure. This is also the case for the inorganic pigments. On the other hand, the code system is entirely satisfactory since the lakes and pigments are standardized for color as well as for chemical composition. As this book goes to press, it appears that D&C Red No. 9, an important lipstick color, may be delisted since there is evidence of carcinogenic potential. At the same time, it is reported that the lithol reds No. 10, 11, 12, and 13 may be reinstated. These colors had been used for over a century but were delisted in 1976 because of the presence of traces of G-naphthylamine. This contaminant may now be reduced to less than 0.002 ppm, thanks to advanced analytical and processing techniques. Since this level appears to be acceptable, lipstick shades that had been formerly established by the author were reinstated alongside the newer substitute formulations.

The formulation of cosmetics

9

HOW TO USE THE COSMETIC FORMULARY Although this section contains over 200 formulations, there is often only a single formula for a particular cosmetic product. A selection is given for some groups, but this may offer a difficult choice unless samples are available. In this case, certain formulations should be tested first as a likely choice. These are listed in the following table. Product

Bath products

Reference

Shampoos Shaving products Soaps Suntan products

2. 13, 16,.193222-330 32, 39 41, 43 §2C, 53A, 55B 66 73 92, 93 101, 105, 110C 111 117, 118 128 132 141 to 158 162, 165 173, 177, 178, 184, 185, 186, 188A 192, 195, 196 201, 205 208, 210

Miscellaneous

230

Creams Hand lotions Dentifrices Deodorants

Depilatories Gels Hair bleaches Hair conditioners Hair dyes Hair grooms Hair waves Lipsticks Make-up Fragrance products

10

Aerosols

1. AEROSOLS A large number of cosmetics can be packed as aerosols. However, few have found market acceptance as is shown in the following breakdown of sales:

1. 2. 3. 4.

Colognes and perfumes Deodorants and antiperspirants Hair sprays Shaving creams

15% 20 40 20

5. Depilatories, after-bath and

after-shave lotions, quick breaking foams, shampoos

5 - 100%

As can be seen, liquid sprays (above items 1, 2, 3) account for 75% of the aerosol cosmetics and shaving creams form the bulk of the aerosol foams. Formulations for the following aerosols are given under the respective titles: Bath sprays Hair net Shampoo Shaving cream Suntan butter

Ref 1 Ref 116 Ref*l77 Ref 191, 192 Ref 206

The formulation of shampoo aerosol Ref 177 should be noted since this type of product is believed to have good potentials. A specially equipped laboratory is of course required for pressurizing aerosols. Only a few years back this had to be improvised, but today excellent laboratory equipment is available for both pressure and cold filling. Builder’s Corporation (New York) offers such facilities and also provides information needed for the filling operation. Examples of Trade Formulations From Manufacturer’s Product Label

Edge. Self-foaming shaving gel, dispensed as an aerosol, S.C. Johnson & Son, Racine, Wisconsin. U.S. Patent 3 541 581 Ingredients: Water Palmitic acid Triethanolamine Pentane (1) Sorbitol Fatty acid esters

Isobutane (1) Cellulose polymer Fragrance FD&C Blue No. 1 D&C Yellow No. 10

Remarks:

(1) Post foaming agents and pressurizers for the sepro container with the gel

-

Aerosols

11

Gillette. Aerosol self heating shave cream. U.S. Patents 3441722, 3341418, 3454198

Ingredients: Water Stearic acid Triethanolamine 1,5-Diethyl-4-hydroxy-2-mercapto-6oxopyrimidin (1) Isobutane (2) Laureth-23 Potassium hydroxide Sorbitol Hydrogen peroxide (3)

Sodium lauroyl sarcosinate Propane (2) Fragrance Lauramine oxide (4) Potassium silicate (5) Butane (2) Ammonium molybdate (6) Phenacetin Sodium stannate

Remarks: (1) Reducing agent of the exothermic reaction! (2) Pressurizer of the two sepro containers (3) Oxidation agent packed in sepro together with traces of phenacetin and sodium stannate (4) Lauryl dimethyl amine oxide, e.g. Ammonyx LO, Onyx (5) Buffer or corrosion inhibitor (6) Oxidation accelerator Palmolive.

Aerosol Rapid Shave, regular, Colgate-Palmolive Co.

Ingredients: Water TEA stearate Giycerin Isobutane (1) Ceteth-20 Potassium cocoate

Stearic acid Sodium lauryl] sulfate Lauramide DEA Fragrance Propane (1) Sodium silicate (2)

Remarks: (1) Propellant (2) Corrosion inhibitor 'Apparently a condensation compound of diethylmonoethanolamine with thiourea, the heating elements that are favored in this text.

or monoethanolamine

12

Aerosols

Gillette, Trac IT. Aerosol shaving cream

Ingredients: Water Potassium stearate Peanut oil Isobutane (1) Laureth-23 Sorbitol Mineral oil Stearic acid Propane (1)

Cetyl alcohol Fragrance Menthol Carbomer 941 (2) PEG-15 cocoamine (3) Butane (1) BHA BHT

Remarks:

(1) Propeilant (2) Carbopol 941, Goodrich Chemical (3) Ethomeen C 25, Armak

Noxell.

Aerosol shaving cream, Noxell Corporation, Baltimore

Ingredients:

Water Stearic acid Isobutane (1) Sorbitol Polysorbate-20 (2) Triethanolamine Coconut acid (3) Remarks: (1) (2) (3) (4)

Petrolatum Propylene glycol Ammonium hydroxide Propane (1) Cetyl alcohol Fragrance Sodium metasilicate (4)

Propellant Polyoxyethylene 20 sorbitan monolaurate, Tween 20, ICI e.g. Neo-Fat 255, Armak Corrosion inhibitor

Neet.

Aerosol hair remover, Whitehall Laboratories

Ingredients: Water Isobutane Thioglycolic acid

Stearyl alcohol Sodium silicate Perfume oil

Mineral oil Sodium hydroxide Calcium hydroxide Sorbitol

Paraffin Ceteareth-20 Cetyl alcohol

Bath preparations

13

2. BATH PREPARATIONS The commonly used bath preparations are the following: Aerosol bath sprays. Ref 1 Bath oils, floating. Ref 2 Bath oils, foaming. Ref 3 and 4 Bath oils, opaque lotions. See Shampoos Bath gels. See Gels Bubble bath powders. Ref 5 Milk bath powders. Ref 6 Spa bath salts. Ref 7 Floating bath oils are among the most popular bath preparations. Typical trade formulations consist of perfumed mineral oil. A surfactant is usually added to help the formation of a thin film. The spreading action can be readily observed by placing a drop of bath oil on a surface of water. Isopropyl myristate spreads instantly. Mineral oil forms globules that do not spread at all. Mixtures of the two oils spread poorly and addition of a surfactant is of little help. A ideal bath oil is obtained by using only isopropyl myristate with addition of 5 to 10% perfume. The mixture should be tested since some perfumes impair spreading. See Ref 2. Foaming bath oils rank next in popularity. There are two types, either clear solutions or opaque emulsions. These products are practically identical with shampoos, except for the concentration of perfume which is generally higher. The amount of foam that is desirable is a matter of personal preference and is easily controlled by varying the percentage of surfactant. The perfume concentration varies greatly, usually from 0.5 to 3%. At a higher concentration, the preparation is primarily meant to perfume the bath.

Examples of Trade Formulations From Manufacturer’s Product Label

Vitabath.

(Badedas), Bath Gel, Beecham Co.

Ingredients: Sodium laureth sulfate (1) Disodium monolaureth sulfosuccinate (2) Laureth-7 (3) Cocoamide DEA (4) PEG-8 (5) Fragrance Water Lanolin Lanolin alcohol

Sunflower oil | Horse chestnut extract Citric acid Rutin (6) Calcium pantothenate (7) Vitamin A Vitamin E synthetic Biotin (8) Triethanolamine

14

Bath preparations

Remarks:

(1) (2) (3) (4) (5) (6) (7) (8)

e.g. Standapol ES-2, Henkel Emcol 4300, Witco Chemical Polyoxyethylene 7 lauryl alcohol, e.g. Lipal, PVO Coconut diethanolamide, e.g. Superamide L 9, Onyx Polyethylene glycol 400, e.g. Carbowax 400, Union Carbide A botanical chemical Vitamin Bs Calcium salt Vitamin H

Clairol Herbal Bubble Bath.

Clear lotion

Ingredients:

Water Sodium lauryl sulfate Oleth-20 Disodium monolaureth sulfosuccinate (1) Sodium laureth sulfate Fragrance Laureth-3 Sodium cetyl sulfate (2) Choleth-24 (3) Diisopropyl adipate (4)

Lauryl alcohol 2-Bromo-2-nitropropane-1,3-diol (5) Methyl paraben PEG-75 Lanolin (6) Disodium EDTA Propyl paraben FD&C Yellow No. 5 FD&C Yellow No. 6 D&C Yellow No. 8 FD&C Blue No. 1

Remarks:

(1) (2) (3) (4) (5) (6)

Emcol 4300, Witco Chemical e.g. Duponol W, E.I. DuPont & Co. Polyoxyethylene 24 cholesterol, Solulan C-24, Amerchol Ceraphyl 230, Van Dyk Bronopol, Inolex Lantrol AWS, Malmstrom Chemical

Avon, Smooth as Silk Bath Oil

Ingredients: Mineral oil Isopropyl palmitate Fragrance Alcohol SD 40 B Nonoxynol-4 (1)

Propylparaben Benzophenone-1!1 (2) D&C Red No. 17 D&C Yellow No. 11

Remarks: (1) e.g. Igepal CO-430, GAF Corp. (2) Ultraviolet absorber, e.g. Uvinul 490, GAF Corp.

Bath preparations

15

Formulations Aerosol Shower Smoother

Ref 1 A

2 2 4 #| eS, 17

Oleth-20 (1) Stearic acid Isopropyl myristate Mineral oil, visc. 70 GMS

BiG 82 0.15 0.2 _0.05 83

.01.8 A Water Methylparaben Perfume FD&C Blue No. 1 T 100

(1) Brij 99, ICI Mix A and B at 75°C. Stir until cold. Pressurize with 10% by volume, Freon 114/12, 65/35. This foam rubs out as a slightly tacky film. Floating Bath Oil Instant Spreading

Isopropyl myristate

0.2

D&C Yellow No. 11,

1% (1) Perfume oil

je 0.2

T 100.2

(1) Solution in isopropyl myristate Cold mix. See text.

Foaming Bath Oil No. 1 Na laureth-3 sulfate (1) Water FD&C Yellow No. 5,1%

Citric acid

B...0,52 C 2

26 30.5

Petfame Lauramide DEA (2) Sodium chloride

Water T 100.7

(1) Standapol ES-40, 60% active, Henkel (2) Standamid LD, Henkel Mix A and Bat 50°C. When Bis dispersed, add solution C and preservatives.

16

Bath preparations Foaming Bath Oil No. 2

Ref4

A 40 52

0.1 92.1

TEA lauryl sulfate (1) Water Methylparaben

Bz 4 Qi 8

Perfume Igepal CO-730 (2) Lauramide DEA (3) T 100.1

(1) Standapol T, 60% active, Henkel (2) Nonoxynol-15, perfume solubilizer, GAF Corp. (3) Standamid LD, Henkel

Mix A and B at 50°C. Bubble Bath Powder

Duponol C (1) Calgon (2)

80 wide 81

Sodium sesquicarbonate Perfume T 100

(1) Sodium lauryl sulfate 100%, E.I. DuPont de Nemours (2) Sodium hexametaphosphate, Hooker Chemical Co. Simple mixing. Milk Bath Powder

Ref6 A

19 0.75

1625 B 10 31

Titanium dioxide FD&C Red No. 40, 1% FD&C Yellow No. 5, 1% Water = 19 after drying

C 50 30 1 -) 81

Lactose Igepon AC-78 (1) Perfume Preservatives T 100

(1) Sodium lauryl isethionate, 83% active. Gaf Corp. Mix A and B in a pony mixer. Put the resulting slurry on trays and dry in oven. An evenly colored dry powder is obtained. Add to C and pulverize in Fitzpatrick mill. Spa Bath Salts

Sodium sesquicarbonate Calgon Sodium chloride Magnesium sulfate (1)

B

1 1 2 aes 6

Pine needle oil Chlorophyll, oil soluble Igepal CO-730 Alcohol 95% vol T 100

(1) Epsom salt

Mix A and Bin pony mixer. Heat B slightly for uniform mix before adding to A. Package in opaque container to prevent fading of color.

Creams and hand lotions

17

3. CREAMS AND HAND LOTIONS Cream and lotion formulations of every description can be found in the trade booklets. This source of information is very valuable although the number of surfactants that are being promoted is excessive. ! The emulsions or products described in this section fall into the following categories: All purpose creams. Ref 13 Cleansing creams or cold creams. Ref 11, 12 Cleansing cream without beeswax. Ref 14 Cleansing cream, liquifying. Ref 15A Cocoa butter formula. Ref 15B Facial creams (1) Moisturizing creams. Ref 16-18 (2) Emollient creams. Ref 19-22 (3) Conditioning creams. Ref 23-25 Vanishing creams. Ref 26 Waterless hand cleaners. Ref 27 Vitamin E creams. Ref 28, 29 Conditioning beeswax cream. Ref 30 Hand lotions. Ref 31-39 Gel lotions. See Gels

Cosmetic creams are usually described as moisturizing, emollient or conditioning, but these terms are not precisely defined. For our purpose, moisturizing creams are creams of light or soft consistency with relatively low oil content, whereas emollient and conditioning creams can have increasingly higher oil content. The rub-out is an important specification: It should never be watery or too greasy. On rubbing the cream into the skin it should not turn white (soapy), an indication of excess wax. Emulsions can also be classified according to the type of surfactant. Of the many surfactants that are available, only the following few systems find application in the formulary: Beeswax/Borax system: One of the oldest emulsifying systems, extensively used for cold creams. Stearic acid/TEA system: Widely used for creams in pH range of 7.5-8.0. Ethoxylated alcohol systems: Mostly used for anionic acidic creams, and as secondary emulsifiers in other systems. Lauryl sulfate systems: Widely used in shampoos and in the presence of electrolytes.

'McCutcheon’s “Detergents and Emulsifiers Annual” covers over 5000 trade surfactants.

18

Creams and hand lotions

Whether the newer non-ionic creams should be preferred to the older types of emulsions is a question that is not within the scope of this book. Suffice it to mention that both types are widely promoted as is apparent from the label declarations of trade cosmetics. The non-ionic creams are mostly acidic rather than neutral because the ethoxylated alcohols are commonly stabilized with 0.005% citric acid, the pH of these materials varying usually between 3.0 to 4.0 at 5% concentration in water. It should be noted that non-ionic creams (i.e. creams emulsified exclusively with ethoxylated alcohols) are prone to bacterial decomposition. Since the parabens are ineffective when used alone in these creams, additional preservatives must be added. Imidazolidinyl urea in conjunction with the parabens is often recommended for this purpose. Quaternium-15 is also widely used as can be verified in the label declarations. An absolute necessity is the addition of propylene glycol which is a very effective

preservative of the water phase. Many cosmetics now contain several preservatives in a single preparation, particularly when the formulations are designed to meet the bacteria challenge test. These preparations often contain quaternary compounds that sterilize contaminations with common microorganisms such as gram-positive (E. coli, etc), gram-negative (Pseudomonas, etc), or molds and yeasts. Formaldehyde functions similarly, but since it polymerizes it is inactive for accidental contaminations that may occur after packaging the preparations. Few remarks seem necessary about the formulations. Note, however, that

the classical formulas for cold creams and cleansing creams, which were always considered easy to formulate, must be revised due to the high cost of beeswax and the fact that natural spermaceti is presently not available. These materials were used extensively as shown in formula Ref 11. Synthetic spermaceti cannot be used as a replacement since it lacks the required crystalline structure, not to mention its poor odor. As is well-known this material, like many other waxes and fatty acids, is now produced petrochemically from fossil oil, and these new synthetics do not always have the same physical properties as the original products. Filling Cosmetic Creams A first question is whether creams or other cosmetics should be filled hot or cold. Hot filling is necessary when mirror-like surfaces are desirable as in cold cream and make-up. This assumes that the product can be kept fluid for several hours and that proper cooling equipment is available. As is wellknown, emulsions must be cooled before capping to prevent water from condensing under the caps. Cold filling is often preferred for creams since they can be rapidly cooled in the manufacturing kettles. Furthermore, the jars can be capped immediately after filling. Of course, the surface of cold filled creams is often unsatisfactory, but this may not be of importance when the cream is covered with a liner or cellophane disk.

Creams and hand lotions

19

The filling equipment must now be considered. For filling hot, gravity fillers are best since the mass is fluid. However, piston fillers are also used, although the turbulent flow at the outlet may introduce air into the product and spoil the appearance of the surface. A pneumatic flow filler! is ideal since

it does not require an overflow or a firm seal with the container. This ingenious filling machine is operated by a tubular filling sensor that conducts a continuous flow of air at low pressure. As soon as the prearranged liquid level is reached, the pressure increases in the sensor and triggers off compressed air that retracts the nozzle and stops the flow. In small production it is often necessary to resort to hand filling. A special cream filler that fills 4 to 6 jars at a time will now be described. It consists of two bushings (S-in. tubing) cut in half lengthwise, the inner bushing rotating in the stationary outer bushing by means of a handle. When the precisely tooled outlets in these bushings are aligned, there is a full flow of liquid. The flow is slowed at the end by the operator to obtain the proper fill. With six outlets, up to 60 jars can can be easily filled per minute. The jars should of course be crated in a light tray so they can be pushed in rapid succession under the outlets and conveyed to a cooling tunnel. This unit could also be used for gravity filling of cold liquids, although diversified equipment, including vacuum fillers, is available for this purpose. These fillers require an overflow which is not desirable when the liquid sets to solid form. Furthermore, a firm seal with the containers is necessary during filling but not always possible with flexible plastic packaging. The next operation is the cooling of the containers. For small production

this is best achieved with a forced air cooling tunnel. A suitable design is shown in Appendix. It consists of a 24 x 24-in., 32-ft-long insulated tunnel that encloses completely a slow moving conveyor. This tunnel is connected to an air duct of the same dimensions placed above the tunnel together with a blower B that moves the air over refrigeration coils C kept at — 20°C. Vanes are used to cycle the flow of air in the tunnel. A 20 HP Freon 22 refrigeration unit is not shown in the figure; it is usually suspended from the ceiling or installed on the roof. The temperature in the tunnel is kept at 2 to 3°C; this cannot be lowered because of icing. The cooling time depends on the load in the tunnel and the heat content of the product. The tunnel will cool 1000 units of 4-oz jars of Petrolatum (Brilliantine) from 65°C to 35°C in one hour. The ideal speed of filling for a continuous flow is therefore 16 units per minute. Faster cooling (about twice as fast) is achieved for aqueous creams since they can be poured around 50°C and have a much lower heat of fusion than petrolatum. For large production, tunnels are not adequate because of excessive length. In this case, jars of other goods are preferably moved in layers on wide diameter rotating spirals. As the products move to lower layers or compartments, the temperature steadily drops, although it must be kept above 0°C to prevent icing. \Manufactured by Delamere & Williams, Toronto. Distributed by Pneumatic Scale Corporation, Quincy, Mass.

20

Creams and hand lotions

Examples of Trade Formulations From Manufacturer’s Product Label

Noxema Skin Cream. Noxell Corporation Active ingredients: Camphor, Phenol (less than 1/4%), Clove oil, Eucalyptus oil and Menthol Other ingredients:

Water Stearic acid Linseed oil Soybean oil Fragrance Pond’s Dry Skin Cream.

Propylene glycol Gelatin Ammonia Calcium hydroxide

Chesebrough-Pond’s

Ingredients:

Water Mineral oil Petrolatum Arachidyl propionate (1) Isopropyl palmitate Stearic acid Glycerin Glyceryl stearate Sorbitan oleate (2)

Ceresin Cetyl alcohol TEA Laureth-23 (3) Fragrance Carbomer-934 (4) Methyl paraben Propyl paraben Quaternium-15 (5)

Remarks:

(1) (2) (3) (4) (5)

Ester of arachidyl alcohol (Arachidic acid is readily available) e.g. Arlacel 80, ICI

e.g. Brij 35, ICI Carbopol 934, Goodrich Chemical Dowicil 200, Dow Chemical

Pond’s Cold Cream

Ingredients:

Mineral oil Water Beeswax Ceresin Remarks: (1) Carbopol 934, Goodrich Chemical

Sodium borate Fragrance Carbomer-934 (1) Methyl paraben

Creams and hand lotions

Avon, Rich Moisture Hand Cream.

21

Light consistency for tube packaging

Ingredients: Water Stearic acid Glycerin Cetyl alcohol Sesame oil PEG-40 stearate (1) Mineral oil Sorbitan sesquioleate (2)

Lanolin Fragrance Methyl paraben Propyl paraben Lonolin alcohol Pentasodium pentetate (3) BHA (4)

Remarks: (1) (2) (3) (4)

Possibly Arlacel 165, ICI e.g. Arlacel 83, ICI A sesquestrating agent, e.g. Versenex 80, Dow Chemical Butylated hydroxyanisol, e.g. Tenox BHA, Eastman

Ultima IT. CHR Moisture Creme Concentrate, Charles Revson Inc, Division of Revlon

Ingredients:

Water Isopropyl myristate Lanolin oil Propylene glycol Hydrogenated soy glyceride (1) Mineral oil Sweet almond oil TEA stearate Hydrogenated vegetable oil (2) Stearic acid Sorbitan stearate (3) Cetyl alcohol

Collagen (4) Synthetic spermaceti Fragrance Polysorbate-60 (5) Glutaral (6) Methylparaben Propylparaben Quaternium-15 (7) Dilauryl thiodipropionate (8) Trisodium EDTA Trisodium phosphate

Remarks: (1) (2) (3) (4) (5) (6) (7)

Myverol 18-06, Eastman Chemical Products Myverol 18-50, Eastman Chemical Products e.g. Arlacel 60, Span 60, ICI Protein from connective tissues in animals. Collasol, Croda Polyoxyethylene 20 sorbitan monostearate, ICI Glutaraldehyde (Preservative), Union Carbide Dowicil 200, Dow Chemical

22

Creams and hand lotions

Vitamin E Beauty Cream. ter, N.Y? Active ingredient:

The Health Savings Center, Dist. Rockville Cen-

Vitamin E, 100 1.U. per gram (10%)

Other ingredients: Water Propylene glycol White Petrolatum Mineral oil

Stearic acid Stearyl alcohol

Glyceryl monostearate Triethanolamine Methylparaben Imidazolidinyl urea Sodium lauryl sulfate Propylparaben

Revion Eterna “27.” Beauty cream

Ingredients: Pregnenolone acetate (1) Water Mineral oil Beeswax Propylene glycol Isopropyl myristate Petrolatum Sweet almond oil Synthetic spermaceti Lanolin alcohol Avocado oil Sorbitan oleate (2) Lanolin wax (3) Safflower glyceride (4): Sorbitan trioleate (5) Vitamin E Remarks:

(1) (2) (3) (4) (5)

(6) (7) (8)

A steroid (CTFA) e.g. Arlacel 80, ICI e.g. Waxolan, Amerchol Myverol 18-98, Eastman Chemical e.g. Span 85, ICI Nicotinamide (CTFA) A lanolin sterol (CTFA) Vitamin B 6 hydrochloride (USP)

Niacinamide (6) Cholesterol Lanosterol (7) Cetyl alcohol Sodium borate Fragrance Pyridoxine (8) Corn oil BHA BHT Methyl paraben Propyl paraben Butyl paraben Trisodium EDTA Carotene D&C Green No. 6

Creams and hand lotions

Helena Rubinstein, Natural Moisture Cream. Ingredients: Water Mineral oil Stearyl alcohol Natural moisturizing factor (1) Cocoa butter Petrolatum Isostearic acid Beeswax PEG-40 stearate (2) Dimethicone (3) Sorbitan tristearate (4) Lanolin

23

For dry skin

Triethanolamine Safflower oil Peach kernel oil Avocado oil Sesame oil Methyl paraben Fragrance Hydroxyethyl cellulose (5) Tocopherols (6) Propyl paraben Rose oil

Remarks: (1) (2) (3) (4) (5) (6)

100% Natural moisturizers, Patent applied for Polyoxyethylene 40 monostearate, Myrj 52, ICI e.g. Dow Corning 200 Fluid, or Silicone L-45, Union Carbide Span 65, ICI e.g. Cellosize QP, Union Carbide Vitamin E acetate

Dorothy Gray, Satura Throat Cream

Ingredients: Water Aluminum hydroxide Alcohol SD 40 Beeswax Propylene glycol Dioctyl succinate (1) Stearyl alcohol PEG-20 lanolin Zinc stearate

Remarks: (1) Wickenol 159, Whickhen Products (2) e.g. Arlacel 165 (3) e.g. Ceraphyl 424, Van Dyk (4) Veegum, Vanderbilt Co. (5) Vitamin A in corn oil (6) Dowicil 200, Dow Chemical

Glycol stearate (2) Myristyl myristate (3) Petrolatum (and) lanolin (and) lanolin alcohol Magnesium, aluminum silicate (4) Fragrance Sodium chloride Corn oil (and) retinyl palmitate (5) Quaternium-15 (6)

24

Creams and hand lotions

Orlane, Paris, Creme Superhydratante B 21 Ingredients: Water Mineral oil Isopropyl myristate Glyceryl stearate Palmitic/stearic triglyceride (1) PEG 50 stearate (2) PEG 8 stearate (3) Stearic acid Cholesterol Panthenol Serine (4) Sorbitol

’

Arginine glutamate (5) Fragrance Sodium PCA (6) Urea Methyl paraben Propyl paraben Triethanolamine Vitamin E synthetic Lactic acid Allantoin (7) Vitamin A

Remarks:

(1) (2) (3) (4) (5) (6) (7)

e.g. Vegetable oil 1400, PVO e.g. Myrj 53, ICI e.g. Myrj 45, ICI Amino acid, Ajinomoto Ajinomoto Sodium pyroglutamate, Ajinomoto Schuykill Chemical Co.

Moon Drops, Emollient Eye Balsam, Revion Ingredients:

Water Mineral oil Sweet almond oil Isopropyl palmitate Beeswax Microcrystalline wax Lanolin Propylene glycol Sorbitan tristearate Lanolin wax Hydrogenated castor oil Lanolin alcohol Sunflower glyceride Polysorbate 61 (1) Remarks:

Urea Glucose glutamate (2) Hydrolyzed animal protein Sodium lactate Sodium PCA (3) Sodium borate Fragrance Methylparaben Propylparaben Butylparaben BHA Trisodium EDTA Carotene Magnesium sulfate

(1) Tween 61, ICI (2) Wickenol 545, Wickhen Products, Inc (3) Sodium pyroglutamate, Ajinomoto Co.

Creams and hand lotions

Eye Cream, Helena Rubinstein Ingredients: Water Lanolin Mineral oil Petrolatum Sesame oil Beeswax Hydrogenated cotton seed oil

Spermaceti, synthetic Paraffin Lanolin alcohol Methylparaben Fragrance Zinc phenol sulfonate Vitamin A

Remarks: A beeswax borax emulsion

Nivea, Moisturizing Cream.

Beiersdorf Inc, South Norwalk, Conn

Ingredients: Water Mineral oil Petrolatum Glycerin Microcrystalline wax Lanolin alcohol Paraffin Magnesium sulfate

Balm Barr, Cocoa butter formula.

Decyl oleate Octyl dodecanol Aluminum stearate Fragrance Formaldehyde Citric acid Magnesium stearate

The Mennen Co.

Ingredients: Water Cocoa butter Hydrogenated coconut oil (1) Mineral oil Petrolatum Glyceryl stearate Sorbitol Stearic acid Cetyl alcohol Triethanolamine

Remarks: (1) Cobee 92, PVO (2) e.g. Ethomeen C/25, Armak (3) Dowicil 200, Dow Chemical (4) An antioxidant, Olin Corporation

PEG-15 cocamine (2) Fragrance Carbomer-934 Quaternium-15 (3) Methylparaben Propylparaben Stearic hydrazide (4) FD&C Yellow No. 5 D&C Red No. 19

25

26

Creams and hand lotions

Examples of Trade Formulations (Lotions) From Manufacturer’s Product Label

Avon

Vita Moist Body Lotion

Ingredients

Water Stearic acid Sesame oil Glycerin Acetylated lanolin alcohol Squalene (1)

Triethanolamine Glyceryl stearate Sodium aluminum silicate (2) Methyl paraben Fragrance Propyl paraben

Remarks:

(1) A saturated branched hydrocarbon which imparts a cosmetic feel like mineral oil. It is obtained by hydrogenation of natural oils such as shark liver oil. (2) e.g. Zeolex, Huber Corp. Vaseline Intensive Care Lotion.

Chesebrough-Ponds

Ingredients: Water Glycerin Glyceryl stearate Stearic acid Mineral oil Cetyl alcohol Laureth-23 (1) Trisopropanolamine Lanolin Isopropyl palmitate

Fragrance Methyl paraben Propylene glycol Carbomer 934 (2) Propyl paraben Simethicone (3) Trisodium EDTA D&C Red No. 19 D&C Yellow No. 10

Remarks: (1) Lauryl alcohol 23 POE, e.g. Brij 35 ICI (2) Carbopol 934, Goodrich Chemical (3) e.g. Antifoam A, Dow Corning

Creams and hand lotions

Jergen’s Hand Lotion. Ingredients:

27

Regular lotion, white

Water SD Alcohol 40 B Glycerin Cetyl alcohol Spermaceti (synthetic) Propylene glycol stearate Triethanolamine stearate (1) Peanut oil Sodium tallowate PEG-150 (2)

Sodium borate Beeswax Propylene glycol dipelargonate Fragrance Sodium carbomer 941 (3) Methyl paraben Lanolin Salicylic acid Sodium cocoate Propyl paraben

Remarks: (1) Reaction product of stearic acid and triethanolamine (2) e.g. Carbowax 6000, Union Carbide (3) Reaction product of Carbopol 941, Goodrich Chemical Jergen’s Lotion for Dry Skin.

Yellow color

Ingredients: Water Glycerin Cetyl alcohol Ceteareth-20 (1) Palm oil glyceride Glyceryl dilaurate Mineral oil Petrolatum Dimethicone (2)

Isopropyl palmitate Stearic acid Allantoin Methyl paraben Sodium carbomer-934 (3) Propyl paraben Quaternium-15 (4) FD&C Yellow No. 5 FD&C Red No. 3

Remarks: (1) Cetyl stearyl alcohol 20 POE (2) Dimethylpolysiloxane, e.g. Dow Corning 200 Fluid (3) Carbopol 934 (Goodrich Chemical), in part neutralized with sodium hydroxide (4) Dowicil 200, Dow Chemical

28

Creams and hand lotions

Rain Tree, Moisturizing Lotion.

Noxell Corp

Ingredients:

Water Mineral oil Stearic acid Glyceryl stearate Lanolin oil Oat flour

Methyl paraben Triethanolamine Fragrance Carbomer-941 Imidazolidinyl urea (1) EDTA

Remarks:

(1) Germall 115, Sutton Labs

Oil of Olay. Olay Co., Wilton, CT Ingredients (Slightly rearranged): Water Mineral oil Potassium laurate, myristate, palmitate and stearate (1) Sodium laurate, myristate, palmitate and stearate (2) Cholesterol Cetyl palmitate Butyl paraben Sodium carbomer 934 (3)

Potassium carbomer 934 (3) Propyl paraben Methyl paraben Castor oil Myristyl alcohol Cetyl alcohol Stearyl alcohol Fragrance FD&C Red No. 4

Remarks: (1) Indicates a postassium soap base (2) Indicates a sodium soap base (3) Neutralized carbopol 934, Goodrich Chemical PhisoDerm. Lathering skin cleanser and conditioner (Facial foam lotion). Winthrop Labs, Division of Sterling Drug, Inc

Ingredients: Sodium octoxynol-3 sulfate (1) White Petrolatum Water Petrolatum and lanolin Lanolin alcohol Remarks:

(1) Triton X-200, Rohm & Haas Co. (2) Triton X-15, Rohm & Haas Co. (3) To adjust pH to 5.5 How to use:

Work up into lather, rinse thoroughly.

Sodium benzoate Octoxynol-1 (2) Methyl cellulose Lactic acid (3)

Creams and hand lotions Revlon, Moon Drop Moisture Balsam. Ingredients: Water Sweet almond oil Mineral oil

29

A hand lotion

Glucose glutamate (2) Sodium lactate Sodium PCA (3) Sodium lauryl sulfate Methyl paraben Propyl paraben Fragrance p-Hydroxy anisol Sodium dehydroacetate (4) Trisodium EDTA FD&C Yellow No. 5 FD&C Yellow No. 6

Propylene glycol Urea TEA Stearate Acetylated lanolin alcohols Sorbitol Hydrogenated soy glyceride (1) Lanolin oil Glyceryl stearate Hydrolyzed animal protein Remarks:

(1) (2) (3) (4)

Myverol 18-06, Eastman Chemical Products Wickenol 545, Whickhen Products Sodium pyroglutamate, Ajinomoto Co. A bactericide

Rubinstein

Rinse-off Cleanser.

A cleansing lotion with

100%

Natural

Moisturizers: Rosewater, Safflower oil, Peach kernel oil, Avocado oil, Sesame oil

Ingredients: Mineral oil Water Sorbitan palmitate (1) Polysorbate-40 (2) Lanolin Stearic acid Triethanolamine Sodium octoxynol-3-sulfonate (3) Cocoa butter Peach kernel oil Avocado oil Remarks:

(1) (2) (3) (4)

Arlacel 40, or Span 40, ICI e.g. Tween 40, ICI Triton X-200, Rohm & Haas Carbopol-941, Goodrich Chemical

Sesame oil Safflower oil Methylparaben Sodium lauryl sulfate Fragrance Carbomer-941 (4) Disodium EDTA Propylparaben Tocopherol Rose oil

30

Creams and hand lotions

Revlon Super Skin Cleanser.

A liquid emulsion

Ingredients: Water Mineral oil Propylene glycol Propylene glycol dicaprylate/dicaprate (1) Isopropyl myristate Triethanolamine stearate Hydrolyzed animal protein Glyceryl stearate Stearyl alcohol Steareth-20 Sweet almond oil Avocado oil

Peach juice Carrageenan (2) Lemon juice Lemon oil Peppermint oil Chamomile oil Rosemary oil

Armoise oil Fragrance TEA-Carbomer-941 Methylparaben Propylparaben Imidazolidinyl urea

Remarks:

(1) e.g. Tegester PG 8-10, Inoiex (2) e.g. Gelcarin, Marine Colloids, Inc Clinique, Extremely Smoothing Body Lotion.

Estee Lauder Mfrs

Ingredients: Purified water Mineral oil Stearic acid Glyceryl stearate Petrolatum Lecithin Sperm wax (1) Cetyl alcohol

MEA borate (2) Lanolin alcohol Imidazolidinyl urea Sodium dehydroacetate Methyl- & propylparaben FD&C Yellow No. 5 FD&C Red No. 33

Remarks: (1) Spermaceti, natural (2) Monoethanolamine borate Clinique, Dramatically Different Moisturizing Lotion. Ingredients: Purified water Mineral oil (and) lanolin alcohol (1) Sesame oil Propylene glycol TEA stearate Remarks:

(1) Amerchol L-101, Amerchol (2) Amerchol CAB, Amerchol

Estee Lauder Mfrs

Glyceryl stearate Petrolatum (and) lanolin alcohol (2) Methyl- & propylparaben FD&C Yellow Nos. 5 & 6 D&C Red No. 33

Creams and hand lotions

31

Pre-Tan Starter, Germaine Monteil Cosmetiques. “Naturally scented to prevent photo-sensitive skin reactions.” A light cream lotion, moist rub-in. Ingredients: Water Glycerin PPG-3 myristyl ether (1) Glyceryl stearate Dimethylaminopropyl stearamide (2) Acetylated lanolin Mineral oil Lanolin alcohol Tyrosine (3) Allantoin Hydrolyzate of elastin (4) Panthenol Hydroxypropyl methylcellulose (5) Remarks: (1) (2) (3) (4) (5) (6) (7) (8) (9) (10)

Cetyl alcohol Dimethicone Hydrogenated vegetable oil PEG-40 stearate (6) Quaternium-7 (7) Sorbitan tristearate (8) Propylparaben Imidazolidinyl urea Methylparaben Methylbenzethonium chloride (9) Galbanum coeur (10) Hexylcinnamic aldehyde Methylionone gamma pure

e.g. Witconol APM, Witco Chemical e.g. Tegamine S-13, Inolex Aminoacid Collagen Methocel, Dow Chemical e.g. Myrj 52, ICI e.g. Emcol E 607 S, Witco Chemical e.g. Span 65, ICI e.g. Hyamine 10X, Rohm & Haas Essential oil

Glo-Fine, Moisturizing Cocoa Butter Lotion. Valley Stream, N.Y. A beeswax type lotion

Ingredients: Water Mineral oil Ozokerite Beeswax PEG 400 distearate (1) Spermaceti

B&W

Formulators

Cocoa butter Sodium borate Methylparaben Propylparaben FD&C Yellow No. 6 Fragrance

Remarks:

e.g. PEG-8 distearate, Stepan, Kessco Division

Inc,

32

Creams and hand lotions

Supplegen, All-Day Moisturizing Cream.

Ingredients: Water Mineral oil Propylene glycol Glyceryl stearate Collagen Stearic acid Myristyl myristate Lauryl lactate Hydrogenated vegetable oil Glycerin Dimethicone Cetyl alcohol PEG-100 stearate

'

Germaine Monteil Cosmétiques

Propylparaben Imidazolidinyl urea Carbomer-940 Sodium benzoate Sorbitan sesquioleate Methylparaben Emulsifying wax NF (1) Myristyl myristate (2) Polysorbate-60 Triethanolamine Fragrance FD&C Yellow No. 5 FD&C Red No. 4

Remarks: (1) Yellow wax, NF (beeswax) (2) e.g. Ceraphyl 424, Van Dyk

Supplegen, Liquid Cleanser.

Germaine Monteil Cosmétiques

Ingredients: Water PPG-3 myristyl ether (1) Sorbitan stearate Polysorbate-60 (2) Propylene glycol Glycerin Stearic acid Beeswax Collagen Polysorbate-20 (3) Propylparaben Remarks: (1) (2) (3) (4) (5)

‘Methylparaben Triethanolamine Lanolin alcohol Imidazolidiny! urea Glyceryl stearate Squalane (4) Acetylated lanolin Fragrance Glutaral (5) FD&C Red No. 4 FD&C Yellow No. 5

e.g. Witconol APM, Witco Chemical Tween 20, ICI Tween 60, ICI e.g. Robane, Robeco Chemicals Glutaric dialdehyde, a preservative, Union Carbide

Creams and hand lotions

33

Formulations Cold Cream No. 1

Ref 11 A

15 4 50

Beeswax Spermaceti, natural (1) Mineral oil, visc. 70

69

B

1.1 30 C 0.35 0.15 31.6

Borax Water Rose perfume Methylparaben T 100.6

(1) Or paraffin (2) Mix A and B at 75°C. Fill hot. Set Pt 39°C. Cold Cream No. 2

Ref 12

A

10 47 4

Beeswax Mineral oil, visc. 70 Ozokerite No. 4

ees.

B 38 0.7. 0.1

C _0.5

61

39.3

Water Borax Methylparaben

Rose perfume T 100.3

Mix A and Bat 75°C. Fill hot. Set Pt is low (32°C). After cream has solidified, it does not melt when kept in oven at 42°C. All Purpose Cream B 20

Ref 13 A

3 0.35 1.5 1.5 IS 4 é) 28.35

Stearic acid Laureth-23 (1) Ozokerite No. 4 Paraffin Mineral oil, visc. 70 Petrolatum, white USP Cetyl alcohol

A 3 B41 3 0.1 60 C05

67.

GMS TEA Propylene glycol Methylparaben Water (Perrome

T 95.95

(1) Brij 35, ICI Mix A and B at 75°C. Fill hot. Set Pt 40°C.

34

Creams and hand lotions Cold Cream No. 3

Ref 14 A

5

0.6 3 2

Sau 35.6

Cetyl vicinal glycol (1) Stearic acid Lanolin alcohols (2) Cetyl alcohol Mineral oil, visc. 70

B

0.4 5 59 0.1 C 0.5 65

Borax Propylene glycol Water Germall 115 Perfume T 100.6

(1) Adol 158, Sherex Chemical, Viking Chemical Div. (2) Superhartolan, Croda Mix A and B at 75°C. Keep stirring at 75°C for at least 10 minutes for complete emulsification. Homogenize and fill hot. Set Pt 38°C.

Ref 15A A 15 5 79 99°

Cleansing Cream No. 2 Liquifying Type, Anhydrous Ozokerite No. 4 Petrolatum, white USP Mineral oil, visc. 70

B

1

"lee

Magnesium stearate Perfume

oT TO0

Heat waxes and oil to 95°C. Add B. Fill at about 60°C. Magnesium stearate adds whiteness to cream. Cream liquifies on skin although Set Pt is high.

Cocoa Butter Formula for the Skin Anhydrous

Ref 15B Stearic acid Ozokerite No. 4 Petrolatum, white USP Mineral oil, visc, 70

5 0.15 0.05 aL Ss

Heat waxes and oil to 95°C. Fill hot.

Cocoa butter D&C Red No. 17, 0.1% in isopropyl palmitate D&C Yellow No. 11, 1% in isopropyl palmitate T 100.2

Creams and hand lotions

35

Moisturizing Cream No. 1

Oleth-20 (1) Laneth-16 (2) Cetyl alcohol Petrolatum, white USP Mineral oil, visc. 70 Isopropyl myristate GMS —_

B

1.5. 35 0.1 C 0.25 45

D

I

4.55 86.35

Glycerin Water Methylparaben Perfume Carbopol 934, 1% dispersion T.EA 10% soln T 101.05

(1) Brij 99, ICI (2) Solulan 16, Amerchol Prepare stock of carbopol dispersion, preserve with 0.15% methylparaben. Mix A and B at 75°C. Add perfume and carbopol dispersion and mix until uniform. Sprinkle T E A solution over the batch and stop stirring as soon as the proper consistency is obtained. Fill cold. Moisturizing Cream No. 2 Mineral oil, visc. 70 GMS Stearic acid Petrolatum, white USP

B 60 0.5 7 0.15 C 0.05

67.7

Water Duponol C Propylene glycol Methylparaben D&C Orange No. 4, 1%

199.7

Mix A and B at 75°C. Set Pt 40°C. Moisturizing Cream No. 3

Mineral oil, visc. 70 GMS Stearic acid Cetyl alcohol Stearyl alcohol Lanolin Hydrog. coconut oil (1) Cetyl vicinal glycol (2)

in

B

1 0.15 0.15 0.1 03 0.2 70

Propylene glycol Methylparaben Propylparaben Germall 115 TEA Borax Water

71.9

T 88.4

(1) Cobee 92, PVO (2) Adol 185, Sherex Chemical, Viking Chemical Div. Mix A and Bat 75°C. Set Pt 45°C. Fill cold.

36

Creams and hand lotions Emollient Cream No. I

Ref 19 A

Propylene glycol Duponol C Water D&C Orange No. 4, 1% Methylparaben Pw02e7

GMS Petrolatum, white USP Mineral oil, visc. 70 Stearic acid Cocoa butter

12

4 13 5

pal 35

Mix A and B at 75°C. Set Pt 45°C. Fill at 55-60°C. For satisfactory surface gloss, filling temperature must be high. Emollient Cream No. 2

TEA Glycerin Methylparaben

Cetyl alcohol Petrolatum, white USP Laneth-16 (1) Mineral oil, visc. 70 Isopropyl myristate Stearic acid GMS

Water

73.95

T 100.45

(1) Solulan 16, Amerchol Mix A and B at 75°C. Set Pt 45°C. Fill at 55°C. Firm consistency, not fluid at 53°C. Emollient Cream No. 3

wn

Oleth-20 (1) Laneth-16 (2) GMS Isopropyl myristate Cetyl alcohol Petrolatum, yellow NF Mineral oil, visc. 70

Glycerin Germall 115, parabens Water FD&C Red No. 40, 1% Perfume

295-3

N \o 1m)

(1) Brij 99, ICI (2) Solulan 16, Amerchol

Mix A and B at 75°C. Add C at 60°C. Set Pt 41°C.

Creams and hand lotions Emollient Cream No. 4

Stearic acid Isopropyl lanolate (1) Lanolin alcohols (2) GMS Mineral oil, visc. 70 Propylparaben

B

08 5 0.15 65 C 0.3.

71.25

TEA Glycerin Methylparaben Water Perfume

T 101.4

(1) Amerlate P, Amerchol (2) Superhartolan, Croda

Mix A and B at 75°C. Set Pt 42°C. Conditioning Cream No. 1 Beeswax Petrolatum, white USP Petrolatum, yellow NF Mineral oil, visc. 70 Lanolin oil (1) Ozokerite No. 4

B

0.35 2 0.15 33 C.0:5. 36

Borax Laneth-16 (2) Methylparaben Water >Perfume T 100

(1) Lantrol, Emery Industries (2) Solulan 16, Amerchol

Mix A and B at 75°C. Set Pt 38°C. Conditioning Cream No. 2

Beeswax, white Beeswax, yellow Petrolatum, white USP Lanolin oil (1) Mineral oil, visc. 70

B

0.75 6) 0.15 33 C 0.5

(1) Lantrol, Emery Industries (2) Solulan 16, Amerchol Mix A and B at 75°C. Fill hot.

36.4

Borax Laneth-16 (2) Methylparaben Water #£=Perfume

T 100.4

B7

38

Creams and hand lotions

Conditioning Cream No. 3

Laneth-16 (1)

A

Petrolatum, white USP Oleth-20 (2) Cetyl alcohol Mineral oil, visc. 70 Isopropyl myristate

10 B 3 0.15 0.15 58.3

8

196%,

GMS Lanolin Glycerin Methylparaben Germall 115 Water 2% 100

(1) Solulan 16, Amerchol

(2) Brij 99, ICI Heat A and B to 75°C and mix. Stir until cold. Set Pt 38°C. This cream has a thin consistency and is fairly fluid at 42°C. Vanishing Cream Classical Formulation

Stearic acid Spermaceti Mineral oil, visc, 70

B

1 0.7 5 73

TEA Borax Glycerin Water

_0.1

Methylparaben

79.

8itinl 210023

Mix A and Bat 75°C. Stir to 55°C. Fill hot. Avoid mechanical agitation while filling to obtain a firm consistency. Cream cannot be reheated. See alternate formulation under brushless shaving creams. Waterless Hand Cleaner

Laneth-16 (1) GMS Stearic acid Cetyl alcohol Petroleum distillate (2)

B

5 Zz 0.15 53 C 20:1... 60.25

Glycerin TEA Methylparaben Water Perfume T 100.25

(1) Solulan 16, Amerchol (2) Shell Sol 71, Shell Chemical Mix A and B at 75°C. Set Pt 42°C. Caution: Shell Sol 71 has a low

flash point.

Creams and hand lotions

39

Vitamin E Cream No. 1 10% Vitamin E

Stearic acid Oleth-20 (1) Laneth-16 (2) GMS Vitamin E (3) Mineral oil, visc. 70 Isopropyl palmitate

A

1.5 0.1

Bet 3 51 0.2 _0.1 56.9

Odzokerite No. 4 Propylparaben TEA Propylene glycol Water Germall 115 Methylparaben T 99.6

(1) Brij 99, ICI (2) Solulan 16, Amerchol (3) Tocopherol acetate, Hoffmann-Laroche Mix A and B at 75°C. Fill at 45°C. Set Pt 39°C. Cream of this type may invert to W/O emulsions, which is recognized by inspection (oily appearance and application). This is corrected by reheating the cream for white color and fairly dry application. Low priced vitamin E dilutions are sometimes used in the trade. The vitamin content must of course be checked for proper label declaration. Colorimetric analytical procedure according to AOAC method No. 43094 is recommended. Vitamin E Cream No. 2 5% Vitamin E

Ref 29 A 10

Stearic acid Oleth-20 Laneth-16 GMS Vitamin E Isopropyl palmitate Mineral oil, visc. 70

cS ne

Bros

1 0.4 56

Propylene glycol TEA Germall, parabens Water

60.4

T 100.4

Same procedure and sources of supply as in Ref 28.

40

Creams and hand lotions Conditioning Beeswax Cream Soft Consistency

Ref 30 A

2 2 3 3 1 15 3

29°

Stearic acid POE-20 sorbitol beeswax derivative (1) Beeswax GMS Lanolin alcohols (2) Mineral oil, visc. 70 Petrolatum, white USP

B-'0.5 68 0.1 0.2 2

ce

‘REA Water Methylparaben Perfume Propylene glycol ¢

WO:8aret BIOS

(1) Atlas 1726, ICI. US Patent 2 612 509 (2) Hartolan, Croda Mix A and B at 75°C, hold for 10 minutes at this temperature. Cream thickens at 43°C. This is a light consistency cream, unusually white and glossy, that rubs out very quickly although high in emollient oil. Conditioning Beeswax Cream High Oil Content Fairly Dry Application

Ref 30B A 40 2 4 ] eee

9

Mineral oil, visc. 70 Beeswax Getyl vicinal glycol (1) Stearic acid Lanolin alcohols (2)

B 48 1 0.5. O47, 0.1

50.3

Water Propylene glycol Borax “EA Methylparaben

T 99.3

(1) Adol 158, Sherex Chem., Viking Div. (2) Superhartolan, Croda

Mix A and B at 75°C. Set Pt 39°C.

Creams and hand lotions

41

Hand Lotion No. 1

Ref 31 Stearic acid Arlacel 165 (1) Isopropyl myristate

Bs 86 0.15

Propylene glycol Water Methylparaben

Mineral oil, visc. 70

C

D&C Yellow No. 10, 1%

Propylparaben

0.5

0.25

89.9

Perfume

T 100

(1) ICI Mix A and B at 75°C. Keep at this temperature for about 10 minutes. Stir until cold. Fresh lotion is quite thin but becomes very viscous after two or three days. Package in plastic squeeze bottle. Preservation of this non-ionic cream is satisfactory without additional preservatives. Hand Lotion No. 2 Alternate Formula Similar to No. 1

Ref 32 A

4

Stearic acid Ceteth-20 (1) GMS Isopropyl myristate Mineral oil, visc. 70

Braz 3 0.1 85

90.1

She |el

Sodium lauryl sulfate (2) Propylene glycol Methylparaben Water

T 100.1

(1) Brij 58, ICI (2) Standapol WAQ Special, Henkel Mix A and B at 75°C. Lotion thickens at 46°C. Package in plastic squeeze bottle. Hand Lotion No. 3 Low Viscosity for Glass Bottles

Stearic acid Mineral oil, visc. 70 Sesame oil P.G. monostearate (1) Lanolin alcohols (2)

A

0.1 1 B 0.1 0.9 4.1 74 80.2

Propylparaben Cetyl vicinal glycol (3) Methylparaben TEA Propylene glycol ~—~Water T 100.6

(1) Propylene glycol monostearate, Stepan, Kessco Div. (2) Superhartolan, Croda (3) Adol 158, Ashland Chemical, Viking Chemical Div. Mix A and B at 75°C. Stir until cold.

42

Creams and hand lotions

Hand Lotion No. 4 High Viscosity for Squeeze Bottle Ref 34 A

2 1 ju 4 4 iT 5

hy

Oleth-20 (1) Laneth-16 (2) Cetyl alcohol GMS Petrolatum, white USP Mineral oil, visc. 70 Isopropyl myristate

Bees 7a 0.2 0.3 0.5

TSaea

Glycerin Water Germall 115 Parabens D&C Yellow No. 10, 1% z

Tul (i)

(1) Brij 99, ICI (2) Solulan 16, Amerchol Mix A and B at 75°C. Stir until cold. Lotion thickens on standing overnight. Hand Lotion No. 5 High Viscosity for Squeeze Bottle Ref 35

A

2 3 Z 17 1 0.1

2aa1

Stearic acid Isopropyl lanolate (1) Lanolin alcohols (2) Mineral oil, visc. 70 GMS Propylparaben

B

08 a 70 0.1 0.2

TEA Glycerin Water Methylparaben Perfume

76.1

T 101.2

(1) Amerlate P, Amerchol (2) Superhartolan, Croda

Mix A and Bat 75°C. Stir until cold. A fluid lotion for glass bottles can be obtained by addition of 1 part Cocoa butter, 0.8 part Vitamin E and 0.2 part of Giv Tan F. Add 0.1 part Dowicil 200, Dow Chemical.

Creams and hand lotions

43

Glycerin and Rosewater Lotion Pearly Cream Lotion

Ref 36 A

3.5 — Stearic acid 0.1 Oleic acid 1 Mineral oil, visc. 70 B 0.25 TEA 45 Water 0.15 Propylparaben

50

C

15.6

4 0.15 30 D 0.25

30.

Carbopol 934,1% dispersion Glycerin Methylparaben Water Rose perfume

1100

Prepare stock of carbopol dispersion preserved with methylparaben. Mix A and B at 75°C. Cool to room temperature and let stand overnight to develop pearliness. Next day, add C and D. Emollient Lotion High Viscosity

Ref 37 A 0.6 1.6 1.6 0.2 0.2 0.3 0.6 0.15

525

Cetyl vicinal glycol (1) Stearic acid GMS Cetyl alcohol Stearyl alcohol Lanolin Castor oil Propylparaben

B

1.0 03 0.15 0.15 93 C 0.25 0.05

94.9

Propylene glycol TBA Borax Methylparaben Water Perfume FD&C Red No. 40, 1%

100.15

(1) Adol 158, Sherex Chemical, Viking Chemical Div.

Mix A and B at 75°C. Stir until cold.

44

Creams and hand lotions Cocoa Butter Lotion

Stearic acid Acetylated lanolin (1) Mineral oil, visc. 70 GMS Cocoa butter

1 4 1 0. 0

Water Propylene glycol Duponol C Veegum H V (2) Dowicil 200 (3) T 99.7

(1) Modulan, Amerchol (2) Magnesium, aluminum silicate, Vanderbilt (3) Dow Chemical Mix A and B at 75°C. Stir until cold.

Conditioning Hand Lotion With Beeswax High Viscosity Stearic acid POE-20 sorbitol beeswax derivative (1) Beeswax GMS Laneth-16 (2) Mineral oil, visc. 70 Petrolatum, white USP

B

0.5 73 0.1 0.2 2

TEA Water

Methylparaben Perfume Propylene glycol

62.

5.8

T 100.8

(1) Atias 1726, ICI (2) Solulan 16, Amerchol Same procedure as for Ref 30. Stir lotion until cold. This lotion is the counterpart to the cream Ref 30.

Dentifrices

45

4. DENTIFRICES Dental Creams

The formulation of dental creams is well exemplified in numerous patents. The commonly used ingredients are further revealed in the manufacturers’ label declarations. For three leading brands, the compositions compare as follows: Pepsodent (Lever)

Water

Sorbitol Alumina Hydrated silica Glycerin PEG 32 (1) Sodium lauryl sulfate Dicalcium phosphate (2)

Cellulose gum (5) Flavor Titanium dioxide Sodium benzoate

Crest (Procter

& Gamble)

Water Sorbitol

Colgate (Toothpaste) Water Sorbitol Aluminum hydroxide

Glycerin

Glycerin

Sodium lauryl sulfate Calcium pyrophosphate (3)

Sodium lauryl sulfate Dicalcium phosphate (2) Insoluble sodium metaphosphate (4) Cellulose gum (5) Flavor Titanium dioxide Sodium benzoate

Cellulose gum (5) Flavor Mg AI Silicate

Active ingredients: Stannous phosphate

Sodium monofluorophosphate (6)

See ingredient declarations further below. (1) (2) (3) (4) (5)

Carbowax 1540, Union Carbide Same as calcium pyrophosphate (3) Ca2P.20; (water insoluble), Monsanto

NaPO:;, Monsanto Sodium carboxymethyl cellulose (CTFA)

(6) Na2zPO3F

As can be seen, the abrasives in these creams differ widely, their choice depending on the degree of abrasion that is wanted. This question is fully treated in the cosmetic manuals and the technical trade booklets on phosphates for dentifrices.

46

Dentifrices

The surfactant is sodium lauryl sulfate and the binding agent is sodium carboxymethyl cellulose which is approved for food products. Hydroxyethyl cellulose and carbopol 934 are binding agents that are recommended in formulations Ref 41 and 42 although these products have not been cleared for use in foods. However, these are safe for dentifrices according to the manufacturers. Liquid Dentifrices

Liquid dentifrices (Mouthwashes) are beneficial because of their refreshing flavors. Although the formulation of these products is quite simple, a few pertinent facts should be mentioned: 1. Liquid dentifrices should contain a minimum of 5% ethyl alcohol as preservative and anti-floculant. 2. Special denatured grain alcohols 38 B or 38 F should be used. The first contains 10 lbs of aromatic materials for every 100 gallons of grain alcohol. The second contains 7 pounds of boric acid and 3 pounds of aromatic materials per 100 gallons. These flavors must be compounded from a limited number of government specified ingredients and formulations must be submitted for approval to the Alcohol Tax Unit. 3. The flavor denaturants often contribute a substantial part of the total flavor. 4. The complete flavor must be solubilized or more precisely the water insoluble part of the flavor must be solubilized since at low alcohol concentrations (25% or less) the solubilizing action of the alcohol is practically nil. 5. The solubilizer must be GRAS and should not get cloudy in the presence of alcohol. This practically limits the solubilizer to polysorbate-60, e.g. Tween 60, ICI. Since most liquid dentifrices contain either 25, 15, or 5% alcohol by volume, it is useful to note the corresponding content of denaturant flavor required by law: 25 ml Alcohol 38 B must contain 0.3 g flavor 25 ml Alcohol 38 F must contain 0.09 g flavor and 0.21 g boric acid 15 ml Alcohol 38 B must contain 0.18 g flavor 5 ml Alcohol 38 B must contain 0.06 g flavor As can be seen, the denatured alcohol contributes an appreciable, if not a major quantity of the flavor. A few flavor aromatics are soluble in water, but only sparingly which allows little choice for compositions. The maximum solubility in 100 ml water at 25°C should be noted: Eucalyptol: Methyl salicylate: Menthol: Thymol:

0.200 0.070 0.040 0.085

g g g g

Dentifrices

47

Some of the most popular mouthwashes contain only these flavors. These mouthwashes are easily recognized since they do not foam on shaking, due to the absence of solubilizers. A few specifications for liquid dentifrices must be met, namely:

Freezing point should be below 0°C. Cloud point should be 10°C, or lower. However, for mouthwashes with water soluble flavors, a cloud point of 18°C is normal. Taste should not be bitter. Bitterness is due to the flavors and can be corrected with the addition of saccharin. In the absence of this edulcorant, addition of 5 to 10% sorbitol (70% concentration) is advisable. Mouthwash formulations Ref 43 to 47 do not duplicate the composition of any particular brand, although the flavors are approximations of popular types. Examples of Trade Formulations From Manufacturer’s Product Label Listerine Toothpaste.

Warner-Lambert Co.

Ingredients: Dicalcium phosphate Water Sorbitol Glycerin Sodium lauryl sulfate Titanium dioxide

Sodium carrageenan (1) Flavor Cellulose gum Sodium saccharin Phosphoric acid

Remark:

(1) Sodium carrageenate, e.g. Viscarin TP-4 or Viscarin 402, Marine Colloids Co. Crest Toothpaste.

Procter

& Gamble

Active ingredients: Stannous fluoride in a base of calcium pyrophosphate Other ingredients: Water Sorbitol Glycerin Cellulose gum Stannous pyrophosphate Flavor

Sodium cocomonoglyceride sulfonate Sodium cocoyl sulfate Magnesium aluminum silicate Sodium saccharin FD&C Blue No. 1

48

Dentifrices Colgate Toothpaste Sodium monofluorophosphate

Active ingredient:

~ Other ingredients: Dicalcium phosphate dihydrate (1) | Flavor Water Sodium benzoate Glycerin Tetrasodium pyrophosphate (2) Sodium lauryl sulfate Sodium saccharin Cellulose gum Remarks:

(1) CaHPO,4e2H20 (2) Anti-caking agent Pepsodent Toothpaste.

Lever Bros. U.S. Patent 4 024 239

Ingredients: Sorbitol Water Alumina Dicalcium phosphate Cellulose gum

Ultra-Brite, Toothpaste.

Flavor Titanium dioxide Sodium saccharin Sodium benzoate

Colgate Palmolive Co.

Active ingredient: Sodium monofluorophosphate (1) Other ingredients: Water Glycerin Hydrated silica (2) Alumina Cellulose gum

Remarks: (1) Na2PO3F (2) Silica gel

Sodium lauryl sulfate Flavor Sodium benzoate Titanium dioxide Sodium saccharin

Dentifrices Gleem, a fluoride toothpaste.

49

Procter & Gamble

Active ingredient: Sodium fluoride (1) Other ingredients: Calcium pyrophosphate (2) Water Sorbitol Glycerin Cellulose gum (3) Flavor Sodium cocomonoglyceride sulfonate (4) Sodium cocoyl sulfate (5)

Carnauba wax Magnesium aluminum silicate (6) Disodium phosphate (7) Sodium phosphate (8) Sodium saccharin Urea-formaldehyde resin FD&C Blue No. 1 FD&C Yellow No. 5

Remarks:

(1) NaF (2) Ca2P.0,

(3) (4) (5) (6) (7) (8)

Sodium carboxymethyl cellulose e.g. Poem LS-90, Riken Vitamin Oil Co. (Japan) Sodium lauryl sulfate (derived from coconut oil)

Veegum, Vanderbilt Co. Na2HPO, NaH2PO,

Aim, Toothpaste with fluoride. Lever Bros. A clear gel. U.S. Patent 3 538 230 Active ingredient: Sodium monofluorophosphate (1)

Other ingredients: Sorbitol Hydrated silica (2) PEG-32 (3) Water Sodium lauryl sulfate S.D. Alcohol 38 B

Flavor Cellulose gum Sodium benzoate FD&C Blue No. | D&C Yellow No. 10

Remarks:

(1) Na2PO3F (2) e.g. Cab-O-Sil M-5, Cabot Corp. (3) Polyoxyethylene 1500, e.g. Carbowax 1500, Union Carbide

50

Dentifrices

Aqua-fresh, Fluoride toothpaste. Beecham Products, Inc. A mottled green gel with white toothpaste Active ingredient: Sodium monofluorophosphate (1) Other ingredients:

Sorbitol Water Calcium carbonate Hydrated silica (2) PEG-8 (3) Sodium lauryl sulfate Flavor Cellulose gum

Calcium glycerophosphate Sodium saccharin Sodium benzoate Calcium carrageenan (4) Titanium dioxide Sodium silicate FD&C Blue No. 1 - D&C Yellow No. 10

Remarks: (1) Na2PO3F

(2) Silica gel (3) Polyethylene glycol 400, Carbowax 400, Union Carbide (4) Sea-Kem 4, Marine Colloids, Inc

Listerine Mouthwash.

Warner-Lambert Co.

Active ingredients: Thymol, eucalyptol, methyl salicylate, menthol

Other ingredients: Water Alcohol, 26.9% Benzoic acid

Poloxamer 407 (1} Caramel

Remark:

(1) e.g. Pluronic F-127, BASF Wyandotte Corp. Lavoris Mouthwash.

Vick Chemical Co., Div. of Richardson-Merrell, Inc

Ingredients: Purified water SD Alcohol 38 C, Mod. (5%) Zinc chloride Flavors

Saccharin Clove oil FD&C Red No. 40

Dentifrices Scope Mouthwash.

Active ingredients:

51

Procter & Gamble

Cetyl pyridinium chloride, Domiphen bromide (0.005%), SD Alcohol 38 F (18.5%)

Other ingredients: Water

Flavor

Glycerin

FD&C Blue No. 1

Sodium saccharin Benzoic acid

FD&C Yellow No. 5

Cepacol Mouthwash.

Richardson-Merrell, Inc

Ingredients:

Water SD Alcohol 38 F, 14% Glycerin Polysorbate 80 Odol Mouthwash.

Cetyl pyridinium chloride Phosphate buffers Aromatics FD&C Yellow No. 5

Odol Chemical Co., Watchung, N.J.

Active ingredients: Anise oil Cloves oil Lavender oil Peppermint oil Menthol Pearl Drops, Tooth Polish.

Ingredients: Water Aluminum hydroxide (1) Sorbitol Dicalcium phosphate Remark: (1) Alumina, hydrated

Sodium lauryl sulfate Cresylic esters of salicylic and cresotic acids Alcohol

Carter Products Co. A liquid cream dentifrice Flavor Cellulose gum Sodium saccharin Methylparaben

52

Dentifrices

Formulations Dental Cream No. I Ref 41 A 32 1 B 26 1

0.15

60.15

Glycerin Hydroxyethyl cellulose (1) Water Duponol C

Sodium benzoate

C 39 Dil

ale

40

Calcium phosphate, dibasic NF hydrous (2) Flavor

7 100.15

(1) Natrosol 250, Hercules (2) CaHPO.e2H20 Disperse natrosol into the glycerin and stir until a uniform gel has formed. Add solution B and stir until mass is uniform. Add C and D under slow stirring to avoid formation of foam and introduction of air. The addition of abrasive powders can be done conveniently in a pony mixer. Although a heavy duty mixer is not required, the powder addition should be made prior to complete gelation to facilitate the mixing operation. Liquid Dental Cream No. 2 For Plastic Squeeze Bottle Ref 42

A 33 22.4 0.5 0.1 B 0.7

Glycerin Water Saccharin 10% Methylparaben Carbopol 934

C _3.1

Sodium hydroxide 10%

59.8

D 20 20 E 0.75 0.25

Calcium phosphate (1) Calcium phosphate (2) Flavor Tween 60

ue 41

T 100.8

(1) Dibasic hydrous NF CaHPO,+2H,0, Mallinckrodt (2) Dibasic anhydrous CaHPO,, J.T. Baker Chemical Prepare part A and add B. Use high propeller agitation, adding the carbopol slowly into the vortex. Add C and stir until uniform. Add D in pony mixer until a smooth cream is obtained. Add E. Control: Viscosity of the cream depends on the percentage of carbopol and the particle size of the phosphates. Since particle size may vary, viscosity must be adjusted by controlling the percentage of the phosphates.

Dentifrices

53

Mouthwash No. 1 Amber Tinted, Water Soluble Flavor

Ref 43 25 ml Grain alcohol 95% vol 0.310 Complete flavor. Ref 243 0.210 Boric acid 25.520

0.05 0.5 74 74.55

Caramel color 50% (1) Saccharin 10% Water T 100.07 ml

(1) D.D. Williamson Co., Long Island City, N.Y. 5% Sorbitol may be added, reducing the water accordingly. Chill to 15°C and filter. Do not cool below 15°C to avoid separation of essential oils. For production, use denatured alcohol 38 F as specified in flavor Ref 243. For 100 gal grain alcohol the denaturant may consist of 7 lb boric acid, 1.3 lb methyl salicylate and 1.7 lb thymol. Mouthwash No. 2 Red Tinted, Clove-Cassia Flavor

Ref 44 5 0.26 1

ml Grain alcohol 95% vol Complete flavor. Ref 244 Tween 60

0.3. 0.05 93

FD&C Red No. 40, 1% Zinc chloride NF Water

0.5

Saccharin 10%

fe nay

6.76

93.35 T 100.1 ml Chill to 10°C and filter. Add color after filtration. For production, use denatured alcohol 38 B. See flavor Ref 244. Mouthwash No. 3 Blue Tinted, Methyl Salicylate-Thymol Flavor

Ref 45 15 0.38 1 0.5

16.88

ml Grain alcohol 95% vol Complete flavor. Ref 245 Tween 60 Saccharin 10%

0.25 0.05 83 valver

83.3.

FD&C Green No. 3, 1% Cetyl pyridinium chloride Water

T 100.18 ml

Chill to 10°C and filter. Add color after filtration. For production, use denatured alcohol 38 B. See flavor Ref 245.

54

Dentifrices Mouthwash No. 4 Green Tinted, Menthol-Cassia Flavor

Ref 46

15 0.34 1 0.5

10 26.84

ml Grain alcohol 95% vol Complete flavor. Ref 246 Tween 60 Saccharin 10% Sorbitol 70%

0.05 0.05 0.05 73

FD&C Green No. 3, 1% FD&C Yellow No. 5, 1% Cetyl pyridinium chloride Water

73.15

T 100.0 ml

Chill to 10°C and filter. Add color after filtration. For production, use alcohol 38 B. See flavor Ref 246.

Mouthwash No. 5 Yellow Tinted, Peppermint-Cassia Flavor Ref 47 IS 0.754 1.8 0.5 18.054

ml Grain alcohol 95% vol Complete flavor. Ref 247 Tween 60 Saccharin 10%

0.1 0.05 0.126 82

FD&C Yellow No. 5, 1% Cetyl pyridinium chloride Boric acid Water

82.276 T 100.3 ml Chill to 10°C and filter. Add color after filtration. For production, use alcohol 38 F. See flavor Ref 247.

Deodorants and antiperspirants 5. DEODORANTS

55

AND ANTIPERSPIRANTS

The most commonly used preparations are the following: Aerosol antiperspirants. Ref 51 Cream antiperspirants. Ref 52A & B Cream deodorants, anhydrous. See below Roll-on antiperspirants. Ref 53A & B Stick deodorants. Ref 54, 55A &B Stick antiperspirants. Ref 56, 57 Deodorants should be distinguished from antiperspirants. Deodorants are perfumed preparations that do not affect perspiration, whereas antiperspirants depend on astringent chemicals as active ingredients. Most cream and roll-on antiperspirants, as well as aerosol antiperspirants, are based on aluminum chlorhydrate as active ingredient. Recently, aluminum chloride, which had been used in former years, has been added to the formulations for greater effectiveness. This chemical is highly astringent and also strongly acid, pH = 2. However, with aluminum chlorhydrate acting asa buffer, the mixture has a pH of about 4. Cream deodorants of the anhydrous type are based on mineral oil and a high concentration of zinc oxide in order to obtain a fairly dry application. Although the perfume is the main active factor, zinc oxide acts as a mild deodorant as it slowly neutralizes the lower fatty acids that are present in perspiration. A true deodorant should be mentioned, namely vanishing cream Ref 26. It is highly effective as can be easily shown by mixing a small amount of the cream with a dilute solution of lower fatty acid. The odor disappears instantly due to reaction with excess alkali. The only drawback is that frequent application is necessary as prespiration tends to wash off the cream. This can be minimized with addition of silicones. Preparations in stick form are extremely popular both as deodorants and antiperspirants. Deodorant sticks are based on alcohol or propylene glycol gelled with sodium stearate. Propylene glycol is often preferred since it causes less shrinkage of the sticks; it is also less flammable. Inasmuch as the alcohol must be heated to a fairly high temperature to dissolve the sodium stearate, special safety precautions must be taken. The mixing kettle must be enclosed and provided with a reflux column vented to the outside. Furthermore, to avoid losses of alcohol, a small condenser should be set at the top of the column. The filling equipment should be powered with

explosion-proof motors. Failure to observe these precautions has caused dangerous explosions and fires. It should be noted that sodium stearate can be easily prepared in situ by reacting stearic acid with an equivalent weight of sodium hydroxide. This is more economical and also more rapid since the solution of sodium stearate forms instantly. See Ref 58.

56

Deodorants and antiperspirants

Antiperspirant sticks are similar in composition to the deodorant sticks, except that they usually contain a mild astringent such as sodium aluminum chlorhydroxylactate since aluminum chlorhydrate is not compatible with sodium stearate. However, a special antiperspirant stick can be formulated without the stearate. See Ref 57. Processing Equipment for Aluminum Chliorhydrate Preparations Since aluminum chlorhydrate is strongly acidic, adequate processing equipment is needed. Glass lined kettles are widely used for mixing in acid medium. Filling equipment and pumps must be stainless steel 316 and holding tanks preferably PVC or polyethylene. All contact with iron, copper, brass or aluminum should be avoided. Examples of Trade Formulations From Manufacturer’s Label

Arrid.

Antiperspirant cream deodorant, Carter Products

Active ingredients:

Aluminum chlorhydrate, aluminum chloride

Other ingredients:

Water Glyceryl stearate (1) PEG 40 stearate (2) Spermaceti Glycerin Dimethicone (3) Isopropyl palmitate Lanolin alcohol

Lanolin wax Hydroxypropyl methyl cellulose (4) Fragrance Titanium dioxide Lanolin Propyl paraben Mineral oil

Remarks:

(1) and (2) may indicate Arlacel 165, ICI (3) e.g. Silicon L 45, Union Carbide (4) e.g. Methocel E 4 M, Dow Chemical Odorono.

Antiperspirant cream deodorant, Chesebrough Ponds

Active ingredient: Aluminum chlorhydrate Other ingredients:

Water Glycol distearate (1) Propylene glycol PEG 25 propylene glycol stearate (2) Cetyl alcohol Isopropyl palmitate Glycine Cetyl palmitate Cetyl myristate

Magnesium aluminum silicate (3) Dimethicone (4) Stearamido ethanolamine (5) Fragrance Allantoin Methyl paraben Phosphoric acid Disodium EDTA FD&C Blue No. 1

—

Deodorants and antiperspirants Remarks:

(1) (2) (3) (4) (5)

Presumably ethylene glycol distearate e.g. Atlas G 2162, ICI e.g. Veegum, Vanderbilt Co. e.g. Silicone L 45, Union Carbide e.g. Chemical 39 Base, Sandoz

Right Guard.

Roll-on antiperspirant, Gillette

Active ingredient: Aluminum-zirconyl hydroxychloride complex (1) Other ingredients: Water Glyceryl stearate (2) PEG 100 stearate (3) Dimethicone Magnesium aluminum silicate

Laureth-4 (4) Fragrance Methyl paraben Propyl paraben

Remarks: (1) Wickhen Products (2) and (3) may indicate Arlacel 165, ICI (4) Lauryl alcohol 4 POE, e.g. Brij 30, ICI

Ban.

Antiperspirant cream, Bristol-Myers Co.

Active ingredients:

Aluminum chlorhydrate, aluminum chloride

Other ingredients: Water Glyceryl stearate (1) Propylene glycol Coceth-6 (2) Glycine (3) Isopropyl palmitate

Isopropyl myristate Titanium dioxide Fragrance Isopropyl stearate D&C Yellow No. 10 D(C Red No. 19

Remarks: (1) Possibly Arlacel 165, ICI (2) Coconut alcohol 6 POE, e.g. Promulgen D or G, Amerchol (3) Aminoacetic acid

57

58

Deodorants and antiperspirants Ban.

Roll-on antiperspirant deodorant, Bristol-Myers Co.

Active ingredient: Aluminum chlorhydrate Other ingredients: Water Glyceryl stearate (1) Laureth-23 (2) Laureth-4 (3)

Lapirium chloride (4) Lauric acid D&C Red No. 4 FD&C Yellow No. 5

Fragrance

Remarks: (1) (2) (3) (4)

Possibly Arlacel 165, ICI e.g. Brij 35, ICI e.g. Brij 30, ICI e.g. Emcol E-607 (a quaternary compound Witco Chemical

Ultra Ban.

Antiperspirant lotion, Ultra dry roll-on, Bristol-Myers

Active ingredients: Aluminum chlorhydrate

Other ingredients: Water Glyceryl stearate (1) Laureth-23 (2) Laureth-4 (3) Magnesium aluminum silicate

Lapirium chloride (4) Lauric acid FD&C Green No. 3 FD&C Yellow No. 5

Remarks: Same as above. This product is unscented. Gillette.

Super dry roll-on antiperspirant

Active ingredient: Aluminum-zirconyl hydroxychloride complex (1) Other ingredients: Water Glyceryl stearate (2) PEG 100 stearate (3) Dimethicone (4) Magnesium aluminum silicate (5)

Laureth-4 (6) Fragrance Methylparaben Propylparaben EDTA

Remarks:

(1) Aluminum chlorohydrate and zirconium chlorohydrate, e.g. Chlorhydrol 50% (Reheis) and Wickenol 371 (Wickhen Products) (2) and (3) may indicate Arlacel 165, ICI (4) e.g. Silicone 200 Fluid, Dow Corning Corp. (5) Veegum, Vanderbilt Co. (6) Brij 30, ICI

Deodorants and antiperspirants Mum.

59

Cream antiperspirant, Bristol-Myers

Active ingredient: Aluminum chlorhydrate Other ingredients: Water Glyceryl stearate Propylene glycol Coceth-6 (1) Isopropyl palmitate (2)

Isopropyl myristate (3) Fragrance Titanium dioxide Isopropyl stearate Quaternium-15 (4)

Remarks:

(1) (2) (3) (4)

PEG-6 coconut alcohol e.g. Deltyl Prime, Givaudan Corp. e.g. Deltyl Extra, Givaudan Corp. Dowicil 200, Dow Chemical

Ban.

Solid antiperspirant, Bristol-Myers. An opaque stick

Active ingredient: Aluminum chlorhydrate Other ingredients: Octyl palmitate (1) Stearyl alcohol Paraffin PEG-25 (2)

Propylene glycol stearate Fragrance Titanium dioxide Bia

Remarks: (1) e.g. Ceraphyl 368 (Van Dyk), or Wickenol 155 (Wickhen Products) (2) e.g. Carbowax 1000, Union Carbide

Mennen.

Deodorant stick dry lime

Ingredients: Propylene glycol Water - Sodium stearate Fragrance

Triclosan (1) FD&C Yellow No. 5 FD&C Blue No. 1

Remark:

(1) e.g. Irgassan DP-300, Ciba-Geigy. An antibacterial agent

60

Deodorants and antiperspirants

Formulations Antiperspirant Pump Spray For Glass Bottle and Plastic Pump Ref 51 30 5 30

Alcohol SDA 39 C Propylene glycol Aluminum chlorhydrate 50% (1)

65

35 0.1 0.2 0.8

Water Methylparaben Perfume Tween 60 (2)

souls

=F 100-1

(1) Chlorhydrol 50%, Reheis Co. (2) ICI

Simple mix. Solubilize perfume with tween before adding to batch. Antiperspirant Cream

Ref 52A 7. aay 2 4 4 4 4

Arlacel 165 (1) Cetyl alcohol Stearyl alcohol Paraffin, mp 128°F Mineral oil, visc. 70

B 66 0.5 0.1 Cals

Water Duponol C (2) Methylparaben Aluminum chlorhydrate 50% (3)

re

. 0755,

-Periumie

18

82.1

T 100.1

(1) ICI (2) Sodium lauryl sulfate 100%, E.I1. DuPont de Nemours (3) Chlorhydrol 50%, Reheis Co. Mix A and B at 75°C. Cool to 50°C. Add C. Fill at 45°C. Antiperspirant Cream Alternate Formula

Ref 52B A

l 3 3 3 4 4 ba 18

Ceteth-20 (1) GMS Cetyl alcohol Stearyl alcohol Mineral oil, visc. 70 Paraffin, mp 128°F

B 60 3 2 Gris 3 D _0.5 aie

Water Propylene Laneth-16 Aluminum 50% Aluminum Perfume Oo

glycol (2) chlorhydrate

chloride (3)

(1) Brij 58, ICI (2) Solulan 16, Amerchol (3) AlCl;*6H20 Mix A and Bat 75°C. Cool to 50-55°C. Heat C to 50°C and addto batch, mix while still fluid. Fill cold.

Deodorants and antiperspirants

61

Antiperspirant Cream Vanishing Type

Ref 52C Aula 3 3 3

as

Ceteth-20 (1) Cetyl alcohol Stearyl alcohol Ethylene glycol monostearate (2) Mineral oil, visc. 70 Paraffin mp 128°F

B

2 3 60 Caxs

D

3 0.1 _0.5 83.6

Na laureth-2 sulfate (3) Propylene glycol Water Aluminum chlorhydrate 50% Aluminum chloride (4) Methylparaben Perfume T 101.6

(1) Brij 58, ICI

(2) Kessco No. 70, Stepan, Kessco Division (3) Standapol ES-2, 28% active, Henkel (4) AICl3;*6H20

Mix A and B at 75°C. Cool to 45—50°C. Heat C to 45—50°C and add solution to batch. Mix while still fluid. Fill cold. Roll-On Antiperspirant Ref 53A

A

8 2

Arlacel 165 (1) Laneth-16 (2) Igepal CO-730 (3) Mineral oil, visc. 70 Cetyl alcohol

B 66 0.1 Cc 15

De —N

3 0:54.

84.6

Water Methylparaben Aluminum chlorhydrate 50% (4) Aluminum chloride (5)? .Perhume

199.6

(1) ICI (2) Solulan 16, Amerchol (3) GAF Corp. (4) Chlorhydrol 50%, Reheis Co.

(5) AlCl;*6H20 Mix A and B at 75°C. Cool to 40°C. Add solution C and perfume D. Color with 0.05% D&C Red No. 19, 1%, or D&C Yellow No. 10, 1%. These colors are stable with aluminum chloride.

62

Deodorants and antiperspirants Roll-On Antiperspirant Alternate Formula

Ceteth-20 (1) GMS Water Laneth-16 (2) Propylene glycol

C

D

15 3 0.5 _0.1 18.6

Aluminum chlorhydrate 50% (3) Aluminum chloride (4) Perfume Methylparaben T 100.6

(1) Brij 58, ICI (2) Solulan 16, Amerchol (3) Chlorhydrol 50%, Reheis Co. (4) AICIl;-6H20

Same procedure as for Ref 53. This lotion should stand the heat stability test prescribed for depilatory creams. Stick Deodorant No. 1 Formulation With Alcohol

Sodium stearate (1) Glycerin Propylene glycol

A 75 6 B23

ml Alcohol 95% vol Water Perfume

84 «= T:100 ml

(1) Sodium stearate C 1, Witco Chemical Heat the ingredients A to about 80°C under reflux to dissolve the sodium stearate. Cool to 70°C, add the perfume B and fill the individual plastic cases. Set Pt about 50°C. Cut off the concave top of the stick and cap. For large scale production, cooling tunnels or chambers are needed. See text for safety precautions.

Ref 55A A 10 64 20 “94

Stick Deodorant No. 2 Formulation With Propylene Glycol Sodium stearate (1) Propylene glycol

Water

B33 3

Perfume Igepal CO-730 (2)

ox

6 T 100 (1) Sodium stearate C 1, Witco Chemical (2) GAF Corp.

Same procedure as for stick No. 1

Deodorants and antiperspirants

63

Stick Deodorant No. 2 Alternate Procedure

Ref 55B A

9 64 B 19 yee 94

Stearic acid Propylene glycol Water Sodium hydroxide, pellets

a3 3

= 6

Perfume Igepal CO-730

T 100

Heat A to 75°C to dissolve stearic acid. Add B preheated to 65°C, then add mixture C. Since sodium hydroxide pellets retain 5to 10% water, additional caustic may be required for complete saponification. This is best determined by titration or a sample with 1 N NaOH using phenolphthalein as indicator. The batch is then adjusted accordingly. Antiperspirant Stick No. 1 Formulation

With Chloracel

Ref 56 AC? Z 3

is

Sodium stearate (1) Laneth-16 (2) Sorbitol, 70% soln

A 41 B 47 G

88

Propylene glycol Chloracel 40% soln (3) Perfume and color

TT 100

(1) Sodium stearate C 1, Witco Chemical (2) Solulan 16, Amerchol (3) Sodium aluminum chlorhydroxylactate, 40% soln, Reheis Co.

Heat A to about 80°C until clear. Add chloracel gradually while heating to prevent solution from getting solid. Fill plastic cases at about 70°C. Set Pt 55°C. Antiperspirant Stick No. 2 Formulation With Aluminum Chlorhydrate

Ref 57 A 27 15 10 | 24 54

Oleyl alcohol (1) Ozokerite No. 4 Paraffin, mp 128°F Lanolin

B 30 C 20 1 ata 5]

Dipropylene glycol (2) Aluminum chlorhydrate (3) Perfume T 105

(1) Adol 85, Sherex Chemical (2) Union Carbide (3) Chlohydrol, Impalpable, Reheis Co.

Melt waxes and oils A to 80°C. Add B. When mass is uniform, add C. Cool to 65°C and pour into plastic cases. Set Pt 50°C.

64

Depilatories

6. DEPILATORIES Most depilatories that are now being promoted are based on salts of thioglycolic acid. The main active ingredient is calcium thioglycolate that is obtained by reacting thioglycolic acid with calcium hydroxide:

COOH

|

CH.SH Thioglycolic acid 92

{°F

CaOH)s Calcium hydroxide 74

+

ioe Water 18

COO fre

CHS

Ca.3H20

Calcium thioglycolate trihydrate 184

Calcium thioglycolate trihydrate is also available commercially as a fine powder, purity 94% minimum. Solubility in water is 6.0% at 20°C, 7.5% at 50°C and about 9% at 60°C.

Sodium thioglycolate is prepared similarly by neutralizing the thioglycolic acid with sodium hydroxide. It can also be formed by adding sodium hydroxide or sodium silicate to a solution of calcium thioglycolate; this regenerates calcium hydroxide. As will be seen, these various reactions are used in the formulations given below. It should be noted that the thioglycolates become effective depilatories only after the addition of an excess of calcium hydroxide that raises the pH to 12.5. Although calcium hydroxide is only sparingly soluble in water, it is a strong alkali and as little as 0.5% is sufficient to raise the pH of the glycolate solution from about 10 to 12.5. A higher concentration up to 7% calcium hydroxide is often used, although this does not appreciably increase the pH or allow a shorter time of depilation. The time of depilation actually depends on the relative concentration of sodium and calcium thioglycolates. An excess of calcium hydroxide should be avoided since it acts as a skin irritant, particularly on the cheeks near the nose, an area that is very sensitive to alkalies. Several formulations are offered for discussion. Formula No. | is a standard trade formula based on calcium thioglycolate. It depilates in 5 to 10 minutes depending on the strength of the hair. For use on the face, a patch test is always advisable. Some depilatories give a tingling effect after 1 minute application and should be removed immediately.

Depilatories

65

The use of calcium thioglycolate powder has certain disadvantages. It varies in purity (from 94 to 98%) and also in particle size. This often causes grittiness when the powder is not all in solution. The fact that a mask must be worn when handling the powder should also be noted. Formulations with thioglycolic acid do not have these objectionable features. Moreover, the preparation is simple and quite economical, the cost being less than half the cost with calcium thioglycolate powder. Two initial formulations are shown under Ref 62 and 63. These depilate in 5 minutes with a minimum concentration of free alkali. As can be seen by referring to the formulas, sodium thioglycolate is formed first in the presence of an excess of thioglycolic acid. This excess is neutralized with about 1.4% Ca(OH), to form calcium thioglycolate. The resulting solution is pink due to the presence of about 0.05% iron in calcium hydroxide USP grade. On further addition of 0.6% Ca(OH), the solution turns colorless, the pH rising to 12.5. The creams are white and practically odorless. They should be filled promptly into tubes to prevent oxidation. If kept in stock they should be placed in closed tanks under a blanket of nitrogen. When the creams are prepared without the proper antioxidants and are kept in jars, air slowly penetrates through the caps and causes the cream to turn light yellow due to oxidation, first at the surface, then slowly inside. This discoloration can be somewhat retarded by the addition of stearic hydrazide, a well-known antioxidant that is widely used in soap. However, this chemical as well as other antioxidants (BHA, BHT, etc) will not prevent the formation of the troublesome yellow color. It was found that this discoloration can be controlled by the addition of Dowicil 200, which is normally used as a preservative. Flushing the tubes with nitrogen just prior to filling is also helpful. The manufacturing operation with thioglycolic acid does not present any problems. However, the processing and filling equipment should be stainless steel 316 or 304 to avoid contaminations with iron that can cause pink discolorations. Formulations No. 2 and 3 have a reduced wax content in order to increase the specific gravity. This is sometimes necessary to get the proper fill into the packaging tubes. Since these creams tend to be of softer consistency, they should be passed through a Sony homogenizer at about 45°C. This doubles the viscosity from about 75,000 to 150,000 centipoise. Formulations can of course be widely varied. For instance, formula No. 4, Ref 64 gives a depilatory based almost entirely on potassium thioglycolate. Formulas Ref 61 to 64 are based on ceteth-20. This is also the preferred emulsifier of many trade depilatories. However, excellent creams can also be obtained by means of sodium lauryl sulfate or sodium lauryl ether sulfate as

exemplified in the label declarations of at least two well-known brands. These declarations also reveal that creams of firmer consistency can be obtained with the addition of calcium carbonate. See formula Ref 65.

66

Depilatories

Although cream Ref 65 is excellent in use and appearance, it is not stable at temperatures above 50°C. This requires great care in manufacturing. Should the cream be heated accidentally over 50°C in the manufacturing process after adding the thioglycolic acid, it may turn liquid in less than a week, although it had the proper viscosity originally. To avoid this possibility it is necessary to have a cream that is heat resistant. This is easily achieved by adding 1% ceteth-20 to the formula. The new formulation therefore contains two emulsifiers and this also requires an increase in the wax content to maintain the proper viscosity. Such a cream stays emulsified at 75°C and above; when cooled the emulsion is still stable, although it reverts to a liquid state rather than to the initial cream consistency. This behavior is also characteristic of the best selling hair removers. It is also necessary to note that depilation takes place only if the hair is fully embedded in the cream. It is therefore important that depilatories for the face should not run off after application since the remaining film is ineffective. This requires a firm consistency and sufficient adherence. A revised formulation is shown under Ref 66 which gives an excellent creamy texture without homogenization. Depilatories should be filled promptly after homogenization. Tin or plastic tubes can be used, although packaging in glaminated tubes is now more common. These newer tubes are made of aluminum-like foils laminated with plastic on the outside. Special sealing equipment is required. Quality control includes the determination of the thioglycolic acid content (2.4%) for both the top and bottom of the batch to insure an homogeneous mix. Physical controls include specific gravity, viscosity and pH, all of which are of importance. The cream should also be tested for stability at higher temperatures. All that is necessary is a one hour oven test at 55°C, or a 24 hour test at 40°C. Furthermore, it should be mentioned that depilatories show a loss of about 0.2% thioglycolic acid after one year of shelf-life. As is well-known, this

degradation is due to interesterification of the reactive mercaptan and carboxylic groups of the acid. To compensate for this loss, depilatories often contain 3 to 4% thioglycolic acid, but these higher concentrations do not give better or faster depilation.

Depilatories

67

Examples of Trade Formulations From Manufacturer’s Label Nair, Cream hair remover.

Carter Products

Ingredients: Water Light mineral oil Cetyl alcohol and Ceteareth-20 Calcium hydroxide

Sodium thioglycolate Calcium thioglycolate Silica Fragrance

This product is packaged in glaminated tubes. Neet, Lotion hair remover with Cocoa butter. Whitehall Laboratories. A thinner cream consistency than Neet, cream hair remover

Ingredients: Water Mineral oil Sorbitol Cocoa butter Calcium hydroxide Sodium thioglycolate

Calcium thioglycolate Stearyl alcohol Fragrance Ceteareth-20 Paraffin Cetyl alcohol

This product is packaged in a plastic bottle. Dorothy Gray Depilatory

Ingredients: Water Calcium thioglycolate Stearic alcohol Calcium hydroxide

Cetyl alcohol Ceteth-20 (1) Fragrance Sodium lauryl sulfate

Remark:

(1) e.g. Brij 58, ICI Neet, Cream hair remover.

Lemon scented

Ingredients: Water Cetyl alcohol Thioglycolic acid Mineral oil Coceth-6 (1) Calcium hydroxide

Sorbitol Sodium hydroxide Sodium silicate Perfume Paraffin

Remark:

(1) PEG-6 Coconut alcohol, CTFA This product is packaged in glaminated tubes.

68

Depilatories Nudit, Helena Rubinstein.

Cream hair remover for the legs

Ingredients: Water Calcium thioglycolate Calcium hydroxide Stearyl alcohol Cetyl alcohol

Chalk Sodium laureth sulfate Sodium silicate Fragrance Hydroxyethyl cellulose

Nudit, Helena Rubinstein.

Ingredients: Water Chalk Cetyl alcohol Calcium thioglycolate

Cream hair remover for the face

’

Sodium silicate Calcium hydroxide Fragrance Sodium lauryl sulfate

Note increased percentage of chalk in order to get a firmer cream for use on the face as compared to the cream for the legs. Nudit, Helena Rubinstein.

Brush-on hair remover

Ingredients: Water Cetyl alcohol Chalk Calcium hydroxide Sodium laureth sulfate

Sodium silicate Fragrance Hydroxyethyl cellulose Sweet Birch extract Chamomile extract

A cream of somewhat cellulose.

softer consistency stabilized with hydroxyethyl

Depilatories

69

Formulations Depilatory No. 1 Ref 61

ATS 10 5 5 0.2

Ceteth-20 (1) Mineral oil, visc. 70 Stearyl alcohol Cetyl alcohol Stearic hydrazide (2)

25.2

B 50 0.1 Com 14 5 5 foe |

Water Methylparaben Sodium hydroxide, pellets Water Calcium thioglycolate Calcium hydroxide

T 100.3

(1) Brij 58, ICI (2) Olin Chemicals Div., Stamford, Conn

Mix A and B at 75°C and cool to 50°C. Mix C in the order shown, heat to 55-60°C, strain through SS mesh 100, bring to 45-50°C, add to batch. Stir until cold. Fill cold. Note: 1 g NaOH converts 2.3 g calcium thioglycolate into sodium thioglycolate.

Depilatory No. 2 for the Face

Ceteth-20 Stearyl alcohol Cetyl alcohol Mineral oil, visc. 70 Stearic hydrazide Perfume

B 59 0.3 C 0.3 23.2 a 2.5

88.3

Water Sodium lauryl sulfate (1) Sodium hydroxide, pellets Water Thioglycolic acid 80% Calcium hydroxide

T 100

(1) Standapol WAQ Sp, 28% active, Henkel Mix A and B at 75°C and cool to 50°C. Mix C in the order shown, bring to 45-50°C, add to batch. Homogenize at 45°C. Set Pt 39°C, pH = 12.1, Specific gravity 1.020. Depilatory No. 3 for the Body

Ceteth-20 Stearyl alcohol Cetyl alcohol Mineral oil, visc. 70 Dowicil 200 (1) Perfume

5.3 0.3

Cel 23 3 a 84.3

Water Sodium lauryl sulfate (2) Sodium hydroxide, pellets Water Thioglycolic acid 80% Calcium hydroxide T 100

(1) Dow Chemical Co. (2) Standapol WAQ Sp, 28% active, Henkel

70

Depilatories Depilatory No. 4

Ref 64

A

4 10 1 0.5 B 49.6 0.5

0.1.

65.7

Ceteth-20 Cetyl alcohol Mineral oil, visc. 70 Rose perfume Water Sodium lauryl sulfate (1)

C

Dowicil 200

1.8

27 3 2.5

Potassium hydroxide, pellets Water Thioglycolic acid 80% Calcium hydroxide

34.3

T 100

(1) 28% active, Henkel Same procedure as in Ref 62.

Depilatory No. 5 for the Body

Ref 65 A

3 3 0.5 B 59 0.5 _0.2 66.2

Cetyl alcohol Stearyl alcohol Rose perfume Water Sodium lauryl sulfate (1)

Dowicil 200 (2)

C

0.3 24 3 4 2.5

Sodium hydroxide, pellets Water Thioglycolic acid 80% Calcium hydroxide Calcium carbonate

Baie, 33.8

T 100

(1) 28% active, Henkel (2) Dow Chemical Mix A and B at 75°C. Cool to 50°C. Mix C in the order shown. Calcium carbonate must be added last when the mixture is alkaline. Bring C to 45-50°C and add to batch. Keep mixing at 45-50°C until the batch is uniform. Homogenize. Note: A depilatory for the face can be obtained similarly, except that 2.5% calcim hydroxide and 4% calcium carbonate should be used in order to get a cream of firmer consistency. It should not run off the face.

Depilatories

71

Depilatory No. 6 Ceteth-20 (1) Cetyl alcohol Stearyl alcohol Mineral oil, visc. 70 Rose perfume Water Sodium lauryl sulfate (2)

C

0.35 23 3 2.55 4

Sodium hydroxide, pellets Water Thioglycolic acid 80% Calcium hydroxide Calcium carbonate

ae. 32.9

T 100

(1) Brij 58, ICI (2) Standapol WAQ Sp, 30% active, Henkel Same procedure as for cream Ref 65. Homogenization is not required since the viscosity of the cream is 100,000 ctp. Sp. gr. of the cream is 0.990; this is slightly lower than for cream Ref 65 due to the increase in waxes. Note also the increase in sodium lauryl sulfate (0.75% on a dry base); this was necessary for a stable emulsion (A + B) in the temperature range of 60 to 70°C. An excellent cream can also be obtained by using 2% laneth-16 (Solulan 16, Amerchol) instead of sodium lauryl sulfate. The cream (A + B) is then sufficiently thin at 45°C to allow mixing with part C, also kept at 45°C. This is well below the critical temperature above 50°C. Various other surfactants were tested. However, none of the tests gave a cream that would revert to its original viscosity after being heated to 60°C, nor can any such cream be found on the market at the present time.

Depilatories should not be kept in hot storage places for extended periods of time since this may cause an irreversible loss of viscosity and thin films of cream that are ineffective.

72

Gels

7. GELS Many cosmetics can be formulated as attractive clear gels. The most common are the following: Aerosol gels, e.g. Type “Edge” shaving gel After shave gels. See Shaving Preparations Antiseptic 3% USP peroxide gels. See Peroxide Preparations Bath gels and gelées. Ref 71-76 Cleansing gels. Ref 77 Cologne and perfume gels. Ref 78-80 Dentifrice gels, e.g. Type “Aim,” Lever Bros. Hair setting gels. Ref 81 Hand lotion gels. Ref 82 Make-up gels. See Make-up Preparations Shampoo gels. See Shampoos Suntan and bronzing gels. See Suntan Preparations A few cosmetic gels remain to be developed, particularly a clear lather shaving gel. As a starting point, the reformulation of transparent soap Ref 201 could be considered since this soap has excellent shaving qualities. However, the problem appears to be difficult, although a tentative solution is given under Ref 200 (Shaving Preparations). Most of the gel formulations are based on carbopol. However, for sham-

poos the preferred gelling agent is lauryl myristyl amide. Some gels are based on oleth-3 phosphates as recommended in the literature. These are complex phosphates which must be free of non-biodegradable trialkyl phosphates. Examples of trade formulations are given under the respective cosmetics, namely: Aerosols: Edge, Self foaming shaving gel, S.C. Johnson & Son, Inc Bath preparations: Vitabath (Badedas), Bath gel, Beecham Co. Dentifrices:

Aim, Toothpaste gel, Lever Bros.

Hair grooming cosmetics: Vitalis, Clear Gel, Bristol-Myers Shampoos: Prell, Clear Gel, Procter & Gamble

Gels

73

Formulations

Bath Gel No. 1 Emollient Gel for Tube Packaging Ref 71 A 42 1.5 1.5 45

Propylene glycol Laneth-16 (1) Ceteth-20 (2)

B

0.5 55 Me a 56

Perfume Carbopol 940, 1% (3) eek. T 101

(1) Solulan 16, Amerchol (2) Brij 58, ICI (3) Goodrich Chemical Prepare carbopol dispersion, preserve with 0.15% Methylparaben. Heat A to dissolve waxes. Add ingredients B in succession. To the clear solution A + B, add T E A under good agitation. Stop agitation as soon as gel is formed.

Application:

Non oily. Gel is slightly turbid. Bath Gel No. 2

Ref 72 A 70 1:5

1:5 73

Propylene glycol Laneth-16 Ceteth-20

B

0.2 30 C 6 30:8

Perfume Carbopol 940, 1% TEA T 103.8

Ingredients and procedure same as for Gel No. 1 Application: Somewhat oily due to higher propylene glycol content. Gel is clear.

Bath Gelée No. 3 Frosted Gel for Tube Packaging Ref 73

A 15 50 18 83

Sodium lauryl sufate (1) TEA lauryl sulfate (2) Water

B

4 4 Ce i

12 (1) (2) (3) (4)

Perfume Igepal CO-730 (3) Lauramide DEA (4)

T 95

Standapol WAQ Special, Henkel Standapol T, 60% active, Henkel GAF Corp. Standamid LD, Henkel

Mix A and B at 50°C. Add C, mix until solution is clear. Fill hot. Set Pt about 45°C. Consistency may vary with the type of perfume. If necessary, adjust consistency with lauramide DEA. Preserve like shampoo.

74

Gels

Bath Gelée No. 4 Liquid

Ref 75 Same formulation as for Bath Gelée No. 3, but with 23 parts of water instead of 18. Total of formula is therefore 100. Bath Gelée No. 5 Slightly Frosted

Ref 75 A 45

1o)

PPG-5 ceteth-10 phosphate (1) Na laureth-2 sulfate (2) Water Perfume

B

4 4

Gs 0

Isopropyl myristate

Igepal CO-730 (3) Lauramide DEA (4) Formaldehyde USP

T 100.1

le.) wt

(1) (2) (3) (4)

Crodafos SG, Croda Standapol ES-2, Henkel GAF Corp. Standamid LD, Henkel

Same procedure as for Gelée No. 3

Ref 76

Bath Gelée No. 6 Liquid

DEA oleth-3 phosphate (1) Isopropyl myristate Propyiene glycol Water

20 20 pe 0.1

42.1

TEA lauryl sulfate (2) Na laureth-3 sulfate (3) Perfume Formaldehyde USP T 89.1

(1) Crodafos N 3 neutral, Croda (2) Standapol T, Henkel (3) Standapol ES-40, Henkel

Mix the ingredients in the order shown. For a thicker consistency add 2 parts lauramide DEA.

Gels

75

Cleansing Gel No. 1 Ringing Gel (Croda) Ref 77 AT

4 3 13.5. 3.5

Bas (1) (2) (3) (4)

DEA oleth-3 phosphate (1) B_ 1.5 Oleth-3 (2) 0.5 Oleth-5 (3) y Mineral oil, visc. 70 67 2-Ethyl-1,3-hexanediol (4) 0.1

71

Propylene glycol Perfume Igepal CO-730 Water

Formaldehyde USP T 102.1

Crodafos N 3 neutral, Croda Volpo 3, Croda Volpo 5, Croda Union Carbide. This ingredient is essential for a clear gel. Normally this

product is used as an insect repellent. Heat separately A and B to 75°C. When B is clear, pour into A. Cool to 50°C and fill. Gel turns clear after short standing.

Cologne Gel Clear Liquid Gel

Ref 78 25 5 69

Carbopol 940, 2% Sorbitol 70% ml Alcohol 95% vol

oF

0.4 0.1 0.5

TO

Perfume D&C Red No. 4, 1%

TERA T 100ml

Mix in the order shown.

Perfume Gel Viscous Translucid Gel Ref 79 7.5 12.5 40 0.05

60.05

Perfume Igepal CO-730 ml Alcohol! 95% vol FD&C Blue No. 1, 1% Mix in the order shown.

0.05 40 4 "ek

44.05

FD&C Yellow No. 5, 1% Carbopol 940, 1% TEA 10%

T 104.1 ml

16

Gels Veil Cologne Frosty Liquid Gel

Oleth-20 (1) Isopropyl myristate ml Alcohol 95% vol

15 25 Zo

Carbopol 941, 1% TEA 10%

42.5

T 102 ml

Water

Perfume

Hair Setting Gel

Rose 20 (Ref 153) Cholesterol 20 POE (1) ml Alcohol 95% vol Water

A l bec”? B 70 0.2, 732

PVP, NP K 30 (2) Sodium hydroxide 10% Carbopol 940, 1% D&C Green No. 5, 1% T 98.7 ml

(1) Solulan 24, Amerchol (2) GAF Corp.

Mix in the order shown. Pour clear solution A into B under good agitation. Stop agitation as soon as gel is formed. This gel is clear. Note, however, that most perfumes give a slight turbidity. Gel Hand Lotion Perfume Igepal CO-730 Water Glycerin

6 0.1 20 ee 28.1

ml Alcohol 95% vol Methylparaben Carbopol 940, 1%

TEA 10% T 102.4

Mix in the order shown.

The transparency of the gel may vary with the type of perfume.

Hair bleaches and related preparations

77

8. HAIR BLEACHES AND RELATED PREPARATIONS The common hair bleach preparations are the following:

Facial cream bleaches. Ref 91, 92 Peroxide creams and lotions for hair dyes. See Chapter 10 Peroxide cream activators. Ref 93, 94 Peroxide powder activators. Ref 95 Antiseptic peroxide lotions and gels. Ref 96, 97 Facial cream bleaches packaged in plastic tubes enjoy substantial sales. Actually these preparations are bleaches for facial hair. To be effective they must be mixed with a cream or powder activator prior to use. The hydrogen peroxide concentration of the cream bleaches is usually 6%. However, there is some question whether this commonly accepted maximum applies to the bleaches before or after addition of the activator. If the latter interpretation is correct, the 6% concentration can be somewhat exceeded. This reduces the bleaching time which is normally about 10 minutes. Peroxide lotions or developers for hair dyes are essentially the same as the bleaches. These lotions must be added prior to use, but a separate activator is not necessary since it is always incorporated in the hair dye base. The usual activators are ammonia, ammonium carbonate and ammonium persulfate since better catalysts have not been found in spite of extensive searches. Cream activators are preferred although they inevitably have a slight odor of ammonia. However, powder activators should also be considered since they are totally odorless when formulated with alginic acid and do not release any ammonia in use. Furthermore, powders based on ammonium persulfate raise the peroxide content above the 6% limit and this insures a perfect bleach in less than 10 minutes. Finely powdered ammonium persulfate must of course be used. Attempts to formulate cream activators based on persulfates failed due to the instability of these materials in glycols or other water soluble carriers. Antiseptic peroxide lotions are widely used, particularly as a 3% USP lotion. A similar preparation in the form of a clear gel for tube packaging is given under Ref 97. It has the same uses as the 3% USP peroxide solution with the advantage of an almost dry application. It is ideal for doctors’ offices and in the home whenever an antiseptic is needed. This preparation was found to be stable over many years when made with POE lauryl ethers derived from coconut oil fatty acids. When synthetic lauryl alcohol (produced petrochemically from fuel oils) is used for manufacturing the ethers, the gel is only stable for a little over one year. After that period the gel reverts to a viscous liquid, the peroxide content remaining unchanged. This behavior appears to be due to the fact that lauryl alcohol derived from coconut fatty acids has a straight chain of carbon atoms, whereas the synthetic alcohol is branched.

78

Hair bleaches and related preparations

Certain precautions must be observed in handling hydrogen peroxide to insure the stability of the finished products. Contaminations with metallic ions must be avoided since this causes decomposition of the peroxide resulting in a build-up of pressure. Even a decomposition of less than 0.1% is sufficient to break plastic tubes. The construction material of storage tanks for 35% and 50% hydrogen peroxide is limited to Class I Materials. This comprises the Aluminum Alloys 1060, 1260, 5254 and 5652. Bulk storage installations are suggested when the annual peroxide consumption exceeds 150,000 Ib of 50% material. In most cases, manufacturers will prefer to store the peroxide as received in polyethylene-lined fiber drums. Small quantities of peroxide can also be stored in Teflon TFE, or polyethylene (both pure unpigmented). These materials are also Class I, but the concentration of the peroxide should not exceed 52%. Processing equipment, kettles, stirrers, pumps, and filling equipment should be fabricated with stainless steel 316 or 304. Stainless steel 316 is preferred if the equipment is also used for the production of curling lotions based on ammonium thioglycolate. SS 316 and 304 are Class II, but are satisfactory when the peroxide contact is short. The welding material should be the same as used for the equipment since dissimilar metals in contact with hydrogen peroxide show a tendency for electrolytic corrosion. Aluminum tanks as well as stainless steel processing and filling equipment must be inactivated prior to use with a 5% solution of nitric acid placed in the equipment for about 24 hours. This treatment, called passivation, is only needed initially. However, if the equipment is used for other operations, anew passivation is required. Proper attention must also be given to pipe lines, valves, gaskets, etc. Gaskets and pump packing should be of Teflon; flexible hose, of polyvinyl chloride or polyethylene chemically treated. Engineering materials that should not be used include magnesium alloys, cast steel, copper, brass, bronze, monel and pipe dope. Attention must now be given to the equipment needed for the production of the deionized water that must be used for peroxide preparations. Many ion-exchange units are available for this purpose, e.g. Permutit,* AMF Cuno,** and others. These units filter the water through ion-exchange resins. Theoretically this should yield deionized water pH = 7. Actually the deionization is measured by the electric resistance of the water, which is about 16 megohm for the fresh unit, and about 1 megohm when the unit must be reactivated. In some industrial areas, serviced ion-exchange units can be rented.*** The units *Subsidiary of Zurn Industries, Paramus, N.J. ** American Machinery & Foundry, Cuno Division, Meriden, Conn. ***A firm specializing in this service is Culligan Exchange Service, International Co., Northbrook, Illinois & Brussels, Belgium.

Hair bleaches and related preparations

79

are small, compact cylinders (about 100 x 30cm) that can be assembled in batteries for any size production. When exhausted, these units are replaced. This obviates the need for regeneration and occasional change of the resins. The pH of the deionized water is on the acid side, usually pH 5 to 6; this is satisfactory for the production of peroxide preparations since these are always adjusted to a lower pH by means of phosphoric acid. All manufacturing raw materials must of course be stable with peroxide, and free of metal contaminants. The actual manufacturing procedure of peroxide preparations does not offer any difficulty. Although commercial hydrogen peroxide is perfectly stabilized,' the trade recommends a further stabilization of the dilutions by means of 0.05% phenacetin. Since this chemical is difficult to get in solution in cold water, it is recommended to prepare a solution at 85°C in about 10% of water retained from the batch. The hot solution (at 85°C) is then added to the main portion of cold water. Examples of Trade Formulations From Manufacturer’s Product Label

Helena Rubinstein, Cream Bleach for the Face

Ingredients: Water Hydrogen peroxide Mineral oil Cetyl alcohol

Stearyl alcohol Steareth-20 Stearic acid Phenacetin

Helena Rubinstein, Activating Cream

Ingredients: Water Ammonium hydroxide Cetyl alcohol

Mineral oil Petrolatum Sodium lauryl sulfate

'The stabilizing agent is not revealed by the primary suppliers. It is assumed to be a stannate.

80

Hair bleaches and related preparations Clairol, Highlights Lotion.

A peroxide bleaching lotion

Ingredients: Water Hydrogen peroxide Cetyl alcohol Isopropyl palmitate Stearyl alcohol

Laureth-4 (1) Lauramide DEA Nonoxynol-4 (2) Laureth-23 Phosphoric acid

Remarks:

(1) e.g. Brij 30, ICI (2) e.g. Igepal CO-430, GAF Corp. Clairol, Quiet Touch.

A peroxide powder activator

Ingredients:

Potassium persulfate Ammonium persulfate Sodium metasilicate Sodium stearate Silica (1)

Aluminum distearate Methylcellulose Disodium EDTA Sodium lauryl sulfate

Remark:

(1) e.g. Cab-o-Sil M-5, Cabot Corp. Jolen Cream Bleach.

Jolen Inc, Fairfield, Conn

Ingredients: Water Hydrogen peroxide Glyceryl stearate Isopropyl myristate

Stearyl stearate (1) Propylene glycol Palmitamidopropyl dimethylamine (2) Phosphoric acid

Remarks:

(1) e.g. Lipocol SS, Lipo Chemicals Corp., Paterson N.J. (2) e.g. Tegamine P-13, Inolex Corp. Jolen Accelerator: Ammonium bicarbonate

Hair bleaches and related preparations

81

Formulations Facial Cream Bleach No. 1 6% HO, Ref 91 A

3 3 3 0.1 _3.9 13.

Arlacel 165 (1) Cetyl alcohol Stearyl alcohol Stearic acid Mineral oil, visc. 70

Bi 0.05

C12 D 0.02 te 87.07

Water, deionized Phenacetin Hydrogen peroxide 50% Phosphoric acid 10% (2)

T 100.07 (1) ICI (2) Or 0.0023% commercial phosphoric acid 85% Mix A and B at 75°C. Before mixing, make sure phenacetin in part B is dissolved. Cool to 60°C, and add C and D. Stir until cold. Cream thickens at 45°C. Fill cold. pH of the cream should be between 3 and 4. Facial Cream Bleach No. 1 Alternate Formula

Ref 92

A

l a] 3 3 4 4

Ceteth-20 (1) GMS Cetyl alcohol Stearyl alcohol

B 68 0.05 2 G 42

Mineral oil, visc. 70 Paraffin mp 128°F

D

18

Water Phenacetin Laneth-16 (2) Hydrogen peroxide 50%

0.02 Phosphoric acid 10% Pat &

82.07

T 100.07

(1) Brij 58, ICI (2) Solulan 16, Amerchol

Same procedure as for Ref 91. Cream thickens at 47°C. Set Pt 41°C.

82

Hair bleaches and related preparations Peroxide Cream Activator No. 1

Ref 93 A 8 24 5

Cetyl alcohol Petrolatum white, USP Mineral oil, visc. 70

15

Beals 2 8 0.5 85.5

Water Sodium lauryl sulfate (1) Ammonia 28% Rose Fragrance T 100.5

(1) Duponol C (100%), E.I. DuPont de Nemours

~

Mix A and B at 75°C. Cool to 50°C and pump C into the emulsion to minimize the amount of vapors. An enclosed system should preferably be used, or an exhaust hood placed over the manufacturing area. Fill cold. pH = 11.5. To eliminate dust in handling, Duponol C can be replaced with an equivalent amount of sodium lauryl sulfate, 28% active. Peroxide Cream Activator No. 2

Cetyl alcohol Petrolatum white, USP Mineral oil, visc. 70 Rose Fragrance

B 70 7.5 C 4 D4 85.5

Water Sodium lauryl sulfate (1) Ammonium carbonate (2) Ammonia 28% T 101

(1) Standapol WAQ, 28% active, Henkel (2) Commercial grade, a mixture of ammonium bicarbonate and ammonium carbamate, 30-34% NH; content.

Mix A and B at 75°C. Cool to 50°C and add C, which dissolves easily. Add D as in Ref 93. Fill cold. This cream is equally as active as Ref 93, but has less ammonia odor. Note: Cream bleaches and activators should be packaged in plastic tubes to minimize contamination. The relative quantities to be packaged should be two of bleach for one of activator. Peroxide Powder Activator

Ref 95 Sodium carbonate, anhydrous Ammonium persulfate, fine powder Alginic acid

Slee

Mixing must be done under anhydrous conditions, i.e. in a dry atmosphere. This is also necessary if the ammonium persulfate must be pulverized; this requires great safety precautions to avoid explosions. Alginic acid is an essential element since it absorbs any moisture or free ammonia.

Hair bleaches and related preparations

83

Peroxide Lotion Antiseptic Lotion USP 3% H2O,

Ref 96

A 84 B

10

0.05 94.05

Water, cold, deionized Water

Phenacetin

ame D 0.02

Hydrogen peroxide 50% Phosphoric acid 10%

=o 6.0257

17100.07

Heat water B to 85°C; add phenacetin. When dissolved add at once to main portion of water A under good agitation. Refer to text.

Peroxide Gel 3% H2O2 Antiseptic Gel for Tube Packaging Laureth-23 (1) Oleth-20 (2)

B 54 0.05 Crib

60.05

Water, deionized Phenacetin Hydrogen peroxide 50%

T 100.05

(1) Prepared from lauryl alcohol derived from coconut fatty acids. See text. (2) Brij 98, ICI Mix A and B at 75°C. Cool to about 60°C and add C. Add phosphoric acid as usual. Fill as a liquid at about 50°C. Set Pt 43°C. This gel is a clear ringing gel. If necessary, it can be remelted.

84

Hair conditioners

9. HAIR CONDITIONERS The commonly used hair conditioners are the following: Cream conditioners, cationic. Ref 101, 102, 103A, B, Cream conditioners, anionic. Ref 104A & B Cream rinses, fluid. Ref 105, 106A Clear rinses. Ref 106B Conditioning hair dressings. Ref 107, 108 Hair thickeners. Ref 109 Glycerin hair conditioner, clear gel. Ref 110A & B Self-heating, cationic cream rinse. Ref 110C

C& D

Cationic cream conditioners based on quaternary ammonium compounds have good hair substantivity and are very effective for disentangling and restoring luster to the hair. Cream rinses are also based on quaternaries, but differ from the former preparations inasmuch as they tend to be of gelatinous rather than creamy consistency. They are highly effective due to a minimum concentration of waxes and oils. Hair conditioners are also formulated with amine oxides since these products exhibit mild quaternary properties in acidic solution. An acidic medium is essential because the amine oxides are anionic at PH 7 or above. Hair conditioners Ref 102 and 104A have similar consistencies and physical appearance. The first is based on stearalkonium chloride, a commonly used quaternary compound. The second does not contain a specific active ingredient and is similar to some of the recently promoted conditioners. However, the effectiveness of these newer products can be questioned although they function well as hair grooms and need not be washed out. Hair conditioners based on stearalkonium chloride are usually adjusted to a pH of about 4.0. Since stearalkonium chloride in 1% solution has a pH of 1.5 to 2.0, this must be raised to 4, preferably by addition of monopotassium phosphate, pH = 4.0 at 0.1 N (see Ref 101). Addition of citric acid is also recommended for this purpose in the label declarations. Actually, citric acid disodium salt (pH = 4.0 at 0.1 N) should be used, since addition of citric acid (pH = 2.2 at 0.1 N) cannot raise the pH. Addition of triethanolamine should not be attempted since it destabilizes the quaternary compound. Conditioners based on stearalkonium chloride must be preserved with formaldehyde or preferably methylisothiazolinone (Kathon CG). Although quaternaries are bactericides, they do not inhibit mold formation. Hair conditioners based on stearalkonium chloride are meant to be rinsed out after application. If the conditioner is to be applied like a brilliantine, it is best to use an amine oxide formulation, or reduce the concentration of the quaternary as shown in Ref 103D. Beauty parlors have been offering lately so-called “Hot Oil” conditioners that are dispensed in 1-oz plastic tubes that must be heated in hot water prior

Hair conditioners

85

to use. These conditioners are based on sulfonated vegetable oils, lauryl amides, glycerin and acetamide MEA, each at a concentration of about 10%. Whether these conditioners will stand the test of time remains to be seen. A more conventional new conditioner consists of a heat activated quaternary cream. See label declarations and Ref 110B. Examples of Trade Formulations From Manufacturer’s Label Wella Conditioner.

An amineoxide cream conditioner

Ingredients: Water Glyceryl stearate Dimethylaminopropyl stearamide (1) Cetyl lactate Diisopropyl adipate PEG-8 distearate (2) Stearamine oxide (3)

Mineral oil Sodium chloride Hydrolyzed animal protein Panthenol Fragrance Citric acid Formaldehyde

Remarks: (1) CTFA name is stearamidopropyl dimethylamine, e.g. Tegamine S-13, Inolex (2) e.g. Emerest 2642, Emery Industries (3) e.g. Ammonyx SO (Onyx), Barlox 18 S (Lonza) Wella Instant Conditioner, Balsam lotion. A quaternary cream lotion

Ingredients: Water Stearyl alcohol Petrolatum Cetrimonium chloride (1)

Fragrance Glyceryl stearate Citric acid D&C Yellow No. 10

Remark:

(1) Cetyl trimethyl ammonium chloride, e.g. Arquad 16-50, Armak Clairol, Herbal cream rinse and conditioner.

Ingredients: Water Isopropyl alcohol Hydroxyethyl cellulose (1) Quaternium 18 (2) Fragrance

An opaque lotion

Cetearyl alcohol (3) Methyl paraben Propyl paraben D&C Green No. 5 FD&C Yellow No. 5

Remarks: (1) e.g. Cellosize QP 5200, Union Carbide, or Natrosol 250, Hercules, Inc (2) Dimethyl di(hydrogenated tallow) ammonium chloride, e.g. Aliquat H 226, General Mills (3) Mixture of cetyl and stearyl alcohols

86

Hair conditioners Revlon, Flex Hair Rinse and Conditioner

Ingredients: Water Stearalkonium chloride Hydrolyzed animal protein Cetyl alcohol Ceteareth-S (1) Balsam Canada Propyl paraben

Methyl paraben Citric acid Quaternium-15 (2) Fragrance DM DM Hydantoin (3) FD&C Yellow No. 5 D&C Green No. 5

Remarks: (1) Polawax, Croda (2) Dowicil 200, Dow Chemical (3) 1,3-Dimethylol-5,5-dimethyl hydantoin

Kolestral, True Hair Conditioner.

The Wella Corporation

Ingredients:

Water Cetyl alcohol Lanolin Glyceryl stearate

Petrolatum (and) lanolin alcohols Fragrance Sodium lauryl sulfate Methyl paraben

A cream for tube packaging. Note the absence of quaternaries. Thicket, a cream hair thickener. package

Madric Ltd, New York, N.Y. A 1-oz tube

Ingredients: Water Carnauba wax Carbomer-940 (1) Laneth-10 PVP/VA Copolymer (2) Triethanolamine Remarks:

(1) Carbopol 940, Goodrich Chemical (2) e.g. PVP/VA E-535, GAF Corp. (3) e.g. PVP K 30, GAF Corp.

Perfume PVP (3) Ammonia Methylparaben Propylparaben

Hair conditioners Top Brass, Hair Thickener.

87

Revlon, Inc

Ingredients: Water PVP (1) Triisopropanolamine (2) Carbomer-934 PPG-10 cetyl ether (3) Hydrolyzed animal protein

Vinylpyrrolidone/styrene copolymer (4) Fragrance Formaldehyde Methylparaben Propylparaben

Remarks:

(1) (2) (3) (4)

e.g. PVP NP-K 30, GAF Corp. Union Carbide e.g. Procetyl 10, Croda Polectron 430, GAF Corp. A clouding agent.

TCB Glycerin Curling Activator, pH = 5 balanced. gel in transparent plastic tube

Alberto Culver. Clear

Ingredients: Water Glycerin Oleth-S (1) Mineral oil DEA oleth-3-phosphate (2) Propylene glycol PEG-60 hydrogenated castor oil (3) Laneth-10 acetate (4) Oleth-3 phosphate (5)

Fragrance Quaternium-18 (6) Acetamide MEA (7) Benzyl alcohol Lauryl alcohol (8) Dihydroxyethyl C,2-1; alkoxypropylamine oxide (9) Formaldehyde Quaternium-19 (10) FD&C Yellow No. 6

Remarks:

(1) (2) (3) (4) (5) (6) (7) (8) (9)

Volpo 5, Croda Crodafos N 3 Neutral, Croda e.g. PEG-30 Supersat AWS-3, R.I.T.A. Chemical Corp. e.g. Crodalan AWS, Croda Crodafos N 3 Acid, Croda e.g. Adogen 442, Ashland, or Arquat 2HT-75, Armak N-Acetyl ethanolamine, a conditioner, Scher Bros, Inc e.g. Alfo 12, Conoco Chemicals Combination of dihydroxyethyl cocamine oxide and cocoamidopropylamine oxide, e.g. Aromax C/12 W, Armak and Ammonyx CDO, Onyx Chemical (10) Polymer JR-125 or J-400, Union Carbide

88

Hair conditioners

Tressemmé, Hot oil formula. Ingredients: Water Acetamide MEA (1) Cocotrimonium chloride (2) Oleth-20 Hydroxyethyl! cellulose

Alberto Culver, 1 fl oz tube

PEI-15 (3) PEI-15 hydrochloride Fragrance Methylparaben D&C Red No. 39

Remarks: (1) N-Acetyl ethanolamine, Scher Bros, Inc (2) Coconut trimethylammonium chloride, Arquad-50, Armak (3) Polyethylenimine, Dow Chemical

How to use: Place tube in hot water for one minute. Apply on wet hair. Massage oil into hair for one or two minutes, then rinse with warm water. Thermique, Self-heating hair conditioner.

Régime Inc, Los Angeles, Calif.

Part 1. Cream conditioner, | fi oz Packette (laminated envelope) Part 2. Activating crystals, 5 gram Packette (adjacent envelope) Ingredients (Part 1):

Purified water Hydrolyzed animal protein Quaternium-31 (1) Cetyl alcohol Stearyl alcohol

Quaternium-7 (2) Ceteareth-5 (3) Methylparaben 1-Bromo-2-nitropropane-1,3-diol (4) Fragrance

Ingredient (Part 2):

Activating mineral powder Remarks: (1) (2) (3) (4)

Alkyl dimethyl ammonium chloride, Adogen CG, Sherex Chem. Pyridinium chloride, e.g. Emcol E-607 S, Witco Chemical PEG-S Cetyl/Stearyl ether Bronopol, Inolex

How to use: 1. 2. 3. 4.

Squeeze to Manipulate Work into Rinse with

break middle seal of Packette Packette until heated hair, leave on for 3-5 minutes warm water

Hair conditioners

89

Formulations Hair Conditioner No. 1 Cationic Cream. Not Fluid

Ref 101 APO Z 3 3 as 8.7

Ceteth-20 (1) Stearic acid Cetyl alcohol Ethylene glycol distearate (2)

B

5 80 0.5 at Ssioy

Stearalkonium chloride (3) Water Potassium monophosphate deez

(1) Brij 58, ICI (2) Stepan, Kessco Division (3) Ammonyx-4, Onyx Chemical Mix A and B at 75°C. Set Pt 43°C. pH = 4.0. See text. Hair Conditioner No. 2 Cationic Cream. Semi-Fluid

Ref 102 A

2 3 3 3

Laneth-16 (1) GMS Cetyl alcohol

BY

Mineral oil, visc. 70

C

>

80

11

0.1 _3.9° 89

Stearalkonium chloride (2) Water Sodium chloride Water T 100

(1) Solulan 16, Amerchol (2) Ammonyx-4, Onyx Chemical Mix A and B at 75°C. Cool to 50°C. Add solution C. Cream thickens at 42°C. Set Pt 39°C. Fill cold.

Ref 103A A 0.5 1 1.5 2 0.2 a2

.o)

Cream Lotion Conditioner Cationic Lotion. Fluid

Laneth-16 Arlacel 165 Cetyl alcohol GMS Balsam perfume

|) 80 C 9.7 0.1 94.8

Stearalkonium chloride (1) Water Water Sodium chloride T 100

(1) Ammonyx-4, Onyx Chemical Composition given by the manufacturer: 20% stearyl dimethyl benzyl ammonium chloride, 5% cetyl alcohol, 1% amine oxide.

90

Hair conditioners Cream Lotion Conditioner Cationic. Fluid Alternate Formula

Ref 103B A 0.5 1 2 1

Laneth-16 (1) Ceteth-20 (2) GMS Cetyl alcohol

B}-5

C

rey.

4.5

79.4 0.1 “is $5754

Stearalkonium chloride (3) Water Sodium chloride | Water 0 LD)

(1) Solulan 16, Amerchol (2) Brij 58, ICI (3) Ammonyx-4, Onyx Chemical

Mix A and B at 75°C. Cool to 50°C. Add C. Addition of C turns lotion to white color. Cream Lotion Conditioner Cationic. Fluid

High Viscosity

Ref 103C A 0.5 0.5 1

ne 2

Laneth-16 (1) Ceteth-20 Ethylene glycol monostearate (2)

BisiS

C

82 0.3

Stearalkonium chloride (3) Water Sodium chloride

la, 88.3

Water T 90.3

(1) Solulan 16, Amerchol (2) No. 70, Stepan, Kessco Div. (3) Ammonyx-4, Onyx Chemical Same procedure as for Ref 102. Note high viscosity, although solid content is reduced.

Hair conditioners

Ref 103D A 4

Cream Conditioner Low Quaternary Concentration Not Fluid

Ethylene glycol distearate

B

2

Stearalkonium chloride

0.5

Monopotassium phos-

(1)

(3)

Cetyl alcohol

Stearic acid

phate

Ceteth-20 (2)

80

0.05 _0.25

Water

FD&C Yellow No. 5, 1% FD&C Blue No. 1, 1%

B2:8, ys8,935 (1) Stepan, Kessco Division (2) Brij 58, ICI (3) Ammonyx-4, Onyx Chemical

Mix A and B at 75°C. Pour at 54°C. Set Pt 44°C. pH = 2.9.

Ref 104A A 11.5

—

in

91

Hair Conditioner No. 3 Anionic Cream

Mineral oil, visc. 70 Stearic acid GMS Cetyl alcohol Lanolin Hydrogenated coconut oil (1) Stearyl alcohol Cetyl vicinal glycol (2)

BY 0.1 0.1 0.15 0.4 0.25 78.5

Propylene glycol Germall 115 Methylparaben Propylparaben TEA Borax Water Rose perfume

80.5

T 100

(1) e.g. Cobee No. 92, PVO (2) Adol 158, Sherex Chemical, Viking Chemical Division

Mix A and B at 75°C. Set Pt 42°C. Fill cold.

92

Hair conditioners Hair Conditioner No. Anionic Cream

Ref 104B A 10 15 2 3 iz

GMS Paraffin mp 128°F Stearic acid Mineral oil, visc. 70 Laneth-16 (1)

BZ 1.5 0.1 65 0.1 0.1

32

68.8

Propylene glycol Sodium lauryl sulfate (2) Methylparaben Water FD&C Yellow No. 5, 1% FD&C Yellow No. 6, 1%

T 100.8

(1) Solulan 16, Amerchol (2) Standapol WAQ, 28% active, Henkel Mix A and B at 75°C. Set Pt 39°C. This cream has a dry rub-out. Hair Rinse and Conditioner For Plastic Squeeze Bottle Standard Formula

Ref 105 a)

B

80 2 0.5 2

35.5

Stearalkonium chloride (1) Water Ethylene glycol distearate (2) Ceteth-20 (3) Cetyl alcohol

C 10 0.1 0.4

D

0.15. 0.15

10.8

Water Sodium chloride Hydroxyethyl cellulose (4) FD&C Yellow No. 5 Perfume

T 100.3

(1) Ammonyx-4, Onyx Chemical (2) Stepan, Kessco Div. (3) Brij 58, ICI

(4) Cellosize 52000 QP, Union Carbide Mix A and B at 75°C. Cool to 50°C. Slurry C, and add at once to batch before gel sets. Addition of part C may not be necessary, depending on the viscosity that is desired.

Hair conditioners

93

Cream Rinse Translucid, Pearlescent, Fluid

Ref 106A A. 2

B

84 0.8 0.2 90

Stearalkonium chloride (1) Water Emerest 2642 (2) Perfume

Gil

0.3 0.05 0.05

10.4

Water Sodium chloride D&C Red No. 19, 1% D&C Red No. 22, 1%

1 100.4

(1) Triton X-400, Rohm & Haas Co. This quaternary is not formulated; it should be used for pearlescence. (2) Emery Industries, a formulated emulsifier; CTFA-adopted name is PEG-8 distearate. The regular distearate is not water dispersible and would opacify the rinse. Clear Rinse

Ref 106B Polymer JR 400 (1) Propylene glycol Water

B 0.2 0.8 5

6° 4)

Perfume Tween 60 (2) Alcohol 95% vol

100

(1) Quaternium-19, Union Carbide (2) Polysorbate-60, ICI Mix part A and let stand for about | hour until gel is clear. Stir occasionally. Add part B last. Cocoa Butter Conditioner

Ref 107 Beeswax Paraffin, mp 128°F Mineral oil, visc. 70 Stearyl alcohol

B 22 0.75 0.15 0.1

Water Borax Methylparaben Cocoa butter fragrance

Cocoa butter

DS

Mix A and B at 75°C. Fill hot.

E97

94

Hair conditioners

Pine Tar Conditioner for the Scalp Dark, Artificially Colored Petrolatum, dark (1) Ozokerite No. 4 Paraffin, mp 128°F Mineral oil, visc. 70 Lanolin Hydrogenated coconut oil

Cw D 0.96 0.015 0.010 0.015

Pine tar oil Isopropyl palmitate D&C Violet No. 2 D&C Green No. 6 D&C Yellow No. 11

3 T 100 (1) Petrolatum 3 C, Witco Chemical Melt part A and cool to 70°C. Add parts B and C. Disperse colors D and add to batch. Fill hot. Set Pt 38°C.

Ref 109 A 10 35 5

Hair Softener and Conditioner Also Hair Thickener For Pump Spray Bottle Glycerin Propylene glycol

B 50 0.1

PVP, NP-K 30 (1)

C

20,1 0.1

50.3

50

Water Methylparaben Perfume

Igepal CO-730 (2) T 100.3

(1), (2) GAF Corp.

Heat part A to dissolve PVP. Add B and C.

Hair conditioners

Glycerin Hair Conditioner Clear Gel for Tube Packaging

Ref 110A 20 15 T5. 50

95

Glycerin PPG-S ceteth-10 phosphate (1) Oleth-10 (2)

50 0.1

Water Formaldehyde USP Fragrance

50.1

T 100.1

(1) Crodafos SG, Croda (2) Volpo 10, Croda Procedure: Cold mix. Although glycerin (or propylene glycol) is an effective preservative, the addition of formaldehyde is necessary for sterilization since the preparation is a cold mix.

Ref 110B A 10

10 5 10 35

Glycerin Hair Conditioner Ringing Clear Gel PPG-S5 ceteth-10 phosphate (1)

Oleth-20 (2) Laureth-4 (3) Mineral oil, visc. 70

Bess 10

0.1

Water Glycerin Formaldehyde USP

woe 65.P"-T 100A

(1) Crodafos SG, Croda (2) Brij 99, ICI (3) Brij 30, ICI Mix A and B at 75°C. Pour at about 50°C.

96

Hair conditioners

Self-Heating Hair Conditioner Quaternary Hair Rinse

Ref 110C Part 1. Lotion base A l Ceteth-20 (1) 1 2 2

Laneth-16 (2) Cetyl alcohol Ethylene glycol distearate

a6

FG)

B 50 5

Water Stearalkonium chloride

C 29

Hydrogen peroxide 6%

(4)

bar84

T 90

(1) Brij 58, ICI (2) Solulan 16, Amerchol (3) Stepan, Kessco Division

~ (4) Ammonyx-4, Onyx Chemical

Mix A and B at 75°C. Add peroxide solution.

Part 2. Heating unit

1 .o7)

Water N

—

Thiourea, Onyx Chemical Monoethanolamine, Union Carbide

5 ty Simple mixing Packaging: Pack in two adjacent laminated packettes. For one application, fill 27 grams of the lotion base and 5.1 grams of the heating unit. Accurate filling is necessary since excess of peroxide or monoethanolamine must be avoided after reaction. How to use: Mix part 1 and part 2 in the combined packettes. Apply the hot mixture (50°C) for 5 minutes, then rinse with warm water.

Note: Part 1 was tested for peroxide stability for 24 hours at 95°C and is better than 80%. Part 1 is acidic, and the peroxide is consumed on adding part 2. This increases the acid content which is neutralized by the monoethanolamine.

Hair dyes

97

10. HAIR DYES Although numerous hair dyes are constantly being patented, manufacturers are hesitant in replacing dyes with a long record of efficiency and safety. J.F. Corbett pointed out recently that p-Phenelenediamine —a well-known oxidation dye—was used as early as 1883 and still forms the basis of the permanent hair colorants used today.! A classification of the dyes and intermediates that the industry believes to be safe is given in the Corbett paper. The most frequently used colors are shown in Table I which also gives shade formulations. The colors are divided into three classes. The primary colors (A) are amines that undergo oxidation with peroxide to give benzoquinone imines. The imines react rapidly with couplers (B) to produce indo dyes which form at least part of the final color produced in the hair. The table also shows some semi-permanent dyes under heading (C). These dyes are usually dispersed in a shampoo base which is left on the hair for 20 to 40 minutes before being rinsed out. These same colors are also used as oxidation dyes. The question of the safety of hair dyes cannot be discussed here. The reader should review the paper by Corbett mentioned above in which the author contradicts recent statements in the press that hair dyes may be carcinogenic. These statements were based on findings by Ames that certain dye ingredients are mutagenic toward a special strain of Salmonella typhimurium. While there is no doubt that Ames’ findings are correct, two questions remain to be answered:

1. Whether Ames’ tests imply that the dye intermediates are carcinogenic. 2. Whether the hair dyes formed in the oxidation process are mutagenic in Ames’ tests. The first question can be answered negatively if interpretations of the trade literature are correct. The second question cannot be answered until the tests are made. Ames only tested dye intermediates which are short-lived in the process of dyeing the hair, as they rapidly undergo reaction or are rinsed out altogether. These color forming reactions should be clearly understood. As an example in hair dyeing with p-phenylenediamine and 2,4-diaminoanisole the following chain of reactions takes place: 1J.F. Corbett, Hair Dyes—Their

21-27 (1976).

Chemistry and Toxicology, Cosmetics and Toiletries, 9/,

98

Hair dyes OCH;

— esc...

our Quinone diimine

p-Phenylenediamine

wien

ae

2,4-Diaminoanisole

OCH;

H.N Indamine dye II

This oxidation intermediate further reacts with p-phenylenediamine to form the coloring element indoaniline dye II of similar chain structure. The FDA has questioned the safety of the following widely used dye intermediates:

2,4-Diaminoanisol p-Toluenediamine 2-Nitro-p-phenylenediamine 4-Amino-2-nitrophenol Hair dyes containing these intermediates must carry a warning label. However, there are no other legal restrictions since hair colors were exempted from certification by Congress. Semi-permanent hair dyes do not require peroxide developers, but the hair tint does not last more than 4 shampooings. They are based mostly on nitroso or nitro aniline colors that are somewhat substantive to the hair. These preparations hardly have any advantages over the oxidation hair dyes. However, they seem to be preferred by men and are also used by women who are allergic to peroxide. Semi-permanent hair dyes can also be based on cobalt and chromium complexes of azo dyes, but these dyes are presently not available in the U.S. for hair dyeing. See Proceedings of the Society of Colorists and Dyers 7/, 7105

(1955). Oxidation hair dyes are applied after addition, prior to use, of an equal volume of 6% peroxide solution. The peroxide acts simultaneously as a hair bleach and as an oxidation agent for the dyes. The mixture should gel at once to prevent running off the scalp. A clear or translucent gel is required that must work up into a thin foam for better rub-in and wash-out. These conditions can be met in various ways as can be seen from the ingredient label declarations. However this requires a correct interpretation of the CTFA names

which are often of considerable complexity.

Hair dyes

99

A simple formulation is shown under Ref 111. The gelling agent is oleyl alcohol in the presence of monoethanolamine oleate which is formed in situ. The oleyl alcohol is solubilized with Igepal CO-630 in order to give a clear gel. Additional ingredients are propylene glycol, a solubilizer of the dyes, and isopropyl alcohol, a thinning and clarifying agent that also helps the solubilization of the dyes. These ingredients must be added before the water to prevent gelling. Sodium sulfite keeps the dye lotion from darkening on ageing; it acts as an antioxidant but does not reduce the dyes. The last item added is ammonia which is essential since it activates the peroxide. In some preparations it is partially replaced with free monoethanolamine in order to minimize the odor of ammonia. Another formulation is given under Ref 112. It contains less oleic alcohol and solubilizer, but requires the addition of POE-5 oleamide, a hair dye complexing agent that disperses and gels in water. A self-heating hair dye lotion may be obtained by adding 3% of sodium sulfite. However this may impair the transparency of the preparation and possibly cause a chemical reduction of the dye intermediates. It is therefore preferable to use thiourea as a non-toxic heating element. An addition of 1% thiourea to the hair lotion raises the temperature from 25 to 50°C after the peroxide solution has been added. The strongly exothermic reaction oxidizes the thiourea into urea and sodium sulfate. For complete oxidation 1 g thiourea requires 29 g peroxide, 6% solution. Examples of Trade Formulations From Manufacturer’s Product Label Ogilvie Hair Color.

Cream for tube packaging (Oxidation hair dye)

Ingredients: Water Cetyl alcohol Oleth-7 Glyceryl stearate Decyl oleate Potassium oleate

May contain: Toluene-2,5-diamine 4-Methoxy-m-phenylenediamine 4-Amino-2-hydroxytoluene m-Aminophenol p-Aminophenol

Ammonia Fragrance Polyacrylic acid EDTA Sodium hydrosulfite Silica Resorcinol Pyrogallol 1-Naphthol-2,7-naphthalenediol 2-Amino-4-nitrophenol 2-Nitro-p-phenylenediamine Disperse Violet 4 (1)

Remark: (1) CTFA name for Celliton Fast Violet 6 BA-CF, an anthraquinone dye, GAF Corp.

100

Hair dyes

Clairol Great Day. Hair dye for men (not an oxidation hair dye). U.S. Patents 3168442, 3642423, 3733175 Ingredients: Water HC Yellow 2 (4) Lauramide DEA (1) Ethanolamine (2) Hydroxyethyl cellulose Citric acid BHT Sodium m-nitrobenzene sulfonate (3) Fragrance Isopropyl alcohol

Disperse Blue 1 (5) Disperse Black 9 (6) 2-Amino-4-nitrophenol (7) Disperse Violet 11 (8) HC Yellow 3 (9) | HC Blue 1 (10) HC Red 3 (10)

Remarks:

(1) (2) (3) (4) (5) (6) (7) (8) (9) (10)

Lauric diethanolamide Monoethanolamide Monsanto Chemical CTFA hair color name, a nitroaniline derivative Celliton Blue GA EX, an anthraquinone derivative, GAF Corp. Nacelan diazine black JS, an azo dye, Allied Chemical Color Index 76530 Nacelan Violet 5 RL, an anthraquinone dye, Allied Chemical A nitro-o-phenylenediamine derivative (CTFA) A nitro-p-phenylenediamine derivative (CTFA)

Note predominance of nitro colors for direct dyeing without peroxide. Application time of the preparation is 30 minutes. Clairol Color preparation.

Hold.

Must

be applied

after treatment

Ingredients:

Water Olealkonium chloride Quaternium 39 (1)

Phosphoric acid Fragrance

Remark: (1) Reten 205M, 210 or 220, Hercules, Inc

of the above

Hair dyes

101

L’Oréal, Preference permanent hair color. An oxidation hair color. 2 fl oz Ingredients: Water Cocamide DEA (1) Butoxyethanol (2) PEG-2 tallow amine (3) SD Alcohol 39 B Polyglyceryl-4-oleyl ether (4) Oleyl alcohol Polyglyceryl-2-oleyl ether (5) Propylene glycol

Oleic acid Sodium monodiethylaminopropylcocoaspartamide (6) Ammonium hydroxide Pentasodium pentetate (7) Ammonium acetate Sodium bisulfite Fragrance

Color intermediates for Dark Auburn: Hydroquinone Phenylmethylpyrazolone p-Aminophenol p-Phenylenediamine p-Methylaminophenol sulfate

Resorcinol m-Aminophenol 2-Methyl-5-hydroxyethylaminophenol

Remarks: (1) (2) (3) (4) (5) (6) (7)

e.g. Carsamide C-3, Carson Chemical Butyl cellosolve, Union Carbide e.g. Ethomeen T/12, Armak Tetraglyceryl monooleyl ether, Capital City Products Diglyceryl monooleyl ether, Capital City Products Supplier not listed in CTFA e.g. Vertenex 80, Dow Chemical

L’Oréal, Creme color developer.

2 fl oz

Ingredients: Water Peroxide Ceteth-2 (1) Oleamide DEA (2)

EDTA Acetic acid Phosphoric acid Acetanilid

Glycerin

Oxyquinolene sulfate

Remarks:

(1) Brij 52, ICI (2) e.g. Clindrol 200-0, Clintwood Chemical

102

Hair dyes Colorsilk, Ammonia-free hair color. Revlon. An oxidation hair color. 2 fl

OZ Ingredients: Water Ethanolamine (1) Isopropyl alcohol Linoleamide DEA (2) Cleamide DEA (3) PEG-2 cocamine (4) TEA laurylsulfate

Potassium cocohydrolyzed animal protein Sodim sulfite Fragrance PPG-40 butyl ether (5) Laneth-S (6) Tetrasodium EDTA

Color intermediates for Dark Brown:

y

2,3-Naphthalenediol 4-Nitroso-o-phenylenediamine p-Phenylenediamine . N-Hydroxyethyl-4-nitro-oN-Phenyl-p-phenylene diamine HCl phenylene diamine m-Phenylenediamine 2-Methylresorcinol 4,4-Diaminophenylamine sulfate 4-Amino-o-cresol p-Aminophenol 2-Chloro-p-phenylenediamine o-Aminophenol sulfate Resorcinol 4-Ethoxy-m-phenylenediamine Pyrogallol sulfate 1,5-Naphthalenediol m-Aminophenol HCl Remarks: (1) (2) (3) (4) (5) (6)

Monoethanolamine, Union Carbide e.g. Monamid 15-70W, Mona Industries e.g. Clindrol 200-0, Clintwood Chemical e.g. Ethomeen C/12, Armak e.g. Ucon LB-1145, Union Carbide e.g. Polychol 5, Croda

Colorsilk, Cream color developer. 2 fl oz

Ingredients: Water Hydrogen peroxide Cetearyl alcohol

Sodium lauryl sulfate Phenacetin Sodium phosphate

Ceteareth-20

Phosphoric acid

Mineral oil

Hair dyes

103

Miss Clairol, Hair color. An oxidation hair dye. 2 fl oz Ingredients: Water Oleic acid Octoxynol-1 (1) Isopropyl alcohol Propylene glycol Nonoxynol-4 (2) Glycerin Ammonium hydroxide

Ethoxydiglycol (3) Sodium lauryl sulfate Glycol Fragrance EDTA Erythorbic acid (4) Sodium sulfite

Dye intermediates for Sunlit Brown: Resorcinol 2-Methylresorcinol 4-Amino-2-hydroxytoluene p-Aminophenol

m-Aminophenol N,N Bis (2-hydroxyethyl) p-phenylene-diamine sulfate p-Phenylenediamine

Remarks: (1) (2) (3) (4)

Triton X-15, Rohm & Haas Co. Igepal CO-430, GAF Corp. Carbitol, Union Carbide Isoascorbic acid, Merck & Co.

Miss Clairol, Color hold shampoo.

0.3 fl oz

Ingredients: Water Amphoteric-18 (1) SD Alcohol 40 Quaternium-19 (2)

DMDM Hydantoin Imidazolidinyl urea Phosphoric acid Fragrance

Remarks: (1) Monateric 805, Mona Industries, Inc (2) Polymer JR-125 or JR-400, Union Carbide

Other colors: Blonde, Red, Brown, Gray, Black. Cream Clairoxide and applicator bottle are sold separately.

Developer or

104

Hair dyes

Breck, Shampoo-in hair color.

Shulton, Inc. An oxidation hair dye. 2 fl.oz

Ingredients: Water Nonoxynol-9 (1) Oleyl alcohol Isopropyl! alcohol

Ammonium tallate (2) SD Alcohol 40 Ammonium hydroxide Fragrance

Additional ingredients for Dark Brown:

p-Phenylenediamine Toluene-2,5-diamine sulfate Resorcinol (3) Phloroglycinol (4) Trisodium HEDTA

Sodium sulfite 4-Ethoxy-3-phenylene diamine sulfate 2 2-Amino-5-nitrophenol Pyrocatechol (5)

Remarks: (1) e.g. Igepal CO-630, GAF Corp. (2) Ammonium salt of tall oil acid. The acid is available under the name Acintol, Arizona Chemical (3) 1,3-Dihydroxybenzene (4) 1,3,5-Trihydroxybenzene (5) 1,2-Dihydroxybenzene

Developer.

2 fl oz

Ingredients: Water Hydrogen peroxide Vinylpyrrolidone/styrene copolymer (1) PEG-8 laurate (2) PEG-75 (3) Remarks: (1) (2) (3) (4) (5) (6)

Lanolin Laureth-23 (4) PEG-4 oleate (5) Glycol stearate (6) Phosphoric acid Other ingredients

e.g. Polectron 430, GAF Corp. A clouding agent e.g. PEG 400 monolaurate, Stepan, Kessco Div. e.g. Carbowax 4000, Union Carbide e.g. Brij 35, ICI e.g. PEG 200 monooleate, Stepan, Kessco Div. Ethylene glycol monostearate

Hair dyes Protein Conditioner. Ingredients:

105

4 grams

Hydrolyzed animal protein Water Methylparaben

Benzalkonium chloride Propylparaben

How to use: Mix Color, Developer and Protein conditioner. Rinse and shampoo. Clairol Color Foam, Aerosol hair color.

Apply for 20 minutes.

“No Peroxide, No Ammonia.”

“Washes out in 5 or 6 shampoos, 3 or 4 weeks.” Ingredients: Water Ethoxydiglycol (1) Hydroxyethyl cellulose (2) Hydrofluorocarbon 152 A (3) Tall oil acid (4) PEG-S0 tallow amide (5) Lauramide DEA

Isobutane (6) aye & lial Erythorbic acid (7) Fragrance Ethanolamine (8) Glycol

Colors for Dark Brown:

H C Yellow No. 4 Acid Orange 3 (9) Disperse Violet No. 11 Disperse Black No. 9

H C Yellow No. 2 H C Red No. 3 H C Blue No. 1 Disperse Blue No. 1 (10)

Remarks:

(1) (2) (3) (4) (5) (6) (7) (8) (9) (10)

Carbitol, Union Carbide e.g. Cellosize QP, Union Carbide Propellant, e.g. Genetron 152 A, Allied Chemical e.g. Acintol, Arizona Chemical Ethomid HT/60, Armak Propellant Isoascorbic acid, Merck & Co. Monoethanolamine, Union Carbide Xylene fast yellow ES, Sandoz Colors & Chemicals Artisil Blue SAP Conc., Sandoz Colors & Chemicals

H C Colors are identified in CTFA. Other Clairol Foam shades are available in Blonde, Red, Brown, Gray and Black.

106

Hair dyes

Formulations Hair Dye Lotion No. 1 Base

Ref 111 A 10 15 aP) 2.2 10 BUUES 69.2

Oleic acid (1) Oleyl alcohol (2) Nonoxynol-9 (3) Monoethanolamine (4) Propylene glycol Isopropanol

B0.2""EDTA'6) 0.5 Sodium sulfite (6) 0.1 Protein 25 Water C23 Ammonia 28% NH;

3083.0: (1) (2) (3) (4) (5) (6)

Pel00

Double distilled Adol 85, Sherex Chemical Igepal CO-630, GAF Corp. Union Carbide Versene, Dow Chemical NaHSO; anhydrous

Mix in the order shown while stirring. Dissolve the dyes in the propylene glycol at 50-60°C before adding to batch. The pH of the hair lotion should be 10. Check the shade by tinting a skein of wool dipped for 30 minutes in the mixture with peroxide. Hair Dye Lotion No. 2 Base

Ref 112 A 10 8 7 15S ) 10 10 65

Oleic acid Oleyl alcohol POE-S oleamide (1) Nonoxynol-9 TEA (2) Propylene glycol Isopropanol

B

0.2 0.5 0.1 29.2 Cran hae 35

EDTA Sodium sulfite Proteine Water Ammonia 28% NH;

T 100

(1) Oleamide O/15, Armak (2) Commercial grade, Union Carbide, 85% TEA, 13% DEA

Other ingredients, same as for Ref 111. Same procedure as for Hair dye lotion No. 1.

Hair dyes

107

Hair Dye Lotion No. 3 Ammonia-Free Ref 113

Same formulation as hair dye lotion Ref 111, replacing ammonia with 6 parts monoethanolamine to be added to part A. Addition of peroxide prior to use causes formation of a gel as required for these preparations. Hair Dye Lotion No. 4 For Shampoo-In

Ref 114 Same formulation as hair dye lotion Ref 112, using 50 parts of this lotion diluted with 5 parts isopropanol and 45 parts of water. Addition of isopropanol is necessary to prevent premature gelling of the hair lotion. This preparation gives a clear gel when adding an equal volume of 6% peroxide solution prior to use. Color intermediates for Brown To 100 g hair lotion, add: 0.05 0.2 0.2 0.05 0.1 0.05 0.1 0.75

2,3-Dihydroxynaphthalene (1) 4-Chlororesorcinol (2) p-Phenylenediamine (3) 2,4-Diamino anisole (3) 2,5-Toluenediamine sulfate (3) 4-Nitro-o-phenylenediamine (3) 4-Amino-2-nitrophenol (3) Dissolve in propylene glycol

(1) An antioxidant, Lowenstein Dyes Co., U.S. Pat 3 415 608 (1968) (2) Lowenstein Dyes, Inc, Brooklyn, N.Y. (3) Ashland Chemicals, Meadows, N.J.

Southland

Chemical

Div.,

Great

The above hair dye intermediates are the most widely used. They can be described as follows:

p-Phenylenediamine: Gray pink crystalline powder for black. 2,5-Toluenediamine sulfate: Off-white powder for black. 2-Nitro-p-phenylenediamine: Red-brown crystalline powder for brown. 4-Nitro-o-phenylenediamine: Red crystalline powder for brown. 2,4-Diaminoanisol sulfate: Off-white to violet powder for blues and grays. 4-Amino-2-nitrophenol: Dark reddish-brown powder for gold blond and red. To these, one should add the commonly used phenolic hair dye modifiers, particularly resorcinol, pyrocatechol, pyrogallol and phloroglucinol.

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108 Hair dyes

Hair grooming preparations 11. HAIR GROOMING

109

PREPARATIONS

The hair grooming preparations commonly used are the following: Hair sprays. Ref 116, 117 Hair dressings, alcoholic. Ref 118-120 Brilliantines, liquid. See below Brilliantines, solid. Ref 121 Brilliantines, washable. Ref 122 Hair dressings, emulsified. Ref 123A & B Hair dressings, gels. See Gels Hair pomades. Ref 124 See also Hair conditioners Hair sprays, aerosols or atomized sprays are very popular since they have the advantage of setting the hair in any desired style. Most of these products are solutions of PVP or resins in alcohol. Since the concentration of alcohol is usually high, 50% or more, these sprays are quite flammable and should be sold with a prominently displayed caution label. Alcoholic hair dressing lotions are also widely used because of their ease of application without excessive greasiness. Liquid brilliantines are much less in demand today. These brilliantines are perfumed mineral oil, but sparkling solutions are a prerequisite. Citrus perfumes have best solvency in mineral oil although other perfumes can be used in formulations that consist of 50% mineral oil and 50% isopropyl myristate. Besides satisfactory solvency, perfume oils must be dry. This may require a treatment with anhydrous sodium sulfate to remove traces of moisture. Perfumes should also preferably be light in color. Solid brilliantines are based on petrolatum with or without addition of lanolin. These preparations are most effective to keep the hair well groomed. Washable brilliantines that allow easy removal of excess grease are the most recent addition to hair grooming preparations. Emulsified hair dressings are widely used in barber shops. They are often water in oil emulsions that must be carefully formulated as they tend to be

unstable. Finally, pomades must also be mentioned since they are becoming increasingly in demand.

110

Hair grooming preparations

Examples of Trade Formulations From Manufacturer’s Product Label

Vitalis, Hair dressing lotion. Bristol-Myers Ingredients:

S.D. Alcohol No. 40 PPG-40 butyl ether (1) Water Benzyl benzoate

Fragrance Dihydroabietyl alcohol (2) FD&C Yellow No. 10

FD&C Yellow No. 6

Remarks: (1) Ucon LB-1715, Union Mie ace (2) Hercules, Inc

Vitalis Clear Gel. Bristol-Myers Co. Packaged in tubes Ingredients: S.D. Alcohol No. 40 Water Dipropylene glycol PPG-27 glyceryl ether (1) Glycerin PPG-S5S glyceryl ether (2) Diisopropyl adipate (3) PPG-40 butyi ether (4)

PEG-15 Cocamine (5) Carbomer 940 (6) Triisopropanolamine Hydroxypropyl cellulose (7) Fragrance FD&C Yellow No. 5 FD&C Yellow No. 6

Remarks: (1) (2) (3) (4) (5) (6) (7)

Emcol CD-18, Emcol CC-43, e.g. Crodamol Ucon LB-1715,

Witco Chemical Witco Chemical DA, Croda Union Carbide

Ethomeen C 25, Armak

Carbopol 940, Goodrich Chemical Klucel, Hercules, Inc

Alberto Culver VO 5 Hair Dressing.

A brilliantine

Ingredients: Mineral oil, light Petrolatum PEG-8 dilaurate (1) Paraffin Isopropyl myristate

Remark:

(1) Polyethylene glycol 400 dilaurate

Fragrance BHA D&C Violet No. 2 D&C Green No. 6

Hair grooming preparations Pantene, Corrective hair lotion conditioner.

The Panthenol Co., Division

of Hoffmann-Laroche Ingredients:

SD Alcohol 40 Butyl ester of PVM/MA co-

Pantyl (4) Phytantriol (5) Myristol (6) Hydrolized animal protein Benzophenone-4 (7) Fragrance

polymer (1) Aminomethyl propanol (2) Dimethicone copolyol (3) Stearealkonium chloride Panthenol Remarks:

(1) (2) (3) (4) (5) (6) (7)

Gantrez ES, GAF Corp. 2-Amino-2-methyl-1-propanol, Commercial Solvents e.g. Silicone Fluid SF 1066, General Electric Not identified A botanical sterol Presumably myristyl alcohol UV Absorber, e.g. Uvinul MS-40, GAF Corp.

Pantene Hair Lotion for Men.

The Panthenol Co.

Ingredients: SD Alcohol 40 Water Fragrance Glycerin PPG butyl ether-1715 (1) Pantyl (2)

Panthenol Phytantriol (2) Menthol Sodium hydroxide FD&C Blue No. 1 D&C Red No. 33

Remarks: (1) Ucon LB-1715, Union Carbide (2) See above ingredients of Pantene

Wellaflex, Hair net. The Wella Corporation Ingredients:

SD Alcohol 40 Isopropyl alcohol Water Ester of PVM/VA copolymer (1)

PEG-75 lanolin (2) Diisopropyl adipate (3) Remarks: (1) e.g. Gantrez AN-119, GAF Corp. (2) e.g. Solan, Croda (3) e.g. Crodamol DA, Croda

111

Aminomethylpropanol PVP Panthenol Plant protein Fragrance

112

Hair grooming preparations

Brylcream.

Beecham Co. A water in oil hair grooming cream

Ingredients: Calcium hydroxide (1) Mineral oil Beeswax

Fragrance Stearic acid

Remark:

(1) Calcium hydroxide solution, e.g. Lime water USP Wildroot.

Colgate Co. A water in oil hair grooming lotion

Ingredients:

Water Mineral oil Lanolin Microcrystalline waxes Polyglyceryl-4-oleate (1) Fragrance

- Polysorbate-60 (2) PEG-8 (3) Propylene glycol cocoate (4) Sodium borate Formaldehyde

Remarks:

(1) (2) (3) (4)

e.g. Witconol 14, Witco Chemical Tween 60, ICI Polyethylene glycol 400, e.g. Carbowax 400, Union Carbide Propylene glycol dicoconate (CTFA)

VO-5 Hair Spray, Non-aerosol. Ingredients:

Alberto Culver Co. Caution: Flammable

SD Alcohol 40 (1) Butyl esters of PYM/MA copolymer (2) Amino methylpropanol (3) Ammonium polyethylene tetrafluoro hydroxyethyl phosphates (4) PEG Octadecyl hydroxydimethyl ammonium sulfate Fragrance Remarks:

(1) Ethyl alcohol 95% vol. (2) e.g. Gantrez ES 425, GAF Corp. (3) 2-Amino-2-methyl-l-propanol, a neutralizing agent, e.g. AMP Regular, Commercial Solvents Co. Specific gravity 30/30°C of this cosmetic is 0.804. Dry residue is 6g/100 ml. Addition of the phosphates does not reduce the flammability.

Hair grooming preparations Vitapointe.

113

Clairol. A cream hair dressing. Tube packaging

Ingredients: Mineral oil Water Beeswax Aluminum stearate (1) Imidazolidinyl urea

Phenoxyethanol (2) Fragrance Stearic acid Propylparaben Calcium oxide

Remarks:

(1) e.g. Aluminum stearate 22, Witco Chemical (2) Phenyl cellosize, Union Carbide This formulation appears to be an emulsified gelled mineral oil. A water in oil emulsion 50/50, pH = 4.5. Top Brass, Hair groom.

Revlon. A cream emulsion. Tube packaging

Ingredients: Water

Mineral oil Propylene glycol laurate (1) PPG-12 buteth-16 (2) Propylene glycol Castor oil Petrolatum Hydrogenated soy glyceride (3) Glycerin Polysorbate-60 (4) Sorbitan stearate Beeswax Candelilla wax

Hydrolyzed animal protein DEA-oleth-10 phosphate (5) Lanolin wax (6) Imidazolidinyl urea Sodium carbomer-934 Chloroxylenol (7) DIPA carbomer 934 Methylparaben Propylparaben p-Hydroxyanisol (8) Dehydroacetic acid (9) Fragrance

Remarks:

(1) (2) (3) (4) (5) (6) (7) (8) (9)

e.g. Kessco PGML-X 533, Stepan, Kessco Div. Ucon 50-HB-660, Union Carbide Hydrogenated soybean oil Tween 60, ICI Crodafos N 10 Neutral, Croda e.g. Lanfrax, Malmstrom Chemical Ottasept Extra, Ottawa Chemical e.g. Antioxidant No. 221, R.W. Greef Co. A bactericide

114

Hair grooming preparations

Formulations Spray Hair Net

Ref 116 47 50 255° 99.5

ml Alcohol 95% vol Water “PVP NP. Kso'@)

0.2 0.3 Rey 0.5

Laneth-16 (2) Perfume T 100 ml

(1) GAF Corp. (2) Solulan 16, Amerchol Mix in the order shown. Dispense with atomizer. Waterless formulations are often preferred since they dry faster. Caution: Flammable. Spray Hair Net Standard

Ref 117 93 6.5

ml Isopropanol PVP NP K 30

99.5

0.3 0.2,

laneth-16 Perfume

0.5

T100mi

Same procedure as for Ref 116. Caution: Flammable. Hair Dressing Alcohol Lotion No. 1 Standard

Ref 118 70 15 ib)

ml Alcohol 95% vol Water Ucon LB 1715 (1)

100

0.25 0.25

FD&C Yellow No. 5, 0.1% Perfume

0:32.

-Ti100;S:n

(1) PPG butyl ether-1715, Union Carbide Hair Dressing Alcohol Lotion No. 2 Protein Type Ref 119

Teh =) 15 aa

100

ml Alcohol 95% vol Water Ucon LB 1715 Protein

0.5 0.05 0.05

Perfume FD&C Blue No. 1, 0.1% FD&C Yellow No. 5, 0.1%

0.6 © 100.6ml

Hair grooming preparations

115

Hair Dressing Alcohol Lotion No. 3 Type Ciba-Geigy

Ref 120 71 oa) 3) _0.2

9.2

ml Alcohol 95% vol Water Dicrylan 325 WA-SO (1) Protein

0.2 0.05 1 A} ef

1.25 (1) Polyacrylic resin, Ciba-Geigy

Perfume FD&C Blue No. 1, 0.1% Propylene glycol

T 100.45 ml

Caution: Flammable Solid Brilliantine

Ref 121 60

Petrolatum, white USP

0.1

D&C Yellow No. 11,

30 10

Mineral oil, visc. 70 Paraffin, mp 128°F

1

1% (1) Perfume

5 oy

he

100

(1) Solution in isopropyl myristate Melt waxes and fill at 60°C. Set Pt 40°C. Washable Brilliantine

Ref 122 20 30 10 5

65

Petrolatum, white USP Mineral oil, visc. 70 Oleth-20 (1) Laneth-16 (2)

2.5 2.5 30 0.5

35.5

Ozokerite No. 4 Stearic acid Lanolin Perfume

T 100.5

(1) Brij 99, ICI (2) Solulan 16, Amerchol Melt waxes and fill hot. Set Pt 37°C.

Emulsified Hair Dressing

Ref 123A A 5.5 1.5 3.5

10.5

Cetyl alcohol Petrolatum, white USP Mineral oil, visc. 70

|e

oe 86 C 0.5

89.5 (1) Standapol WAQ Special, Hendel

Mix A and B at 75°C. Stir until cold.

Sodium lauryl sulfate (1) Water Perfume and preservative

T 100

116

Hair grooming preparations Emulsified Hair Dressing Water in Oil Emulsion

Ref 123B A 35 8 1

3

47

Mineral oil, visc. 70 Beeswax POE-20 sorbitol beeswax derivative (1) Sorbitan sesquioleate (2)

B. 52 1 0.1

—,

53.1

Water Propylene glycol Methylparaben

T 100.1

(1) Atlas G-1726, ICI. U.S. Patent 2 612 509 (2) Arlacel 83, ICI Mix A and B at 75°C. Stir until cold. Hair Pomade High Viscosity

Ref 124 60 10 18 5 wae

95

Petrolatum, white USP Lanolin Castor oil Stearic acid Cetyl alcohol

4 10 i 1

Multiwax 180 M (1) Isopropyl palmitate Perfume D&C Green No. 6, 0.1% (2)

Toa

Tul

(1) A microcrystalline wax of plastic consistency, Witco Chemical (2) Solution in isopropyl myristate. Imparts a blue color. For green color, add D&C Yellow No. 11. Melt waxes and fill at about 55°C. Set Pt 43°C.

Hair waving and hair relaxing preparations

117

12. HAIR WAVING AND HAIR RELAXING PREPARATIONS The commonly used hair waving and hair relaxing preparations are the following:

Cold wave, clear lotions and neutralizers. Ref 126 Cold wave, opaque lotions and neutralizers. Ref 127 Heat activated permanent hair curling lotions. Ref 128 Bisulfite hair curling lotions. Ref 129A, B & C Hair straighteners. Ref 130A, B& C Most hair waving preparations are based on ammonium thioglycolate and ammonium or sodium bisulfite which have long been known for conditioning the structure of the hair. Neutralizers further help in setting the hair and remove any excess of the active ingredients. It should be noted that hair curling preparations and hair relaxers can be used interchangeably. Only the method of application differs, the former being used after the hair has been wound on curlers, whereas the hair is combed after application of the relaxers. The time of application is the same in both cases, or about 20 minutes. For home use, bisulfite preparations are particularly recommended

since they are mild in action. Most hair straighteners —including those of leading manufacturers —are still based on sodium hydroxide as active ingredient. These preparations can only be recommended for professional use, since they may irritate the scalp and possibly injure the eyes when improperly handled. Hair curling preparations based on ammonium thioglycolate can be heat activated with hydrogen peroxide. When the two lotions are mixed prior to use, heat is evolved as shown in the following reaction: S.CH2COOH 2HS.CH2COOH

+

H202

=

+

2H,O

+

91.1 kcal

S.CH2,COOH Thioglycolic acid

2x

92

Hydrogen peroxide

-

34

Dithioglycolic acid

=

182

Water

+

36

The evolution of heat favors the curling action and also takes out the chill of the application. Another advantage appears to be the formation of ammonium dithioglycolate which is said to promote even curling. The preparation can be dispensed as a foam from a squeeze bottle fitted with a special valve of fused beads.! The curling time is about 20 minutes for an initial temperature of 40°C. In developing a preparation with desired heat specifications, it is useful to note that 1 gram hydrogen peroxide 100% (or 16.7 g of the usual 6% solution) releases 2680 calories and consumes 5.4 g thioglycolic acid 100% (or 6.75% of ‘Manufactured by Diamond

International Corp., Calmar Division.

118

Hair waving and hair relaxing preparations

the commercial 80% acid). If the combined weight of the reacting lotions is 120 g, this raises the temperature to 50°C, assuming the reactants are at room temperature (27°C). This allows controlling the temperature at any desired level. Most commercial heat activated curling lotions raise the temperature to 40°C, although 50°C would seem better. The concentration of thioglycolic acid in any preparation must be carefully determined. An upper limit is not specified in the U.S. but in many countries

the maximum is 9.5%. In France 8% is the limit for lotions used professionally. In the case of heat activated curling lotions, the effective thioglycolic acid (TGA) content can be determined by analysis after addition of the peroxide, or this can be estimated by calculation. For the formulation given under Ref 128, the breakdown is as follows: TGA content in 96.2 g of lotion TGA consumed in heating reaction Effective TGA Weight of mixture A + B TGA in mixture A + B

15.0g 5.4¢g 9.62 116.4¢ 8.2%

This composition conforms to the analysis of leading brands of heat activated permanents for professional use. The concentration of effective thioglycolic acid is somewhat high, but this also reduces the time of application. Lesser concentrations of thioglycolic acid are used for home permanents, usually about 5.7%. One leading home permanent based on monoethanolamine thioglycolate analyzed 11.9% thioglycolic acid. This permanent had a pH of 8.3 as compared to the normal pH of 9.5.

Manufacturing Equipment The selection of the proper equipment for processing and filling curling lotions based on ammonium thioglycolate is of great importance since traces of iron cause purple discolorations. Manufacturing equipment is practically limited to the following construction materials:

1. 2. tanks 3.

Glass lined kettles. These are ideal, but expensive and easily chipped. Plastic kettles, Teflon or polyethylene. These are preferred for holding and are also inexpensive. Stainless steel 316 for mixing kettles, pumps and filling equipment.

Stainless steel equipment must be initially treated with a solution of 5% nitric acid to remove all traces of free iron. This operation, called “pickling” is similar to the “passivation” of peroxide equipment. Although stainless steel 316 is widely used for processing thioglycolate lotions, it is recommended to transfer the batches to plastic holding tanks as soon as completed to minimize the contact with iron. Stainless steel 316 is essential. Stainless steel 304, which is widely used in the cosmetic industry, invariably causes the pink discoloration.

Hair waving and hair relaxing preparations

119

In the construction of the equipment, metallic couples must be avoided as they generate electromotive forces that become immediate sources of pink discolorations. Propeller mixing in plastic tanks is possible but offers some problems since an enclosed system is necessary to control the vapors of ammonia. One solution is to recycle the batch by means of a pump that distributes the liquid within the tank. Raw Materials

The raw materials should of course be as low as possible in iron to minimize the pink discoloration. Perfumes and essential oils are sometimes contaminated with iron that darkens the oils; this is easily corrected by means of 2 treatment with concentrated phosphoric acid, using 0.1%. If the main ingredient, the thioglycolic acid, is pink, it should be decolorized with 0.025% of sodium hydrosulfite. Finally, if the thioglycolic acid is off odor, aeration with nitrogen is necessary. If in spite of all precautions, the batch is still slightly pink, this is again corrected by the addition of 0.025% sodium hydrosulfite, Na2S.O0,. An absolute minimum should be used because of the su/fide-like odor of this chemical. Incidentally, this material should not be confused with sodium thiosulfate Na2S203°5H.2O ineffective.

(Hypo), or sodium

dithionate

Na2S20c6*2H2O

which

are

Bisulfite Curling Lotions Curling lotions based on sodium bisulfite are getting increasingly popular for home use. The bisulfite content of these preparations is usually about 7%. The pH is an important factor. This should be 9.9, a level that is best achieved by first neutralizing the acidic bisulfite with the theoretical amount of monoethanolamine and subsequent addition of alkalies to bring the pH to the proper level. A formulation of this type is shown under Ref 129. Note that the relative proportions of bisulfite to monoethanolamine (MEA) is NaHSOs: MEA = 104:62, or 0.6 parts of monoethanolamine for 1 part of sodium bisulfite. If a slight foam is desirable for the application, this can be obtained by adding a small percentage of Igepal CO-730. The preparation can also be heat activated by addition of peroxide. This requires additional bisulfite to maintain the initial concentration that is necessary for curling. The exothermic reaction that takes place is as follows: NaHSO;

+

H.20,2

=

NaHSO,

Sodium

Hydrogen

Sodium

bisulfite 99

peroxide 34

bisulfate

+

H.20

+_

85.5 kcal

Water

The time of application for the curling lotions is 25 minutes. After rinsing, a neutralizer should be applied. These again consist of peroxide lotions similar

120

Hair waving and hair relaxing preparations

to those used for thioglycolates. However, due to the milder action of the bisulfites, a concentration of 1.5% H2O> is all that is necessary. Curling lotions can also be based on ammonium bisulfite NHsHSOs which | is commercially available as a 45% solution. The bisulfite content of the curling lotion may vary between 7 and 10%. Since this solution is acidic it can be neutralized with monoethanolamine. However, at least one of the lotions on the market is simply adjusted with ammonia to a pH of 6.0. At this level the preparation is practically odorless. A different type of curling lotion has been promoted recently. The curling agent is monothioglycerin CH2OH»CHOH~+CH2SH, an acid (mercaptan), which is packaged as a 50% solution in glycerin. This mixture is added prior to use to a lotion containing ammonia (about 0.25% NH:;) to form ammonium thioglycerin 10% solution with a pH of about 7.0. Although this solution is not heat activated, the temperature rises about 4°C due to heat of neutralization. It is applied to the hair which is kept under a heater or drier for 25 minutes to achieve curling. A distinctive feature of the preparation is the neutralizer which is heat activated. This is obtained by mixing 20 ml of a solution of monoethanolamine bisulfite (12.5% as NHsHSO;) to 100 ml of a solution of 3.4% hydrogen peroxide. The temperature rises to 40°C, the bisulfite being oxidized to sulfate, whereas the peroxide concentration reduces to 2%. This neutralizing solution is applied for five minutes before rinsing out. This system is a model of cosmetic formulation that should be carefully studied. Note that it is not necessary to activate the curling lotion since the hair is kept under a heater. On the other hand a warm neutralizer reduces the chill of the application, not to mention that the neutralization is accelerated at the higher temperature. Note also the formation in situ for a more active curling agent. Quality Control

The quality control of hair waving preparations consists primarily in checking the concentrations of the active ingredients and the pH of the lotions. Procedures are given in the Appendix. Examples of Trade Formulations From Manufacturer’s Product Label Zotos Texture Foam.

Part A. Part B. Part C.

Heat activated permanent

91 ml Curling lotion 20 ml Thermolizer 118 ml Neutralizer

Hair waving and hair relaxing preparations

121

Ingredients (After mixing Part A with Part B): Water Phenacetin (3) Ammonium thioglycolate Methyl paraben Ammonium dithioglycolate (1) Disodium phosphate Laureth-23 Ammonium phosphate (4) Protein Fragrance Styrene/acrylic copolymer (2) Remarks:

(1) (2) (3) (4)

Reaction product of Part A and Part B Cloud ingredient Peroxide stabilizer in Part B Reaction product

Ingredients (Part C — Neutralizer): Water Hydrogen peroxide Zotosol Mineral oil Stearyl alcohol Cetyl alcohol

Ceteth-20 Olealkonium chloride Methyl paraben Phenacetin Phosphoric acid

L’Oréal Extra Body Perm. 4 fl oz opaque lotion for home use. Normal hair. Ingredients (A — Lotion): Water Thioglycolic acid Ethanolamine Ammonium hydroxide Potassium cocohydrolyzed animal protein (1) Vinyl pyrrolidone/styrene copolymer (2)

Polysorbate 80 (3) Fragrance EDTA Hydrolyzed animal protein

Remarks:

(1) Maypon 4 C, Stepan Chemical (2) Polectron 430 GAF Corp., a clouding agent (3) e.g. Tween 80, ICI Ingredients (B—Neutralizer, 4 fl oz opaque lotion for the above Perm): Water

Hydrogen peroxide Quaternium 44 (1) Quaternium 47 (2)

Fragrance Citric acid Phenacetin Oxyquinoline sulfate

Remarks:

(1) Cetyl dimethyl hydroxyethyl ammonium chloride (2) Dilauryl dimethyl ammonium chloride

122.

Hair waving and hair relaxing preparations

Breck Wave Lotion. hair

For professional use, 4 fl oz opaque lotion. Normal

Ingredients (A):

Water Ammonium thioglycolate Ammonium hydroxide PEG-75 lanolin

Methyl resinate (1) Polysorbate-20 (2) D&C Yellow No. 10 D&C Red No. 19

Fragrance

Remarks:

(1) Abalyn, Hercules, Inc, used as an opacifier (2) e.g. Tween 20, ICI Ingredients

(B— Neutralizer, 4 fl oz opaque lotion for the above Perm):

Water Sodium bromate (1) Oleth-10 Sodium borate Boric acid Oleth-20 Soybean oil

Vinyl pyrrolidone/styrene copolymer (2) Fragrance Lanolin oil Wheat germ oil Rice bran oil D&C Red No. 19

Remarks:

(1) NaBrO; (2) Polectron 430 GAF Corp., a clouding agent

Lilt, Home permanent. Normal hair

Procter & Gamble. Opaque pink lotion, 3.5 fl oz.

Ingredients (A): Water Ethanolamine thioglycolate Ethanolamine dithioglycolate Ethanolamine Mineral oil Laureth-20

Fragrance Potassium oleate Glycol Oleic acid D&C Red No. 19

Ingredients (B— Neutralizer, opaque lotion, 4 fl oz): Water Hydrogen peroxide

Fragrance Phenacetin

Isopropyl palmitate

Phosphoric acid

Laureth-4

Hair waving and hair relaxing preparations Toni Silkwave, Home permanent. oz. Normal hair

123

The Gillette Co. Opaque lotion, 3.85 fl

Ingredients (A): Water Diisopropanolamine Ammonium thioglycolate Steareth-20 Quaternium-40 (1) Fragrance Potassium cocohydrolized animal protein

Sodium styrene/PEG-10 maleate/ Nonoxynol-10 maleate/acrylate copolymer EDTA Ammonium nonoxynol-4 sulfate (2) D&C Yellow No. 10 D&C Red No. 19

Remarks: (1) e.g. Merquat-100, Merck Co.

(2) e.g. Alipal CO-436, GAF Corp. Ingredients (B— Neutralizer, opaque lotion, 4 fl oz): Water Mineral oil Hydrogen peroxide Sorbitan palmitate (1) Propylene glycol Lanolin Polysorbate-40 (2) Stearalkonium chloride

Remarks:

(1) e.g. Span 40, ICI (2) e.g. Tween 40, ICI (3) e.g. Armeen DM 18 D, Armak

Phenacetin Stearyl alcohol Dimethyl stearamine (3) Benzoic acid Fragrance Hydrochloric acid Sodium stannate

124

Hair waving and hair relaxing preparations

Revlon, Instant Styling Perm.

For home use

Ingredients (A—Pre Perm Conditioner, 1 fl oz (29 ml)): Water Propylene glycol Stearalkonium chloride Hydrolyzed animal protein

Quaternium-23 (1) Fragrance Citric acid

Remark: (1) Gafquat 734 or 755, GAF Corp. Ingredients (B — Perm Lotion, Instant Styling. Opaque lotion, 3 fl oz (88 ml)): Water M E A thioglycolate (1)

Glycerin

Octoxynol-9 (2) Laureth-23

'

Ethanolamine Styrene/acrylate copolymer Hydrolyzed animal protein

Fragrance Pentasodium pentetate (3) Methylparaben Propylparaben

Remarks:

(1) Monoethanolamine thioglycolate (2) e.g. Igepal CA-630 (3) e.g. Versenex 80, Dow Chemical Ingredients (C — Neutralizer, for above Perm lotion. Opaque lotion, 3.5 fl oz): Water Hydrogen peroxide Styrene/acrylate copolymer Octoxynol-9 (1) Laureth-23

Fragrance Phenacetin Citric acid EDTA

Remark: (1) e.g. Igepal CA-630, GAF Corp. Rave.

Chesebrough-Ponds’ Home Permanent

Ingredients

(A— Permanent lotion. Translucent lotion, 4 fl 0z):

Water Sodium bisulfite (1) Ethanolamine Sodium borate

Diethanolamine Sodium carbonate Octoxynol-13 (2)

Remarks:

(1) NaHSO; (2) e.g. Triton X-102, Rohm & Haas Co. Ingredients (B — Neutralizer, for above permanent lotion. Clear lotion, 4 fl oz): Water Hydrogen peroxide Phosphoric acid

Hair waving and hair relaxing preparations

125

Toni Lightwaves, One-step Softperm. The Gillette Co. Ingredients (A —Shaping lotion. Clear lotion, 3.14 fl oz (92.8 ml)): Water Quaternium-40 (2) Ammonium bisulfite (1) EDTA SD Alcohol 40 Ascorbic acid Ceteth-20 Ammonium hydroxide Remarks: (1) NH.HSOs, 50% solution (2) e.g. Merquat-100, Merck & Co.

Ingredient (B—Stabilizer, 0.47 oz (13.3 g). Powder packaged in plastic tube): Urea Ingredients (C — Activator, 0.5 oz (14.2 g). Powder packaged in plastic tube):

Urease (1) Silica (2) Remarks: (1) An enzyme which hydrolizes urea to ammonium carbonate (2) e.g. Cab-o-Sil M-5, to prevent caking Ingredients (D — Conditioner, 0.75 floz (22.2ml). Cream lotion in plastic tube): Water Mineral oil Hydrogen peroxide Sorbitan palmitate (1) Propylene glycol Lanolin Polysorbate-40 (2) Stearalkonium chloride

Phenacetin Stearyl alcohol Dimethylstearamine (3) Benzoic acid Fragrance Hydrochloric acid Sodium stannate

Remarks: (1) Arlacel 40 or Span 40, ICI (2) e.g. Tween 40, ICI (3) e.g. Armeen DM18D, Armak

How to use: 1. Pour Activator and Stabilizer powders into Shaping lotion. Shake for half a minute. 2. Soak each curl with Shaping lotion and wait for 35 minutes. 3. Rinse with water for 2 minutes. Remove rods. 4. Optional: Apply conditioner for 1 minute and rinse.

126

Hair waving and hair relaxing preparations

Pantene Supreme. Heat activated acid balanced wave (pH about 6.7). For all types of hair. The Pantene Co., Distributor Div. Hoffman-LaRoche, Inc.

Package of five components includes: Part Part Part Part Part

1. 2. 3. 4. 5.

Waving lotion additive. To be mixed with Part 2. Tube 20 ml. Waving lotion (Base). Bottle 80 ml. Neutralizer additive. To be mixed with Part 4. Tube 20 ml. Neutralizer (Base). Bottle 100 ml. After Perm lotion (alcoholic). Contains phytosterol conditioners imported from Switzerland. Also contains 18 aminoacids. Tube 18 ml. a

Ingredients (Part 1):

Glycerol thioglycollate (1) Glycerin Remark:

(1) CTFA adopted name for monothioglycerin

Ingredients (Part 2): Water Laureth-23 Ammonium chloride Fragrance Ammonium hydroxide Acrylate copolymer (1) TEA —Cocohydrolyzed animal protein

Remark: (1) e.g. Acryloid B 66, Rohm & Haas Co. Ingredients (Part 3): Water

Monoethanolamine bisulfite Ingredients (Part 4):

Water Hydrogen peroxide Mineral oil Phosphoric acid Cetyl alcohol

Ceteth-2 Sodium lauryl sulfate Disodium phosphate Methylparaben

Hair waving and hair relaxing preparations

127

Perma Strate. Cream hair straightener for professional use. 4 oz. Perma Strate Co., Memphis, Tenn

Ingredients (A): Water Glyceryl stearate (and) sodium lauryl sulfate (1) Ammonium thioglycolate Remark: (1) Tegacid, Inolex Ingredients (B— Perma 0.75 fl oz):

Synthetic spermaceti Ammonium hydroxide Stearamide DEA Fragrance

Strate, Neutralizing rinse for the above preparation,

Water Hydrogen peroxide Octoxynol-9 (1)

Tetrasodium EDTA Phosphoric acid

Remark: (1) e.g. Igepal CA-630, GAF Corp. Ingredients (C — Perma Strate, Shampoo for use after neutralization, | fl oz): Water Sodium laureth sulfate Ammonium laureth sulfate Cocamide DEA Sodium chloride Fragrance

Methylparaben Butylparaben Formaldehyde FD&C Red No. 40 FD&C Yellow No. 6 FD&C Yellow No. 5

Allyn’s Cream Hair Relaxer. Allyn’s International Corp., North Bergen, N.J. Ingredients: Water Mineral oil Glyceryl stearate Propylene glycol Thioglycolic acid Ammonia Stearyl alcohol Laureth-23 Lanolin linoleate

Sodium lauryl sulfate Methylparaben Propylparaben Benzylparaben EDTA Fragrance D&C Yellow No. 11

128

Hair waving and hair relaxing preparations

Formulations Cold Wave, Clear Lotion

Ref 126 A 7.6 2.6 1.5

Ammonium thioglycolate (1)

B 2 0.5

Ammonia, 28% NH3 Ammonium lauryl sulfate

Igepal CO-730 Perfume

0.05 0.15

D&C Yellow No. 8, 1% Methylparaben

2)

T1004

(2) 86

OTT

Water

(1) 60% Thioglycolic acid content. Witco Chemical, Angus Div. (2) Standapol A, Henkel Mix A and B. The pH of the mixture should be 9.2 to 9.3 Directions: Apply for 10 minutes. Rinse thoroughly. Apply neutralizer for 5 minutes. Neutralizer, Clear Lotion

Sodium bromate

Igepal CO-730

84 100

Water

Directions: Apply for 10 minutes. Rinse thoroughly. Apply neutralizer for 5 minutes.

Ref 127 A 7.5 0.6 1.4

88_ 97.5

Cold Wave, Opaque Lotion Ammonium thioglycollate (1) Ammonia 28% NH; Monoisopropylamine (2) Water

B

1 0.5 1 0.1 7 2.6

Igepal CO-730 Perfume Clouding agent (3) Methylparaben

T 1001.

(1) 60% Thioglycolic acid content (2) Union Carbide (3) Polectron 430, GAF Corp. See Ref 128 Mix A and B. The pH should be 9.2 to 9.3. Neutralizer, Cream Lotion

Steareth-20 (1) Cetyl alcohol Mineral oil, visc. 70

B 35 C 14 43

92

as Br

Water Sodium bromate Water

=

100

(1) Brij 78, ICI

Mix A and B at 75°C. Stir until cold. Add solution C.

Hair waving and hair relaxing preparations

129

Heat Activated Hair Curling Lotion

Ref 128 Part A. Curling Lotion Rose perfume Igepal CO-730 Laureth-23 (1) Chelating agent (2)

65 26

6.1 1

98.1

Water Ammonium thioglycolate (3) Ammonia 28% NH; Clouding agent (4)

TT 100

(1) Brij 35 SP, ICI (2) Versene 80 (Dow Chemical), Chel DM-41 (Ciba-Geigy), or Hampex 80 (Hampshire Chemical) (3) 60% Thioglycolic acid content, Witco Chemical, Angus Div. (4) Vinyl pyrrolidone/styrene, 50% active, Polectron 430, GAF Mix in the order shown. Chelating agent added before the thioglycolate should help prevent the red discoloration due to iron. Thioglycolic acid content is 15.6%, pH 9.2 to 9.3, Sp. gr. 1.057.

Package: 91 ml (96.2 g) in a 4-oz bottle. Fill precisely. Part B. Peroxide Heating Lotion A clear solution of peroxide. For heating effect to 50°C use 5% H.20,; for 40°C use 4.4% H20O>. Package: 20 ml (20.2 g) of either solution in a polyethylene tube. Fill within + 0.1 ml to meet temperature specifications.

Part C. Neutralizer

A 84 B 10 0.05

Water, deionized, cold Water, deionized, 85°C Phenacetin

Cu. 0.9 D 4.6 0.02

94.05

6.02

Arlacel 165 (1) Stearalkonium chloride (2) Hydrogen peroxide 50% Phosphoric acid 10%

1 100.7

Ge emCe (2) Ammonyx CA Special, Onyx Chemical Caution: The curling lotion part A should be used only after the peroxide lotion part B has been added. Failure to do so causes excess curling and may damage the hair due to the higher concentration of thioglycolate. Note: Ammonium thioglycolate can be prepared in situ. Note, however, that in order to prepare the commercial 60% product it is necessary to react thioglycolic acid 98% with the theoretical amount of ammonia (1 mole). The higher strength thioglycolic acid can be obtained from Chemische Fabrik Bruno Bock, D-2095 Marschacht, West Germany.

130

Hair waving and hair relaxing preparations Bisulfite Curling Lotion Heat Activated

Bisulfite Curling Lotion Ref 129A 7 87.3 4.2 15

Ref 129B 8.8 84.5 52 Pe)

Sodium bisulfite (1) Water Monoethanolamine (2) Sodium carbonate (3)

100

Sodium bisulfite (1) Water Monoethanolamine (2) Sodium carbonate (3)

100 (1) NaHSO; commercial, mostly sodium meta bisulfite Na2S2Os (2) Union Carbide (3) Na2CO; anhydrous Simple mixing in the order shown. The pH should be 9.9. Prior to use, mix 90 parts of curling lotion Ref 129B with 10 parts hydrogen peroxide, 6% H2O>. This raises the temperature from 25°C to 40°C. It also reduces the bisulfite concentration to 7%.

Curling Lotion With Ammonium Bisulfite Ref 129C 15.6 Ammonium bisulfite (1) 82.2 Water 2.2 Ammonia 28%

100 (1) Commercial, 45% solution Simple mixing. Addition of the ammonia raises the pH from 6.2 to 7.1. This preparation should be free of any sulfite or ammonia odor. Addition of 3% isopropanol is recommended.

Neutralizers of the bisulfite hair waving lotions are usually peroxide solutions at concentrations of about 1.5% H2O>. Hair Straightener Cream No. 1 For Professional Use on a Cold Cream Base

Ref 130A A 10 8 4.5. 4 _1.5 —

28

Laureth-4 (1) Beeswax Cetyl alcohol Mineral oil, visc. 70 Lanolin

B 68 4 2 C 2.6 5.4

82.0

Water Propylene glycol TEA Sodium hydroxide, pellets Water

T110

(1) Brij 30, ICI Mix A and B at 75°C. Add preservative. Cool to 50°C. Add cold solution C. Fill cold.

Hair waving and hair relaxing preparations

131

Hair Straightener Cream No. 2 Active Ingredient: Ammonium Thioglycolate Ref 130B

Ave

4 4 4 4 0.3

Arlacel 165 (1) Cetyl alcohol Stearyl alcohol Paraffin, mp 128°F Mineral oil, visc. 70 Rose perfume

18.3

B 66 0.2 0.5 C 11.7.

D

3.5

81.9

Water Dowicil 200 (2) Duponol C (3) Ammonium thioglycolate (4) Ammonia 28% NH;

T 100.2

(1) ICI (2) Dow Chemical (3) Sodium lauryl sulfate, 100% active, E.I. DuPont de Nemours (4) Thioglycolic acid content 60%, Witco Chemical, Angus Div.

Mix A and B at 75°C (Setting point of this mixture is 48°C). Cool to 50°C and add C. When dispersed, add D. Fill at 45°C. Set Pt

42°C. Thioglycolic acid content is 7.0%; pH = 9.2. Addition of Dowicil inhibits oxidation of the thioglycolate and formation of yellow discolorations.

Ref 130C A 85

Gel Hair Relaxer Carbopol 940, 2% (1) Ammonium thioglycolate (2) Monoethanolamine (3) Ammonia 28% NH; (1) (2) (3) (4)

B 0.1 0.1 0.2 0.1 a 0.5

Versenex 80 (4) Rose perfume Igepal CO-730 (5) Dowicil 200

T 100.1

Goodrich Chemical 60% Thioglycolic acid, Witco Chemical, Angus Div. Union Carbide Dow Chemical

(5) GAF Corp. Mix part A in the order shown. Part B should be added to the water used for the carbopol dispersion. Thioglycolic acid content of the gel is 6.0%; pH = 9.2. The monoethanolamine increases the pH to the proper value. This gel should not be used for hair curling since gels cannot penetrate tightly curled hair and are therefore ineffective.

132

Lipstick

13. LIPSTICK Lipstick formulations can be classified as follows: Staining lipstick. Ref 131 Non-staining lipstick. See text below Transparent lipstick (Yardley patent) Lipstick “Rouge Baiser” (Baudecroux patent) Natural “8 hour” lipstick (New product). Ref 132

Lipstick can be formulated in various degrees of staining quality. The staining color is bromo acid (D&C Red No. 21). To be effective it must be at least in partial solution in the lipstick medium which is normally castor oil. Assuming that the lipstick base contains 60% castor oil, the maximum amount of bromo acid that can be brought in solution is 0.3%. However, up to 1 and 2% bromo acid is used in staining lipstick. There are some objections in using these higher concentrations: 1. 2. lips. 3. to the

Bromo acid has a disagreeable bromine odor. It may cause allergic reactions, particularly dryness and peeling of the The excess bromo acid that is not in solution contributes relatively little staining quality.

It would therefore seem that the concentration of bromo acid should be limited to 0.3%. The present trend of leading firms in reducing stain in lipstick appears to support this view. Nevertheless, staining lipstick is still in demand. An extremely stable lipstick of this nature, tested over a period of many years, is given under Ref 131. Non-Staining Lipstick Non-staining lipsticks appear to be gaining favor, especially in the brown shades now in fashion. Castor oil is no longer indispensable, although it cannot be eliminated altogether on account of its high viscosity. As should be evident, the rub-off or smearing effect depends entirely on viscosity: A low viscosity lipstick applies with great ease and also comes off with little resistance. Vice-versa, a high viscosity lipstick is harder to apply, but forms a more lasting film. Castor oil also serves as a solvent for lanolin, a most important ingredient since it suspends the pigments and develops the color intensity. Of course, heavy mineral oil could also be used in non-staining lipstick and has the advantage of being tasteless and odorless. A non-staining lipstick could also be formulated by leaving out the bromo acid of a regular formulation, or by using an eye shadow type formula. Or we

Lipstick

133

may wish to modify the formulation Ref 131 to get a whiter base for greater brilliancy of the shades. We can reduce the candelilla wax to 17.5% with addition of 2.5% ozokerite and 2.5% paraffin wax to compensate the wax content. Similarly, we can reduce the castor oil to 45% and add 5% sesame oil, leaving the remaining ingredients unchanged. Although candelilla wax imparts a slight brown cast, it cannot be reduced substantially because it gives excellent unmolding and gloss. As mentioned before, castor oil is also indispensable. It is interesting to compare this formulation with Revlon’s Formula 2 which is described as follows in the ingredient label declaration: Oils Castor oil Sesame oil Lanolin oil Isostearic acid

Colors D&C Orange 17, Barium lake D&C Red 7, Calcium lake D&C Red 9, Barium lake FD&C Yellow 5, Aluminum lake Iron oxides Titanium dioxide, Mica

Viscous solids Lanolin Petrolatum Hydrogenated vegetable oil Isopropyl lanolate

Preservatives Methylparaben Propyl paraben p-Hydroxyanisol

Waxes Candelilla wax Paraffin wax Ceresin (ozokerite) Stearic acid Cetyl alcohol Lanolin alcohols

Sun screen Octyl Dimethyl

Remarks:

P

ABA

Fusing ingredients Hectorite (a bentonite clay) Quaternium-18 (a quaternary compound)

Note the absence of bromo acid, beeswax and carnauba wax.

Transparent Lipstick

This type of lipstick has been patented by Yardley, U.S. 3 148 125 (1964), and German Patent 1 930 954 (1970). Formulations are based on polyamid resins (Versamid 335, General Mills). One serious problem is controlling syneresis (sweating). See stick rouge Ref 158. Baudecroux Lipstick

This product is mentioned for the record as an early attempt to formulate an indelible lipstick with propylene glycol and eosine, the sodium salt of bromo acid (German Patent 557609, 1932). Its main defect, besides poor appearance, is the extreme bitterness of eosine.

134

Lipstick

Natural “8 Hour” Lipstick Lipsticks presently in use are unsatisfactory from several points of view. The film gives a very greasy feeling on the lips —although this is sometimes interpreted as a beneficial moisturizing effect —it wears off quickly especially when eating and soils everything touched with the lips. It is therefore not surprising that from time to time so-called indelible lipsticks are offered on the market in spite of the fact that they are truly not indelible, but merely stain the lips to some extent. These lipsticks are unsatisfactory because the lakes and pigments are not retained in a lasting film. Furthermore, the residual stain does not have the color intensity that is desirable. A first difficulty in the development of an indelible lipstick fee always been to find a satisfactory solvent for the bromo acid. Even when this is achieved, the stain does not have sufficient color intensity. In fact, the solvents that are used often weaken the stain and invariably produce a stain with a violet cast, whereas an intense true red is desired. Attempts to develop lipsticks with film forming materials such as cellulose derivatives also failed because the films have a tendency to peel off and cause a disagreeable stretching of the lips. Lipsticks made according to the proposed formulation Ref 132 do not have these drawbacks. They impart a deep stain in any desired shade, and are truly indelible to the extent that no retouching is necessary for at least 8 hours, although the stain can be washed off with soap. A further advantage is that the lipstick mass is practically odorless and can be delicately perfumed. The “8 hour lipstick” is meant to be applied only once every 8 hours. Of course, after 8 hours of wear, in most cases in the evening, a new application

may be desirable for full color effect. However, at that time, a non-staining fashion shade is probably what is wanted and can be readily applied over the

residual stain. The basic color of the new lipstick is FD&C Red No. 3. Additional shades, including brown, can also be obtained but cosmetic D&C colors must be used since suitable food colors are not available. However, it is felt that a natural red lipstick made with a food color should appeal to most, at least as a day shade. The new lipstick is very economical, a 5-gram stick lasting over nine months. It was tested in continuous use for this length of time without causing any drying or peeling of the lips. The lipstick is applied as usual and can be blotted off after 5 minutes, although this is not necessary. Besides, this releases only a trace of excess color and none thereafter even when wiping strongly. If greater brilliancy of the lips is desired, a colorless gloss can be applied. See Gloss Ref 133. The color of the stick can be shaded by addition of D&C Red No. 6 and D&C No. 8 lakes. These lakes readily disperse without milling. However a total of 1% color should not be exceeded since lakes rub off as in regular lipstick. Pastel shades can be obtained by addition of titanium dioxide, but

Lipstick

135

this requires milling. Furthermore, the titanium dioxide wears off and retouching the lips becomes necessary. Variations in color of the stain can be achieved with D&C Orange No. 10. However, the orange stain that is obtained weakens after one year shelf life.! Brown stains can be obtained with Brown No. | (FD&C Replacement by H. Kohnstamm). Purple stains, if desirable, could be obtained with D&C Red No. 28, but D&C Red 21 (bromo acid) should not be used.

Notes on Formulating Lipsticks Before testing new lipstick formulations it is necessary to check the wax content that will insure an easy unmolding operation. This can be determined by means of the Tables I and II. These tables show optimum stick compositions for single waxes in castor oil and mineral oil. Any deficiency in the percentage of a specified wax must be compensated pro rata in order to produce a stick that will unmold. Of course factors of miscibility and surface gloss must be taken into account. The operational stability test should also be made. To illustrate these various points, let us consider the following lipstick formula: 11.5 9 5 BS 5 54 8 0.5 108

Candelilla wax Beeswax Cetyl alcohol Petrolatum Butyl stearate Castor oil Pigments Perfume

A laboratory prepared sample gave an excellent application. The shade is bright since the wax base is white due to a low candelilla content and the absence of lanolin, both of which impart a brown cast. The perfume also develops better since these two ingredients have fatty or waxy odors. Although the lipstick unmolds well in the laboratory, note that the wax content is deficient according to Table I. In the above formulation, candelilla wax accounts for 50% of the wax requirement (11.5% vs 23%). Similarly, beeswax accounts for 33% and cetyl alcohol for 10% of the wax requirement. The deficiency in wax is therefore 7%. Furthermore, beeswax should not have been used since it invariably causes a pitted surface (pinpoints), in this case after six months shelf life. However, the main defect of the formulation is that it plasticizes after two hour heating, making it unfit for molding. This could have been anticipated in the operational stability test mentioned in the introduction. 'This color is manufactured by Hilton-Davis Chemical Co., Thomasset Colors Div.

136

Lipstick

Note On Processing Lipstick The standard texts should be consulted for processing lipstick. Note however that a three roller mill is no longer necessary for grinding the pigments. Less expensive high capacity corundum stone mills are now available for this purpose and they have the advantage of giving a smaller particle size.' Corundum stone mills are made by Fryma A.G. Rheinfelden, Switzerland. Table I Waxes in Castor Oil Stick Consistency

Wax Beeswax Candelilla wax Carnauba wax Cetyl alcohol Spermaceti Stearic acid

% Wax OT 23 18 50 50 40

Unmolding Bad Good Good Bad Bad Bad

Film gloss Good Good Good Dull Dull Dull

Stick gloss

Consistency

Dull Fair Dull Dull Dull Dull

Hard Hard Hard Soft Hard Brittle

Beeswax stick is not stable, develops “pin points.” Should not be used in lipstick. Carnauba stick shows vertical lines of shrinkage. Note that mixtures of castor oil with ozokerite or paraffin wax cannot be molded because of limited solubility. At best, 10% wax can be dispersed giving petrolatum-like consistencies.

Table II Waxes in Mineral Oil'

Stick Consistency

Wax

% Wax

Unmolding

Beeswax Candelilla wax Carnauba wax Cety] alcohol GMS Ozokerite MP 68°C Paraffin MP 52°C Spermaceti Stearic acid

60 30 15 35 60 40 60 60 60

OK OK OK OK Bad OK OK OK OK

Setting point

Stick gloss

SE AIL 60°C 36°C SOE 45°C

Dull Good Good Dull Dull Good Good Dull Dull

46°C

Consistency Plastic Hard Hard Fairly hard Brittle Hard Brittle Brittle

Brittle

‘Mineral oil viscosity 130 Saybold at 100°F.

'W. Dinkel, Processing of Lipsticks. See Cosmetics and Toiletries, 92, 2, 30-34 (1977).

Lipstick

137

Examples of Trade Formulations From Manufacturer’s Product Label

Avon Pink Beauty Lipstick Ingredients: Castor oil Isopropyl lanolate (1) Beeswax Caprylic/Capric triglyceride (2) Candelilla wax Calcium carbonate (3)

Isopropyl palmitate Carnauba wax Microcrystalline wax (4) Ozokerite BHA (5) Titanium dioxide

May contain: D&C Red No. 3, Aluminum lake D&C Red No. 7, Calcium lake D&C Red No. 9, Barium lake

Iron oxides D&C Red No. 36, Barium lake

Remarks: (1) e.g. Amerlate P, Amerchol (2) e.g. Neobee M-5 or Vegetable oil 1400, PVO Co. (3) This ingredient is unusual in a lipstick composition. Its function may be to slowly neutralize the free acids of beeswax, thus preventing the “pinpoints” that invariably develop in stick formulations containing beeswax. (4) Butylated hydroxyanisole, an antioxidant

Hazel Bishop Lipstick. Toiletry Products of America, Hazel Bishop Div. Kenilworth, N.J. “Light red lipstick with gloss and color that stays on” Ingredients: Ozokerite Carnauba wax Talc Fragrance Propylparaben

Castor oil Butyl stearate Candelilla wax Spermaceti Lanolin alcohol Beeswax May contain:

D&C D&C D&C D&C D&C

Red Red Red Red Blue

No. No. No. No. No.

19, Aluminum lake 21, Aluminum lake 27, Aluminum lake 9, Barium lake 1, Aluminum lake

FD&C Yellow No. 5, Aluminum lake Titanium dioxide Red iron oxide D&C Orange No. 17, Barium lake

138

Lipstick

A later declaration shows a slightly different order in the listing of the ingredients, namely: Castor oil Propylene glycol monostearate Candelilla wax Ozokerite Isopropyl palmitate Carnauba wax Lanolin alcohol Talc Petrolatum Fragrance Beeswax Propylparaben Butyl stearate Maybelline Lipstick.

Frosted light pink

Ingredients:

Castor oil Octyl dodecanol (1) Candelilla wax Octyl palmitate (2) Isopropyl lanolate Myristyl lactate (3) Ceresin Carnauba wax Octyl dimethyl PABA (4) Wheat germ glycerides Trihydroxy stearin (5) Oleyl alcohol

Propyl paraben BHA Butyl paraben Bismuth oxychloride (6) Mica (6) Titanium dioxide D&C Red No. 3, Aluminum lake D&C Red No. 9, Barium lake D&C Red No. 21 D&C Yellow No. 5, Zirconium or Aluminum lake

Remarks: (1) (2) (3) (4) (5) (6)

Eutanol G, Henkel Ceraphyl 368, Van Dyk Ceraphyl 50, Van Dyk Octyl p-dimethylaminobenzoate, Escalol 507, Van Dyk Thixcin, NL Industries, Inc Nacreous pigment

Lipstick

139

Helena Rubinstein, Skin Life Lipstick Ingredients:

Castor oil Lanolin oil Mineral oil Ceresin Isostearic alcohol Carnauba wax

Candelilla wax Lanolin Fragrance Hydrolyzed animal protein Propylparaben BHA

May contain: D&C Red No. 3, D&C Red No. 6, D&C Red No. 7, D&C Red No. 7, Titanium dioxide Iron oxides

Aluminum lake Barium lake Zirconium lake Calcium lake

Chap Stick, Lip Balm.

D&C Red No. 19, Aluminum lake D&C Red No. 21 D&C Red No. 21, Aluminum lake D&C Orange No. 17, lake Mica Bismuth oxychloride

Miller-Morton, Richmond, Virginia

Active ingredients: 44 % Petrolatums 1.5% Padimate 0 (1) 1 Lanolin

1.5% Isopropyl myristate 0.5% Cetyl alcohol

Remarks: (1) 2-Ethyl hexyl PABA, a sunscreen

Remaining ingredients (Waxes) are not declared Blistik, Medicated Lip Balm.

Blistex, Inc, Oak Brook, Ill.

Active ingredients:

Octyl dimethyl PABA

Allantoin

Other ingredients: Mineral oil Paraffin Petrolatum Ceresin Carnauba

Cetyl alcohol Beeswax Lanolin Fragrance

140

Lipstick

Formulations

The formulation of lipstick is usually reported on a total percentage basis. The formulations in this text are given in parts of colors for 100 parts of base. The consistency of make-up does not depend on the added powders, certainly not at the lower concentrations. This is clearly exemplified for cover mark make-up Ref 146. In the case of lipstick, note also that the colors are often milled separately with the castor oil. This being understood, the formulation can be reported quite simply.

Ref 131 AWTS 10 22 4.5 44.5

Lipstick Base

Lanolin Petrolatum, white, USP Candelilla wax Stearic acid

A

2 2.5. B 50 Cuil

55.5

Butyl stearate Cetyl alcohol (1) Castor oil Perfume

TT 100

(1) Do not use stearyl alcohol. Although this material is interchangeable with cetyl alcohol in emulsions, it crystallizes conspicuously outside of molded lipstick within a few days of storage. Procedure: Heat separately the castor oil part B with the D&C Red No. 21 (bromo) shown below for the colors of the various shades. Bring the temperature to 85°C to partially dissolve the bromo. Add the remaining colors and pass through roller mill. This is essential for proper dispersion and development of the colors. To the hot color mass, add the melted waxes part A and perfume C. Store in vegetable insets as used in cafeteria steam tables. Remelt on the steam table as required for production. Bring the temperature to 85°C and mold. Glaze the lipsticks that have been inserted in the containers as usual by means of a Bunsen flame. Lipstick Shades (Red) Parts Color for 100 Parts of Lipstick Base Light

1 4.5 1 1

TS,

D&C Red No. 21 C 15-010 CC 19-025 C 19-003

Medium

1 1 2 2 0 .5 6.5

D&C Red No. 21 C 15-010

C 19-025

C 19-003 C 23-009

Dark

D&C Red No. 21 C 15-010 2 19-025 2 C 19-003 0. C 21-003 0.5 ] ]

6. Ns

Lipstick Pink

1 0.3 0.6 0.6 3.5 2.5 #7)

141

Bright Red

D&C Red No. 21 C 15-010 C 19-025 C 19-003 C 21-003 Titanium dioxide

1 0.8 1.6 1.6 0.7 0.3 0.4

8.5

6.4

D&C Red No. 21 C 15-010 C 19-025 C 19-003 C 21-003 C 15-007 Titanium dioxide

See Color Index for codes.

Original Primary Shades Formulations With Lithol Reds! Light 1 D&C Red No. 21 4.5 D&C Red No. 9, barium lake 2.5 D&C Red No. 11, calcium lake 8.0

Medium 1 D&C Red No. 21 5.5 D&C Red No. 11, barium lake 0.5 D&C Red No. 36, barium lake 7.0

Dark

1 D&C 3.5 D&C 1 D&C 0.5 D&C 6.0

Red Red Red Red

No. No. No. No.

Pink

21 11, barium lake

1 D&C Red 3.5 D&C Red 34, calcium lake 1.5 D&C Red 19, aluminum lake 2.5 Titanium 8.5

Mauve

No. 21 No. 19, aluminum lake No. 8, sodium lake dioxide

Bright Red

1 D&C Red No. 21 2.5 D&C Red No. 34, calcium lake 2.5 D&C Red No. 11, calcium lake

1 4 0.7 0.3 0.4

6.0

64

D&C Red D&C Red D&C Red D&C Red Titanium

No. 21 No. 11, barium lake No. 19, aluminum lake No. 8, sodium lake dioxide

'1Lithol reds are still being used in foreign cosmetics and may be relisted in the U.S. See Color Index.

142

Lipstick Natural “8 Hour” Lipstick True Red

Ref 132 A 10 10 2) 10

35

Paraffin, mp 128°C Candelilla wax Lanolin Ozokerite No. 4

B 30 35 Case D 0.25

Dipropylene glycol (1) Oleyl alcohol (2) FD&C Red No. 3 (3) Perfume

67.25 1102.25

(1) Union Carbide (2) Adol 85, Sherex Chemical (3) Erythrosine, H. Kohnstamm. See note below.

Melt waxes A at 85°C. Dissolve color C in B, heating to 85°C. Add melted waxes and perfume. Keep at 85°C in covered vessel. Mold as usual. Glazing is not required since the stick has natural gloss. Set Pt is 62°C. FD&C Red No. 3 from another source was found to be only partially soluble. Cosmetic colors, although meeting all the FDA specifications, may show variations in their physical properties (and possibly in chemical configuration) due to differences in the manufacturing process. Stability The stability of lipstick Ref 132 was tested for a period of over seven years shelf life. Appearance and performance remained satisfactory although a few sweating spots were observed. Accelerated oven tests cannot be conducted for these lipsticks in view of the comparatively low vapor pressure of dipropylene glycol. Setting Point The setting point of the lipstick can be raised to 68°C by reducing the candelilla wax to 5 parts and adding S parts of carnauba wax. However, this stick showed signs of sweating after two days, although these disappeared almost as quickly. Droplets were identified as propylene glycol which is present in the dipropylene glycol as an impurity. The setting point can also be raised to 75°C by the addition of 5 to 10% hydrogenated castor oil. Although paraffin wax has a low melting point, it should not be eliminated since it is a key element in controlling syneresis.

Lipstick

143

Pan Lip Glosser No. 1 For Fingertip Application

Ref 133 A

12.5 12.5 _/5_

Lanolin alcohols (1) Candelilla wax Hydro methylabietate (2)

B

100

1 0.1

Titanium dioxide D&C Red No. 9

ie

crit

(1) Superhartolan, Croda (2) Hercolyn, Hercules

Melt waxes A, add B and homogenize. Pour into pans at about 10kGR Pan Lip Glosser No. 2 For Fingertip Application

Ref 134 A

10 10 fife 5

100

Isopropyl lanolate (1) Lanolin alcohols (2) Hydro methylabietate (3) Candelilla wax

Bol 1

os

2

Titanium dioxide D&C Red No. 9

T 102

(1) Amerlate P, Amerchol (2) Superhartolan, Croda (3) Hercolyn, Hercules

Same procedure as for Ref 133. This cosmetic could serve as a Rouge since it imparts gloss and color. Lip Gloss For Roll-On Application

Ref 135 A 90 10

Castor oil Lanolin

B 5 1

100

6

Timica pigment “Sparkle” (1) Perfume

T 106

(1) The Mearl Corp., New York

Heat A to about 70°C to dissolve lanolin. Add B and homogenize. Stir until cold.

144

Make-up preparations

14. MAKE-UP PREPARATIONS The make-up formulations developed for this text are the following:

Cake make-up Liquid make-up Cream make-up Molded make-up Molded fashion plate Cover mark for blemishes Spot stick for blemishes Cream eye shadow Stick eye shadow

Ref 141 142 143 144 145 146 147 148 149

Cream mascara Tablet mascara Eyeliner Face powder Powder compact

Ref 150 1S) 152 153 154

Cream rouge

155A, 155B

Dry rouge Gel blush Stick rouge

a

156 157 158

See Section 13 for Lipstick and Lip Gloss. All Formulations were carefully tested for stability and quality. A limited number of shades are given with each item. In the development of shades, it is recommended to prepare single color bases and blend these in separate tests. This procedure is more rapid than attempting to work with dry color mixes. Formulations

are again shown in two columns.

In most cases, the first

column gives the base for a total of 100 parts. The second column illustrates the composition of a typical shade, the total of which is usually between 10 to 40 parts. This is to be added to 100 parts of the base. Within these limits, the consistency and application of the make-up is independent of the variable amount of powder added. In particular, the setting point of the preparation is not altered.

Examples of Trade Formulations From Manufacturer’s Product Label

Avon delicate beauty liquid make-up (Brown)

Ingredients: Water Glycerin Isopropyl palmitate Stearic acid Cetyl alcohol Magnesium aluminum silicate (1) Myristyl myristate

Methylparaben Cellulose gum (2) Propylparaben BH A (3) Titanium dioxide Iron oxides Triethanolamine

Remarks:

(1) e.g. Veegum, Vanderbilt Co. (2) Sodium carboxymethyl cellulose (CTFA) (3) Butylated hydroxyanisole, an antioxidant

Make-up preparations

145

Helena Rubinstein, The Fashion Liquid Make-Up (Brown)

Ingredients: Water Lanolin alcohol Hybrid sunflower oil Mineral oil Propylene glycol Glyceryl stearate Kaolin Oleic acid Stearic acid Triethanolamine Sodium borate

Lecithin Methylparaben Magnesium aluminum silicate (1) Fragrance Cellulose gum Silk powder Dioctyl sulfosuccinate (2) Propylparaben Titanium dioxide Iron oxides

Remarks:

(1) Veegum, Vanderbilt Co. (2) e.g. Aerosol OT, American Cyanamid Co. Noxell, Cover Girl Cream Make-Up (Ivory brown) Ingredients: Water Propylene glycol Mineral oil Decyl oleate (1) Glycerin stearate Stearic acid Isopropyl lanolate Myristyl myristate (2) Triethanolamine Caprilic/Capric triglyceride

Bentonite Fragrance Methylparaben Propylparaben Dimethicone (4) Kaolin Talc Titanium dioxide Iron oxides

May contain: Ultramarine blue Remarks:

(1) (2) (3) (4)

Ceraphyl 140, Van Dyk Ceraphyl 424, Van Dyk e.g. Vegetable oil 1400, PVO e.g. Silicone L-45, Union Carbide or Dow Corning 200 Fluid, Dow Corning

146

Make-up preparations

Maybelline, Cream Blush. tion (Cinnamon brown)

A molded fashion plate for fingertip applica-

Active ingredient:

Padimate (1) Other ingredients:

Caprylic/Capric triglyceride (2) Castor oil Microcrystalline wax Cetyl lactate (3) Quaternium-18 hectorite (4) Ozokerite Magnesium carbonate Kaolin

Calcium silicate (5) Carnauba wax Beeswax Propylparaben Methylparaben Butylparaben BHA

May contain: Iron oxides Titanium dioxide D&C Red No. 3, Aluminum lake D&C Red No. 6, Barium lake D&C Orange No. 17, lake

Mica FD&C Blue No. 1, Aluminum lake D&C Yellow No. 5, Aluminum lake Bismuth oxychloride

Remarks:

(1) (2) (3) (4)

Amyl dimethyl PABA, Escalol 506, Van Dyk Vegetable oil 1400 or Neobee M-5, PVO e.g. Ceraphyl 28, Van Dyk Reaction product of hectorite clay and Aliquat H 226, General Mills Chemicals (5) Microcel E or C, or T-41, Johns Manville

Maybelline, Cover Stick. A cover mark molded like lipstick (Light) Ingredients: Mineral oil Ceresin Kaolin Lanolin oil Talc Max Factor, Erase.

Butylparaben Propylparaben BHA Titanium dioxide Iron oxides A molded cover mark stick

Ingredients:

Mineral oil Ozokerite Kaolin Lanolin

Lanolin oil Fragrance Titanium dioxide Iron oxides

Make-up preparations Covermark.

Lydia O’Leary, Distr.

147

A pomade for fingertip application

Ingredients: Mineral oil Titanium dioxide Beeswax Talc

Magnesium carbonate Iron oxide Propylparaben Fragrance

Maybelline, Cream Make-Up (Ivory brown)

Active ingredient: Padimate (1)

Other ingredients: Water Dioctyl adipate (2) Mineral oil Isopropyl myristate Glyceryl stearate Propylene glycol Tale Octyl palmitate (3) Stearyl alcohol Glycerin Oleic acid Stearic acid

Lanolin alcohol Sodium lauryl sulfate PEG-66 trihydrostearin (4) Triethanolamine Magnesium aluminum silicate (5) Methylparaben Paraffin Butylparaben Simethicone (6) Propylparaben Fragrance

May contain: Iron oxides Ultramarine blue

Titanium dioxide Mica

Remarks:

(1) (2) (3) (4) (5) (6)

Amyl dimethyl PABA, e.g. Escalol 506, Van Dyke e.g. Wickenol 158, Wickhen Products e.g. Wickenol 155, Wickhen Products Paricin 545 W D, N.L. Industries Veegum, Vanderbilt Co. Antifoam A, Dow Corning

148

Make-up preparations

Max Factor, Pan Cake.

A pressed powder for wet sponge application

Ingredients: Talc Mineral oil Stearic acid PEG-6-32 (1) Sulfated castor oil (2) Glyceryl stearate S.E. Lanolin Cetyl alcohol

Triethanolamine Fragrance Methylparaben Propylparaben Butylparaben Sorbic acid Titanium dioxide Iron oxides

Remarks:

(1) Mixture of PEG-6 and PEG-32, Polyethylene glycol 1500, Union Carbide (2) e.g. Monopol Oil MDD, Nopco Chemical Max Factor, Pan Stick. A molded cake applied like lipstick (Brown) Ingredients: Mineral oil Carnauba wax Paraffin Beeswax Ozokerite Fragrance

Maybelline, Eye Shadow Cream. Frost)

Methylparaben Propylparaben Sorbic acid Titanium dioxide Kaolin Iron oxides

In vial tube with applicator (Silver Blue

Ingredients: Petroleum distillate (1) Talc Dihydroabietyl alcohol (2) Polyethylene (3) Trihydroxystearin (4) Polydimethylcyclosiloxane (5) Synthetic spermaceti Magnesium carbonate Remarks: (1) (2) (3) (4) (5) (6)

Butylparaben Simethicone (6) BHA Mica Titanium dioxide Ultramarine blue Chromium hydroxide green Iron oxides

e.g. Shell Sol 71, Shell Chemical Hercules, Inc e.g. Polyethylene AC-617, Allied Chemical Thixcin, NL Industries Dimethylpolysiloxane, dimethicone (CTFA) Antifoam A, Dow Corning

Make-up preparations Maybelline, Ultra Frost Frost No. 2)

Eye Shadow.

A pressed powder eye shadow (Blue

Ingredients:

Talc Octyl palmitate (1) Zinc stearate Methylparaben Propylparaben

Bismuth oxychloride (2) Mica Titanium dioxide Ultramarine blue Chromium hydroxide green

May contain: Isopropyl isostearate (3) Magnesium stearate

Iron oxides

Remarks: (1) Ceraphyl 368, Van Dyk, or Wickenol 155, Wickhen Products (2) Nacreous pigment (3) Wickenol 131, Wickhen Products Revion, Eye Shadow.

Extra creamy pressed powder (Shy Brown)

Ingredients: Talc Zinc stearate Kaolin Water (1) Mineral oil Lanolin alcohol Isostearic hydrolyzed animal protein (2)

Isopropyl myristate TEA isostearate Methylparaben Propylparaben Sodium dehydroacetate (3) Trisodium EDTA Phenyl mercuric acetate

May contain: Titanium dioxide Iron oxides Mica Ultramarine blue Bismuth oxychloride (4)

Ultramarine violet Chromium hydroxide green Chromium oxide green Carmine Ultramarine pink

Remarks:

(1) (2) (3) (4)

149

Water for allowing pressing of powder, not retained after drying e.g. Oil soluble protein IP, Croda Bactericide Nacreous pigment

150

Make-up preparations

Maybelline Eyeliner.

Waterproof for brush application (Velvet black)

Ingredients: Petroleum distillate (1) PVP Beeswax Quaternium-18 hectorite (2) Butylparaben

Propylparaben Simethicone (3) BHA Iron oxides

Remarks:

(1) e.g. Shell Sol 71, Shell Chemical (2) Reaction product of a clay with dimethyl di(hydrogenated tallow) ammonium chloride, e.g. Aliquat H226, General Mills (3) Antifoam A, Dow Corning Maybelline Eyeliner, or Eyebrow Pencil (Brown)

Ingredients of the pencil core: Japan wax Hydrogenated vegetable oil Lanolin Ceresin Hydrogenated cotton seed oil Silica Sorbitan stearate Eye Shadow, Diane Von Furstenberg.

Polysorbate-60 Methylparaben Propylparaben Butylparaben BHT,BHA Iron oxides

D.V.F. Inc, Distr.

Ingredients: Talc Mica Titanium dioxide Isostearyl neopentanoate (1)

Zinc stearate Imidazolidinyl urea Methyl & propyl paraben

May contain: Iron oxide pigments Manganese violet Ultramarine blue Remarks:

(1) Ceraphyl 375, Van Dyk

Chromium oxide green Carmine Red No. 40

Make-up preparations Maybelline Comb-on cream mascara.

151

“Separates, colors & curls” (Brown)

Ingredients: Petroleum distillate (1) Polyethylene (2) Dihydroabietyl alcohol (3) Aluminum stearate (4) Candelilla wax

Methylparaben Butylparaben Propylparaben DHA Iron oxides

Remarks:

(1) (2) (3) (4)

e.g. Shell Sol 71, Shell Chemical e.g. Polyethylene AC-617, Allied Chemical Hercules Inc Whittaker, Clark & Daniels

Lashbrite, Cream mascara.

Del Laboratories, Farmingdale, N.Y. (Black)

Ingredients:

Stearic acid Imidazolidinyl urea Isostearic hydrolized protein Ammonium hydroxide Mineral oil and Aluminum stearate and PEG-2 stearate EDTA

Water Acrylic-Acrylate copolymer Cetyl alcohol Isopropyl myristate PEG-2 stearate (1) Propylene glycol Rayon

May contain: Titanium dioxide

Iron oxides Ultramarine blue Ultramarine violet Remark:

(1) Diethylene glycol monostearate Maybelline, Cake mascara.

A tablet (Brown)

Ingredients: Stearic acid Triethanolamine Carnauba wax Talc Methylparaben Remark:

(1) Antifoam A, Dow Corning

Propylparaben Simethicone (1) BHA Iron oxides

152

Make-up preparations

Almay, Cream mascara.

Almay Inc, New York, N.Y.

Ingredients: Water Beeswax Acrylic/Acrylate copolymer Stearic acid Propylene glycol Oleth-20 PVP/VA copolymer

Microcrystalline wax Calcium stearate Aluminum hydroxide Sodium borate Imidazolidinyl urea Methylparaben Propylparaben

May contain:

Titanium dioxide Talc Ultramarine blue

'

Chromium hydroxide green Ferric ferrocyanide Tron oxides

Elizabeth Arden, Loose Powder

Ingredients: Talc Zinc oxide Kaolin SD Alcohol Isopropyl myristate Magnesium stearate Fragrance

Cetyl alcohol Lanolin oil Magnesium carbonate Lanolin Water Methylparaben Propylparaben

May contain: D&C Orange No. 17, lake D&C Red No. 7, Calcium lake

D&C Red No. 3, Aluminum lake Iron oxides

Chesebrough-Pond’s Angel Face Powder

Ingredients: Talc Zinc stearate Hydrolized silica Coty, Air Spun Face Powder.

Fragrance Iron oxides

Ivory Tone (Beige)

Ingredients:

Talc Zinc oxide Magnesium carbonate Mineral oil Lanolin May contain:

D&C Yellow No. 5, Zirconium lake

Cetyl alcohol Imidazolidinyl urea Fragrance Titanium dioxide Iron oxides

D&C Red No. 3, lake

Make-up preparations

153

Chesebrough-Pond’s, Angel Face Pressed Powder Ingredients:

Talc Zinc stearate Mineral oil Dimethicone (1) Remark: (1) e.g. Dow Carbide

Lanolin Fragrance Iron oxides Titanium dioxide

Corning 200 Fluid, Dow

Corning, Silicone L-45, Union

Maybelline Pressed Powder (Beige)

Ingredients: Talc Mineral oil Calcium carbonate Isopropyl myristate Methylparaben

Imidazolidinyl urea Magnesium stearate Propylparaben BHA Fragrance

May contain:

Titanium dioxide

Iron oxides

Ultramarine blue

Max Factor, Cream Puff. A powder compact

Ingredients: Talc Mineral oil Beeswax Polysorbate-60 Lanolin

Sorbitol sesquioleate Fragrance Methylparaben Propylparaben

Also contains (Except Translucent Shade): Zinc stearate

Calcium carbonate

May contain: Titanium dioxide Ultramarine blue Iron oxides Note: This type of compact may be pressed without addition of water.

154

Make-up preparations

Max Factor, Maxi-Glow Cream Blush. greasy consistency

A molded fashion plate of non-

Ingredients: Ozokerite Propylene glycol BHA BHT Propyl gallate (3) t-Butyl hydroquinone (4)

Isopropyl myristate Mineral oil Cetearyl octanoate (1) Carnauba Talc Beeswax Myristyl myristate (2) May contain:

Titanium dioxide Mica Bismuth oxychloride Iron oxides Chromium oxide greens

D&C Orange No. 17, lake D&C Red No. 6, Barium/strontium lake D&C Red No. 7, Calcium lake D&C Red No. 9, Barium lake FD&C Yellow No. 6, Aluminum lake

Remarks:

(1) (2) (3) (4)

Pur-Cellin oil, Dragoco e.g. Ceraphyl 424, Van Dyk Tenox PG, Washman Chemical Tenox TBHQ, Eastman Chemical

Moist Rouge, permanent)

Stein

Cosmetic

Co., New

York.

A cream

rouge

(Non-

Ingredients: Mineral oil Paraffin Beeswax Lanolin Cetyl alcohol

Fragrance Isopropyl myristate Propylparaben Calcium carbonate

May contain: Titanium dioxide Iron oxides Iron oxides (and) talc D&C Red No. 36, Barium lake D&C Red No. 19 & 21, Aluminum lake

D&C Orange No. 4, Aluminum lake D&C Red No. 9, Barium lake D&C Red No. 7, Calcium lake D&C Red No. 6, Barium lake

Make-up preparations Rosy Amber Cream Blusher. Mfrs. A cream rouge

155

Clinique Laboratories Distr., Estee Lauder

Ingredients: Propylene glycol dicaprylate-dicaprate (1) Myristyl propionate (2) Talc Propylene glycol dipelargonate (3) Hydrogenated castor oil (4) Alkylated PVP (5) Calcium silicate Carnauba

Microcrystalline wax Magnesium carbonate Zinc stearate Lecithin | Quaternium-18 hectorite (6) PEG-40 sorbitan peroleate (7) Tocopherol Ascorbyl palmitate Propylparaben

May contain:

Titanium dioxide and mica Bismuth oxychloride Iron oxides

Lakes of FD&C Yellow Nos. 5, 6 Lakes of D&C Orange Nos. 5, 17 Lake of FD&C Blue No. 1

Lakes of D&C Red Nos. 3, 6, 7, 9,

19.215.27; 30,33, 36 Remarks: (1) (2) (3) (4) (5) (6) (7)

e.g. Tegester PG 8-10, Inolex Lonzest 143-S, Lonza, Inc Emerest 2388, Emery Industries Baker Castor Oil Co. Not in CTFA e.g. Bentonite 38, NL Industries, Inc Arlatone T, ICI

156

Make-up preparations

Formulations

Cake Make-Up for Sponge Application Ref 141 Manufacturing Process The manufacture of cake make-up consists of three separate operations. First, basic powders are prepared for the various shades. A powder base is then prepared by addition of oil and hydrophilic bases. Finally, the powder base is pressed into a compact. Basic Powders

A series of attractive shades can be formulated as follows: Base 850 150 = 1000

Natural

Talc, French Titanium dioxide

1000 5.7 5.4 PemtOiisl

Brunette

Peach

Base C 33-128 C 33-120

1000 1 ile 1010

Beige

1000 Base 11 C 33-120 3-50.C+33=123 3.5 C 33-115 1018

1000 15 2 1.5 1018.5

Base C 33-128 C 33-120

Dark brunette

Base C 33-120 C 33-128 C 33-115

1000 13 7 6.5 1026.5

Base C 33-120 C 33-115 C 33-128

Mix these powders as usual and pulverize with micro-pulverizer.

Procedure codes.

is the

same

as

for

face

powder.

See

Color

Index

Powder Base

80 10 10 0.5 100.5

Pulverized powder (above) Oil base A (below) Hydrophilic base B Perfume

Oil Base A

10 40 _50

100

Lanolin Petrolatum, white USP Mineral oil visc. 70

Hydrophilic Base B

50 50

100

Glycerin Carbowax 1500

for

Make-up preparations

157

Note: Base A imparts a smooth finish, whereas Base B allows wet sponge application. These bases must be added separately since they are not miscible. Procedure: Heat mixtures A and B separately until liquid. Place the pulverized powder in a pony mixer and add mixtures A and B while still liquid. Mix for half hour and pulverize twice through a Fitzpatrick mill using a Y-inch screen.

Pressing: Fill aluminum pans as for compact powder and press with a die by means of compressed air at 85 lbs per square inch. For a smooth finish with imprinted trade mark, a thin rubber sheet (Dental dam) should be stretched over the die. Two pulverizers are needed in this process. The Mikro-Pulverizer gives the proper color development of the dry powders, but cannot be used to pulverize the oiled powders which would jam the feed inlet. The oiled powders easily pass through the Fitzpatrick screen. Liquid Make-Up

Ref 142 Base

A

4 I 3 zo 0.1 Be 2 2 5 0.1 74

95.7

Stearic acid Lanolin alcohols (1) Mineral oil GMS Propylparaben TEA Laneth-16 (2) Propylene glycol Methylparaben Water

Make-up (Brunette)

A + B 95.7 @ 5 > 0.8 0.2 D 0.3

Base Talc Titanium dioxide C 33-120 Red oxide A 6205 Perfume

107

(1) Superhartolan, Croda (2) Solulan 16, Amerchol Mix A and B at 75°C. Add pulverized pigments C and perfume D at about 65°C. Mill hot and strain through SS mesh. Alternate procedure: Disperse the pulverized pigments in the oil phase A, then add part B. This procedure eliminates the milling operation.

158

Make-up preparations Cream Make-Up Non-Aqueous

Ref 143 Cream base

A

10 67.5 10 12.5

100 _

Make-up (Brunette)

Lanolin Mineral oil, visc. 70 Paraffin mp 128°F Microcrystalline wax (1)

A 100 B 40 1.6 C 0.4 wierd4]

Cream base Zinc oxide C 33-123 Perfume

142

(1) “Victory” White wax, Petrolite Corp., Bareco Div.

Pulverize pigments B and add to melted cream base A. Mill hot and strain. Pour into jars. Set Pt 42°C. Molded Make-Up

Ref 144 Wax base

A

65 5 30

Make-up (Brunette)

Mineral oil, visc. 185 (1) Lanolin Ozokerite mp 68°C

100

A 100 B 20 20 1 C 0.4

141.4

Wax base Talc Titanium dioxide C 33-120 Perfume

(1) Protol USP, Sonneborn, or Primol 185, Exxon

Same procedure as for Cream make-up. Pour into plastic push-up cases. Fashion Plate For Fingertip Application

Ref 145 Base A

10 10 17 63

Carnauba wax Paraffin mp 128°F Lanolin Isopropyl myristate

_—

Fashion plate (Brunette) A B

C

100

100 20 20 5 1 0.5

146.5

Base Talc Titanium dioxide C 33-120 Red oxide A 6205 (1) Perfume

(1) H. Kohnstamm & Co. Melt waxes A and bring to about 70°C. Pulverize pigments B and add to A. Mill hot and strain. Pour into pans. This plate has a firm glossy surface. Product take-off for fingertip application is adequate.

Make-up preparations

159

Cover Mark

For Fingertip Application to Cover Blemishes

Ref 146 Base

A

10

Cover mark (Brunette)

Candelilla wax Ozokerite No. 4 Lanolin Mineral oil Isopropyl myristate

A B

100 45 45 8 2 C 0.5 200.5

Base Talc Titanium dioxide C 33-120 Red oxide A 6205 Perfume

Same procedure as for Fashion plate. Pour into flat jars or pans.

Set Pt about 38°C. Spot Stick Molded Stick to Cover Blemishes

Ref 147 Base

A

20

Spot stick (Brunette)

Candelilla wax Ozokerite No. 4 Lanolin Mineral oil Isopropyl palmitate

A B

100 45 45 8 2 C _0.5 200.5

Base Talc Titanium dioxide C 33-120 Red oxide A 6205 Perfume

Melt waxes and oils and bring to 80°C. Pulverize pigments B and add to A. Mill hot in roller mill. Pour into lipstick molds at about 45°C) et EE aa°C, This stick is glossy with good application and excellent stability (Non-sweating). Cream Eye Shadow

Ref 148 Base

A

21 10 69

Eye shadow, blue

Spermaceti

A 100

Lanolin Petrolatum, white, USP

B C

—=

100

18 3 0.5 #21:5

Base Ultramarine blue Titanium dioxide Perfume

Pulverize pigments B and add to melted base A. Mill hot and strain through SS #150 mesh. Pour into plastic containers. Additional shades are obtained as follows:

160

Make-up preparations Blue.

18 3

Green

Ultramarine blue Titanium dioxide

15 2.5 4.5

Ot

Cosmetic chromium oxide Ultramarine blue Titanium dioxide

24 Mauve

3 6 12

Violet

Carmine Ultramarine blue Titanium dioxide

11 3 9

om

Ultramarine blue Carmine Titanium dioxide

23 Brown

4 0.1 6

Blue-gray

C 33-115 Cosmetic black Titanium dioxide

12 0.3 0.3 10

0.1

22.6

Ultramarine blue Cosmetic chromium oxide Cosmetic black Titanium dioxide

Pulverize pigments. Quantities are for 100 parts of base A. Stick Eye Shadow

Ref 149

A 24 12 |ys 6 6

60

Wax base Ozokerite mp 68°C Lanolin Petrolatum, white, USP Spermaceti Paraffin mp 128°F

Color base, blue

B 18 3 C.2T 4.5 D 0.5

557

Ultramarine blue Titanium dioxide Mineral oil visc. 340 (1) Butyl stearate Perfume

PTs 13

(1) Kaydol, Witco Chemical, Sonneborn Div. Add pulverized pigments B to cold mixture C and pass through roller mill. Melt A and add milled colors. Heat to 80°C. Add D. Pour into lipstick molds. Glaze as usual.

Additional shades are obtained with powders and quantities as shown under Ref 148. Note that total wax is actually 60 + 27 + 4.5 = 91.5 parts.

Make-up preparations

161

Cream Mascara (Brown) Cream for Brush Application

Ref 150 Ares

Stearic acid GMS Mineral oil Petrolatum, white, USP Lanolin

Bo

citivuasl aA 60 Water 0.15 Methylparaben Gy sé Talc 5 Umber A 8534 (2)

Silicone L 43 (1)

er 71.65

WwCO] rannn

T 101.65

(1) Union Carbide (2) H. Kohnstamm & Co. Mix A and B at 75°C and add pulverized pigments C. Strain through SS #100 mesh. Stir until cold. Set Pt 40°C. Tablet Mascara (Brown) For Brush and Water Application

Ref 151

A 28 10 30

10 78

Stearic acid Lanolin alcohols 15 POE (1) Carnauba wax GMS

B

10 12 eats [4] ae 32

Lanolin TEA Umber A 8534 Preservative T 110

(1) Polychol 15, Croda Melt waxes A to 95°C and add B. Add pigment C (or other pigments) to the base A + B (100 parts). Strain through SS #100 mesh. Pour into mascara molds. Set Pt 70°C. Preservative added is for protection of the preparation when in use.

Ref 152

Eye-Liner (Brown) For Brush Application to the

Stearic acid GMS Mineral oil Lanolin oil TEA Potassium stearate

B

5 62 C 14 6 D-5

92

Eyebrows

Propylene glycol Water Talc Umber A 8534 Acrylic emulsion (1) Preservative

~=Ss«T:100.2

(1) or natural rubber latex Mix A and B at 75°C. Add pulverized pigments C. Strain through SS #100 mesh. Add D and stir until cold.

162

Make-up preparations Face Powder

Ref 153 Manufacturing Process The processing of face powder consists basically in blending and pulverizing cosmetics powders. The pulverization is of course essential for the proper dispersion and development of the colors. The simple procedure outlined below applies for all powders used in make-up preparations such as compact powder, dry rouge, etc. Face Powder (Rachel) A 770 Talc, Italian 180 Zinc oxide 30 Zinc stearate

980

B 10 Magnesium carbonate 5 Mineral oil a, Perfume

C 1.5 C 70-5270 0.6 C 69-002 2 C 33-107

20 T 1000

1

Place ingredients A into a ribbon blender. Mix B and sift into A. Add pigments C. Mix for two hours. Pulverize in Mikro-Pulverizer using screen 0.027” or 0.020”. Some formulators age the perfume mixture B before addition to base A. Face Powder Shades Parts Colors for 1000 Parts White Base (A + B) Natural

0.4 1.0 0.2 0.5

C C C C

19-012 70-5270 69-002 33-107

Da

2.4 0.6 13.0

C 70-5270 C 69-002 C 33-107

16 Brunette

2.0 5.0 6.5 ae 13.5

Type “Soleil d’Or” Coty

C 70-5270 C 69-002 C 33-107

Type “Olive” Max Factor

2.4 0.6 B35

C 70-5270 C 69-002 2C23 32107

4,3. Sun beige

3.0 11.5

C 33-128 C 33-107

! 0.3

48.6

51.4

Glycerin Sodium laureth-3 sulfate (3) Sodium stearate (4) Perfume, color Titanium dioxide

7T 100

(1) Neo-Fat 14, Armak _ (2) Standapol T, 60% active, Henkel (3) Standapol ES-40, 60% active, Henkel, or Carsonol 60% active, Carson Chemical (4) Sodium stearate C 1, Witco Chemical

SES-S,

Heat part A to 75°C. Add B and C, bring temperature to 80-85°C. Add D, heat and stir until sodium stearate is dissolved. Add perfume and color. Disperse titanium dioxide to opacify soap. Mold. Set. Pt 55°C, pH = 8.5. Molded Soap No. 1. Clear

Ref 202 Propylene glycol Myristic acid TEA lauryl sulfate

Cid 14.4 D 16

Glycerin Sodium laureth-3 sulfate Sodium stearate

NaOH, 50% aq. soln

E

Perfume, color

1

Propylene glycol

41.4

T 100

Same procedure as in Ref 201. Set Pt 45°C.

Molded Soap No. 2. Clear Propylene glycol Myristic acid TEA lauryl sulfate NaOH, 50% aq. soln Propylene glycol

C

10 13.4 11 D 16 1

Glycerin Sodium laureth-3 sulfate Sodium lauryl sulfate (1) Sodium stearate Perfume, color

Sie4 | e100

(1) Standapol WAQ Special, Henkel Same procedure as in Ref 201. Set Pt 45°C. Soap is transparent, but shows a slight Tyndal effect. Sodium stearate can be easily produced in situ. See deodorant sticks.

Molded glycerin and transparent soaps

213

Liquid Soap. Pearlescent For Pump Spray Bottle Ref 204 A

10 2 20 2 3

Na laureth-2 sulfate (1) Propylene glycol Ammonium lauryl sulfate (2) Cocoamidopropyl betaine (3) Ethylene glycol monostearate (4)

B 63 0.5 O22 0.1

sass.

37

63.8 (1) (2) (3) (4)

Water Sodium chloride PTAEPA Formaldehyde USP

T 100.8

Standapol ES-2, 30% active, Henkel Maprofix NH, 30% active, Onyx Chemical Varion CADG Technical, 35% active, Sherex Chemical No. 70, Stepan, Kessco Division

Mix A and B at 75°C. The addition of triethanolamine raises the pH to 7.8. This is necessary to accelerate the foam formation in use. Liquid Soap Cream Lotion Formulation

Ref 205 A

15 30 7.5.

Glycerin TEA lauryl sulfate (1) Myristic acid (2)

Bis? 7 C30

a5

10

49

Potassium hydroxide, pellets Water Ammonium lauryl sulfate (3) Water

T 101.5

(1) Standapol T, 40% active, Henkel (2) Neo-Fat 14, Armak (3) Maprofix NH, 28% active, Onyx Chemical Mix A and B at 75°C to saponify the myristic acid. Add C.

This preparation can also be used as a shaving cream lotion.

214

Suntanning preparations

19. SUNTANNING

PREPARATIONS

Suntanning preparations are mostly used in the following forms: Aerosols. Ref 206 Clear lotions. Ref 207 Cream lotions. Ref 208, 209 Creams. Ref 210A & B, 211 Gels, tanning. Ref 212-214 Gels, bronzing. Ref 215, 216 Oils, tanning. Ref 217 Protective balms. Ref 218 The theoretical aspects of sunscreens and suntanning are extensively treated in the cosmetic handbooks. The basic information is well known and need not be reviewed again. Cream lotions are favored by most consumers since they spread easily and are non-greasy. Creams and suntan oils, ranking next, are more water resistant but tend to be somewhat greasy. Of the many other suntan preparations, all offer certain advantages. For instance, alcoholic lotions and gels spread and dry quickly and are ideal for the face. When used at the beach, they must be reapplied after swimming. Suntan balms based on petrolatum offer the best protection against sun, water and wind. They are greasy but ideal for alpinists, skiers and sportsmen. Bronzing gels are make-up preparations that contain inorganic pigments to impart a tan color. Another type of bronzing gel is based on dihydroxyacetone, a colorless chemical that stains the skin temporarily. All of these preparations must contain effective sunscreens. Few of these are recommended in the text, although many others would be equally effective. Examples of Trade Formulations From Manufacturer’s Product Label

Coppertone.

Suntan cream lotion, Plough, Inc

Active ingredient: Homosalate 8% (1) Other ingredients:

Water Propylene glycol Glyceryl stearate Cocoa butter Remarks: (1) Trimethyl salicylate

cyclohexanol

Stearic acid Triethanolamine Fragrance Methyl paraben salicylate,

sometimes

called homomenthyl

Suntanning preparations Bain de Soleil. Charles of the Ritz. A petrolatum suntan gelée Active ingredient: Padimate (1) Other ingredients: Mineral oil Petrolatum Paraffin Ozokerite Isopropyl myristate Remark:

Fragrance Propyl paraben Butyl paraben D&C Red No. 17 D&C Yellow No. 11

(1) Amyl dimethyl PABA, Escalol 506, Van Dyk Coppertone,

Tanning Oil.

Plough, Inc

Active ingredient: Homosalate Other ingredients: Mineral oil Lanolin Cocoa butter

Fragrance Propylparaben

Bain de Soleil. Suntan lotion, Charles of the Ritz. Active ingredients: Padimate O (1)

A cream lotion

Oxybenzone

Other ingredients: Water Mineral oil Glycerin Oleth-3 (2) Polyethylene (3) Polyglyceryl-4-oleate (4)

Polysorbate-80 (5) Methylparaben Quaternium-15 (6) Propylparaben Propyl gallate (7)

Citric acid

Remarks:

(1) (2) (3) (4) (5) (6) (7)

Padimate O is Octyl dimethyl PABA e.g. Volpo 3, Croda A hydrocarbon, e.g. Epolene, Eastman Chemical Witconol 14, Witco Chemical Tween 80, ICI Dowicil 200, Dow Chemical Tenox PG, Eastman Chemical

215

216

Suntanning preparations

Bain de Soleil, Suntan Oil. Charles of the Ritz Active ingredient: Padimate O (1)

Other ingredients: Mineral oil Sesame oil Isopropyl myristate Sorbitan oleate (2) Fragrance Propylparaben

Propylene glycol BHA Propyl gallate (3) Citric acid D&C Red No. 17

Remarks: (1) Octyl dimethyl! PABA . (2) Sorbitan trioleate, Arlacel 85, ICI (3) Tenox PG, Eastman Chemical Bain de Soleil, Suntan Cream.

Charles of the Ritz.

A non-greasy cream

Active ingredient: Padimate O (1)

Other ingredients: Water PEG-2 stearate (2) Glycerin Glyceryl stearate SE (3) Cetyl alcohol Cetyl palmitate (4) Dimethicone (5) Fragrance Carbomer-934 Imidazolidinyl urea

Potassium sorbate Methylparaben Sodium hydroxide (6) Propylparaben Mineral oil Lanolin Paraffin Lanolin aicohol Beeswax

Remarks: (1) (2) (3) (4) (5) (6)

Octyl dimethyl PABA Diethylene glycol stearate Self-emulsifying, e.g. Tegin, Inolex e.g. Kessco 653, Stepan, Kessco Div. e.g. Dow Corning 200 Fluid, Dow Corning For neutralizing carbomer-934

Suntanning preparations

217

Formulations Aerosol Tanning Oil Standard

Ref 206 19 Bes 20

Cocoa butter Cinnoxate (1)

5 75 80

Homosalate (2) Vegetable oil 1400 (3) T 100

(1) CTFA name for Giv Tan F, Givaudan (2) CTFA name for trimethyl cyclohexanol salicylate. Originally developed by Union Carbide as a substitute for menthyl salicylate. (3) Modified coconut oil, VPO

Simple mixing. Pressurize with 30% by vol, Freon 114/12, 65/35. Clear Suntan Lotion

Ref 207

13 13 49 75

TEA salicylate (1) Isopropanol Water

25 0.1 0.2

Propylene glycol Caramel color 10% Perfume

25.3

T 100.3

(1) 70% active. Should contain 15% propylene glycol and 15% water as solubilizer. A non-greasy lotion for the face. Suntan Cream Lotion No. 1 Heavy Consistency for Squeeze Bottle Standard

Ref 208

A

2

Oleth-20 (1) Laneth-16 (2) Stearic acid Cocoa butter GMS Homosalate (3) Petrolatum, white USP

Bez

C

3 1 0.1 0.5

76.6

Ga ey Pee Aye

(1) Brij 99, ICI (2) Solulan 16, Amerchol (3) See Ref 206

Mix A and B at 75°C. Stir until cold.

Water Propylene glycol TEA Methylparaben Perfume

T 100.6

218

Suntanning preparations Suntan Cream Lotion No. 2

Liquid Ref 209 A 2 1 4.5 7 1 4

19.5

Oleth-20 (1) Laneth-16 (2) Petrolatum, white USP Mineral oil, visc. 70 Cetyl alcohol GMS

A

5 1 B m3 715° 0.2 0.3

81

Homosalate (3) Cinnoxate (3) Propylene glycol Water Germall 115 Parabens

71 100.5

(1) Brij 99, ICI (2) Solulan 16, Amerchol (3) See Ref 206 Mix A and B at 75°C. Stir until cold. Lotion thickens at 38°C. Suntan Cream No. 1A Anionic Formulation

Ref 210A A

1 2 3 is A=

laneth-16 (1) Arlacel 165 (2) Mineral oil, visc. 70 GMS

A

2 1.5

Bae

0.1 72.5

13

Tiler

Stearic acid Cinnoxate (3) TEA Methylparaben Water

GOR

(1) Solulan 16, Amerchol (2) ICI (3) Giv Tan F, Givaudan

Mix A and B at 75°C. Stir to 35°C. Cream thickens overnight. Fill cold. Suntan Cream No. 1B Alternate Formula

Ref 210B A

1 1 6 1.5 2.5 BA

13

Laneth-16 (1) Ceteth-20 (2) GMS Cinnoxate Mineral oil Silicone L-45

A>

2 2 Z

Bei 3 dis

37.

Cetyl alcohol Stearyl alcohol Stearic acid TBA Propylene glycol Water

eb te

(1) Solulan 16, Amerchol (2) Brij 58, ICI Mix A and B at 75°C. Cream thickens at 43°C. Fill cold.

Suntanning preparations

219

Suntan Cream No. 2 A Water Repellent Vanishing Cream Stearic acid Spermaceti Silicone L-45 (1) Cinnoxate (2) Water

B 5 13 0.5 0.1 Cua

Glycerin Borax Methylparaben Perfume

Toh acs Th 10056 (1) 1000 cstk, Union Carbide (2) Giv Tan F, Givaudan Mix A and B at 75°C. Fill cold.

Ref 212 A 79 13 Be 0.2 94.2

Suntan Gel No. 1 Clear Gel for Tube Packaging Carbopol 940, 1% (1) TEA salicylate (2) Igepal CO-730

Perfume

B 5 0.2 C 0.8

Propylene glycol Dowicil 200 (3) TEA 10%

es, 6

T 100.2

(1) Goodrich Chemical (2) See Ref 207 (3) Dow Chemical Add B to A. Add C last. A non-greasy gel for the face and all-over tanning. Reapply after swimming. This gel can be medicated with resorcinol, allantoin, acetyl methionine and allantoin panthenol.

Ref 213 0.1 0.4 1 45 46.5

Suntan Gel No. 2 Clear Alcoholic Gel

Perfume Igepal CO-730 Cinnoxate (1) ml Alcohol 95% vol

(1) Giv Tan F, Givaudan Mix in the order shown.

0.05 0.05 50 5

FD&C Blue No. 1, 1% FD&C Yellow No. 1, 1% Carbopol 940, 1% TEA 10%

Salk

—b01.6

220

Suntanning preparations Suntan Gel No. 3

Opaque Alcoholic Gel

41 50 5

Perfume Cinnoxate (1) Isopropyl myristate Igepal CO-730

96

ml Alcohol 95% vol Carbopol 940, 1% TEA 10% Color T 10171

(1) Giv Tan F, Givaudan Mix in the order shown.

Bronzing Gel No. Clear, Staining

40 5 a 50

Perfume Igepal CO-730 Carbopol 940, 1%

ml Alcohol 95% vol Dihydroxyacetone (1) TEA 10% soln T 101.8

(1) Wallerstein Co., Morton Grove, Illinois

Mix in the order shown. This preparation gels slowly after the addition of triethanolamine. Imparts a brown stain to the skin. Bronzing Gel No. 2 Make-up Suntan Shade

Ref 216 A 8 8 0.1 B 0.1 0.1

Oleth-20 (1) Laneth-16 (2) Perfume Dowicil 200 (3) Brilliant gold pigment (4) 0

16.3 (1) (2) (3) (4)

Propylene glycol Water Carbopol 940, 2% FD&C chocolate color, 1% TEA THOist

90PLO Oo oo} Brij 99, ICI Solulan 16, Amerchol Dow Chemicai Timica pigment, The Mearl Corporation

Melt A to 50°C. Add B and C. Stir until uniform. Add D.

Suntanning preparations Suntan Oil

Ref 217 Homosalate (1) Cinnoxate (2) Isopropyl myristate

50 0.25 50.25

Mineral oil, visc. 70 Perfume T 100.25

(1) See Ref 206 (2) Giv Tan F, Givaudan

Simple mixing.

Ref 218 A 12 32 55 99

Protective Sun Balm Pomade

Ozokerite No. 4 Petrolatum, white USP Mineral oil, visc. 70

B

1

Cinnoxate (1)

0.5 ya” 1.5

Perfume

T 100.5

(1) Giv Tan F, Givaudan Melt waxes A. Lower temperature and add B. Set Pt 48°C.

221

222

Miscellaneous cosmetics

20. MISCELLANEOUS COSMETICS This small group consists of the following cosmetics: Astringent lotions. Ref 221 and 222 Beauty mask. Ref 223 Cuticle remover. Ref 224 Make-up remover. Ref 225 Nail buffing polish. Ref 226 Nail enamel removers. Ref 227 and 228 Peel-off mask. Ref 229 Skin bleach cream (hydroquinone). Ref 230 Skin freshener (non-alcoholic). Ref-231 Wrinkle smoother. Ref 232 Nail enamel is not listed in this series. Actually these enamels are manufactured by the lacquer and varnish industry. Readers interested in this phase of cosmetic formulations should consult the work of J.J. Matiello, Protective and Decorative Coatings, vol. I to V, Editor John Wiley, New York, 1943. Little need be said about the various formulations. Skin bleaches based on hydroquinone are presently much advertised. Cream Ref 230 appears to be effective in the case of melanine skin spots which are not over-pigmented. Although this claim is supported for hydroquinone creams in the literature, these preparations should be discontinued if satisfactory results are not visible after daily applications over a period of two months. The formulation of these creams presents some problems as hydroquinone causes product discolorations. Furthermore, acid stable emulsions are required since hydroquinone has a pH of 3.5 in 2% aqueous solution. It was found that addition of ascorbic acid prevents the formation of the brown discoloration that is commonly observed. A white cream of excellent consistency is obtained by means of formula Ref 230. The emulsifiers are Ceteth-20 and Sodium laureth-2 sulfate, a highly efficient combination. This cream should preferably be packaged in tubes to avoid contaminations. Wrinkle smoothers have also been much advertised recently. The active ingredient in these products is sodium silicate in the presence of magnesium aluminum silicate. Since these preparations are highly alkaline (pH = 12), their safety can be questioned although one well-known brand reports 50% favorable acceptance in a consumers testing program. An example of a formulation of this type is shown under Ref 232 which is given for information only. Since it is known that exposure to the sun is a cause of wrinkles, it may be best to simply use a sunscreen cream for the outdoors. Maybelline Moisture Whip Cream makes such a claim.

Miscellaneous cosmetics

223

Examples of Trade Formulations From Manufacturer’s Product Label Line

Tamer.

Temporary

wrinkle

smoother,

Line Tamer,

Inc, Miami,

Florida Ingredients: Water

Sodium silicate Magnesium, Aluminum silicate

Caution:

Propylene glycol Cellulose gum D&C Red No. 19

Do not use near the eye. Caustic.

Avon Nail Enamel.

Non-settling formula.

Ingredients: Butyl acetate Toluene Nitrocellulose Isopropyl alcohol Toluene-sulfonamide Formaldehyde resin (1)

Ethyl acetate Dibutyl phthalate Camphor Stearalkonium hectorite (2) UV Absorber-1! (3)

May contain: Bismuth oxychloride (4) Titanium oxide Mica D&C Red No. 6, Barium lake D&C Red No. 7, Calcium lake D&C Yellow No. 5, Zirconium lake

D&C Violet No. 2 D&C Red No. 19 Iron oxides Chromium hydroxide green Ferric ammonium ferrocyanide

Remarks:

(1) Blender beads to keep preparation fluid (2) Reaction product of a bentonite-like clay with stearalkonium chloride

(3) Tinuvin P, Ciba-Geigy (4) Nacreous pigment Revilon’s Super Clean-up.

Astringent cleanser. A clear lotion

Ingredients: Isopropyl alcohol (1) Water Witch hazel Rose water Lemon juice Propylene glycol Lemon oil

Fragrance Alcloxa (2) FD&C Red No. 4 FD&C Yellow No. 5 FD&C Blue No. 1 D&C Red No. 33

Remarks:

(1) About 60% by weight (2) Aluminum chlorhydroxy allantoinate

224

Miscellaneous cosmetics

Porcelana medicated skin cream.

Jeffry Martin, Dist., Union, N.J.

Active ingredient: Hydroquinone 2%

Also contains: Purified water Myristyl myristate PEG-8 glyceryl monostearate Cetyl alcohol Magnesium aluminum silicate (1) Dioctyl sodium sulfosuccinate (2) Dimethicone (3)

Choleth-24 (4) Fragrance Locust bean gum Sodium sulfite Citric acid Sodium bisulfite Sorbic acid

Remarks:

(1) Veegum, Vanderbilt Co. (2) e.g. Aerosol OT, or OT-100, American Cyanamid; MO-70, Mona Industries (3) e.g. Dow Corning 200 Fluid, Dow Corning (4) PEG-24 cholesteryl ether, Solulan-24, Amerchol Esoterica medicated cream.

or Monawet

Norcliff Thayer, Dist., Tuckahoe, N.Y.

Active ingredient: Hydroquinone

Also contains: Water Glyceryl stearate Isopropyl palmitate Propylene glycol Mineral oil Lanolin oil Stearyl alcohol Steareth-20 Oleyl alcohol Laureth-23

Dimethicone (1) Allantoin ascorbate (2) Sodium lauryl sulfate Fragrance Magnesium aluminum silicate (3) Sodium bisulfite Methylparaben Propylparaben Trisodium EDTA BHA (4)

Remarks:

(1) (2) (3) (4)

e.g. Dow Schuykill Veegum, Butylated

Corning 200 Fluid, Dow Corning Chemical Co. Vanderbilt Co. hydroxyanisole, e.g. Tenox BHA, Eastman

Miscellaneous cosmetics

Nudit, Gentle skin lightener with sunscreen.

i)io)

Helena Rubinstein

Active ingredients: Hydroquinone

Octyl dimethyl PABA (1)

Also contains: Water

Imidazolidinyl urea Sodium sulfite Fragrance Sodium metabisulfite Methylparaben Sodium EDTA Citric acid BHA

Mineral oil Propylene glycol Cetyl alcohol Stearic acid Ceteth-2 (2) PEG-40 stearate (3) Magnesium aluminum silicate Hydroxymethy] cellulose

Remarks: (1) Octyl dimethyl p-aminobenzoate (2) Brij 52, ICI (3) Myrj 52, ICI, R.COO (CH2CH20)4oH, R.CO is the stearoyl radical Bio-Clear, Helena under make-up”

Rubinstein.

“Fresh

smelling medicated

Ingredients: Water Propylene glycol

S D Alcohol 40 Hydrated silica (1) Hydroxyethyl cellulose Hectorite (2) Imidazolidinyl urea Remarks: (1) e.g. Cab-o-Sil (2) Bentonite

M 5, Cabot Corp.

Methylparaben Allantoin Fragrance Camphor Menthol FD&C Blue No. |

gel to wear

226

Miscellaneous cosmetics

Aloe Skin Freshener.

Aloe Charm, Inc, Dist.

Ingredients: Benzophenone-9 Polysorbate-20 Vitamin E Hydrolyzed animal protein Citric acid Camphor FD&C Yellow No. 5 D&C Red No. 33

Water Aloe Witch h azel

Glycerin Propylene glycol Sorbitol

Imidazolidinyl urea Methylparaben Formulations

Astringent Lotion No. 1

Ref 221 50 50 0.3.

ml Alcohol SD 40 Water Zinc sulfocarbolate NF

0.1

0.05

mere

0.5

100.3

0.65

FD&C Yellow No. 5, 0.1% aq. soln. FD&C Blue No. 1, 0.1% aq. soln. Perfume Ref 318

T 100.95

Astringent Lotion No. 2

Ref 222 60 30 90

g Alcohol SD 40 Water

10 pel 11

Propylene glycol Witch hazel extract (1) T 101

(1) Leaf extract, 70% alcohol content, Meer Corp. Bentonite Beauty Mask

Ref 223 A 60 15 1 0.1. B 0.5 _0.5

Water Alcohol SD 40 Laneth-16 (1) Dowicil 200 (2) Perfume Igepal CO-730 (3)

Gor

3 0.1 D 13

TTA

231) (1) Solulan 16, Amerchol

(2) Dow Chemical (3) GAF Corp. (4) Whittaker, Clark & Daniels

Talc Titanium dioxide Red oxide A 6205 Bentonite 660 (4)

Tsl002

Miscellaneous cosmetics

227

Prepare solution A in a pony mixer. Add solubilized perfume B and pulverized pigments C. Add bentonite D gradually while mixing. Control the viscosity of the cream by adjusting the percentage of bentonite. Beauty masks based on bentonite are prone to bacterial decomposition. An effective preservative in addition to alcohol is therefore essential. Water soluble colors cannot be used since they bleed and distract from the good appearance of the cream. Cuticle Remover (Cream)

Ref 224 A «3

Clty tow

Cetyl alcohol Stearyl alcohol Petrolatum, white USP Mineral oil, visc. 70 Ceteth-10 (1)

B

1.5 i

Sodium hydroxide, pellets Standapol WAQ Special (2) 76.5 Water _0.1 Methylparaben 85. boove Fl O01

(1) Brij 56, ICI (2) Henkel

Mix A and B at 75°C. Stir until cold. Fill cold. Application time is 3 minutes. Sodium hydroxide can be reduced to 1%, or also 0.5%; this increases the application time to 5 or 10 minutes, respectively. Make-up Remover Isopropanol Carbitol (1) Acetone Menthol Water

(1) Union Carbide

Nail Buffing Polish Talc Zinc oxide Zinc stearate Rose 20 Pigments to tint

Same procedure as for face powder.

228

Miscellaneous cosmetics Nail Enamel Remover “Extra Gentle”

Ref 227

a =

Methyl carbitol (1) Castor oil

(1) Ethylene glycol monoethyl ether, Union Carbide This formula conforms to the label declaration of a well-known product. Whether methyl carbitol can be safely recommended should be further investigated. Nail Enamel Remover Standard Acetone

PEG 15 tallow polyamine (1) Water Perfume D&C Yellow No. 11

(1) Polyquart H, Henkel

Ref 229 12 48 38.5 98.5

Peel-off Mask Vinol 523 (1) Water g Alcohol SD 40

1 0.5

Propylene glycol Witch hazel extract (2)

135

T 100

(1) Partially hydrolyzed polyvinyl alcohol, Air Products Co., Allentown, Pa. (2) Fluid extract from witch hazel leaves, 78% alcohol content, Meer Corp.

Directions for use: Apply with a wide brush. Let dry completely before removing.

Miscellaneous cosmetics

229

Skin Bleach Cream Active Ingredients: Hydroquinone, Cinoxate Ref 230 >

Ceteth-20 (1) Cetyl alcohol Stearyl alcohol GMS Petrolatum, white USP Mineral oil, visc. 70 Cinnoxate (2)

B 66 0.5 2 3 Zz 0.2 C 0.3.

74

| 4—NY Aimee FRNN

Water Sodium bisulfite Hydroquinone NF Propylene glycol Na laureth-2 sulfate (3) Ascorbic acid Perfume

717100

(1) Brij 58, ICI (2) Sunscreen Giv Tan F, Givaudan (3) Standapol ES-2, Henkel. pH should be 4.0 Mix A and Bat 75°C. Part B should be mixed in the order shown to prevent darkening of the solution. Cream thickens at 45°C, the temperature at which it should be homogenized. Set Pt 38°C. pH = 4, Can be filled hot or cold.

Ref 231 A 90

Aloe Skin Freshener. Clear Lotion

Water Germall Aloe powder (1) Citric acid

B

C

10 0.1 0.2 0.4

Propylene glycol Methylparaben Igepal CO-730 (2) Witch hazel extract (3) D&C Yellow No. 10, 1% Tu tOL25

0.05 ID.J5, (1) Dr. Madis Laboratories, Hackensack, N.J. (2) Nonoxynol-15, GAF Corp. (3) Alcohol extract, Meer Corp.

Dissolve items A in the water. Prepare B, heating slightly to solubilize witch hazel extract. Add to A. Let stand overnight. Filter. Rubout of this lotion is dry due to the presence of propylene glycol.

230

Miscellaneous cosmetics

Wrinkle Smoother Cream Consistency for Tube Packaging Methylparaben Laneth-16 (1) Propylene glycol Water, cold D&C Red No. 19, 1%

(1) (2) (3) (4)

C D

1.5 1.5

Sodium silicate (2) Magnesium aluminum silicate (3) E 2.5 Propylene glycol 20 Water _1_ _—_—Hydroxyethyl cellulose (4) 26.5 T 100.25

Solulan 16, Amerchol Silicate SS-C 200, powdered, Pennsylvania Quartz Co. Veegum, Vanderbilt Co. Cellosize QP 52000, Union Carbide

Heat A slightly to melt wax and dissolve methylparaben. Add B and C. Add D slowly under good agitation. Stir for 10 minutes until the preparation is viscous. Directions for use: Apply sparingly, avoid contact with eyes. The pH of the cream is 11.8 when prepared with the above mentioned sodium silicate. This finely powdered silicate is 98% active and has a SiO2/Na.0 ratio of 2.0. Some manufacturers prefer using Silicate N of the same supplier. This silicate is a syrupy liquid, 37% active, and has a SiO2/Na2O ratio of 3.2. However, this silicate did not give a better cream or a lower pH. In fact, the pH was slightly higher.

Acute toxicological tests for this gel should be determined. This includes primary dermal irritation and primary occular irritation (Draize test). A repeat insult patch test is also advisable.

Chapter II Physical Aspects of Odor A few years ago the author showed that several factors related to odor can be measured with some accuracy.! This is of course a prerequisite if we wish to establish a physical foundation in odor theory. The questions examined deal with volatility and vapor pressure, odor intensity, minimum perceptible and other related subjects. Some of the findings that are basic for perfume development will be reviewed in this chapter.

1. VOLATILITY AND VAPOR PRESSURE An approximate measurement of volatility of the aromatic products is quite simple. Perfumers have always evaluated tenacity, rather than volatility, by placing a few drops of the aromatic material on a small strip of paper kept

under observation until the odor slowly fades. The tenacity is estimated in hours at poorly defined end points. This test can be easily improved. All that is necessary is to record evaporation rates of 1 gram of aromatic oil spread on a blotter of thin filter paper 5 x 25 cm weighing approximately 1 gram. The oil should be evenly distributed drop by drop on the filter paper by means of an eye dropper. Crystalline material must be first dissolved in a volatile solvent, preferably alcohol 100% by vol. These strips are kept at constant temperature (25°C) in a spacious room and weighed at suitable time intervals. Evaporation is reported in milligrams per hour. This test should be run simultaneously with a blotter impregnated with | gram of benzyl acetate. Under proper air conditioning this parallel blotter shows an evaporation rate of 125 mg/hr, i.e. the same value as the vapor pressure of benzyl acetate at 25°C reported in microns. In other words, under these conditions the initial evaporation rates and the vapor pressures are numerically the same. If the blotter with benzyl acetate shows an evaporation rate higher than 125 mg/hr, this indicates excessive air displacement and the evaporation rates must be reduced proportionally for correlation with vapor pressure. Example Determine the approximate vapor pressures of ethyl benzoate and ethyl salicylate, knowing that the following constant evaporation rates were observed on blotters 5 x 25 cm under the experimental conditions:

For ethyl benzoate: For ethyl salicylate: For benzyl acetate:

300 mg per hour at 25°C 100 mg per hour at 25°C 200 mg per hour at 25°C

'Louis Appell, Physical Foundations in. Perfumery, Reprint of 10 articles, American Perfumer,

77 p (1970).

232

Physical aspects of odor

Since the vapor pressure of benzyl acetate is 125 microns at 25°C, the corrected vapor pressures are obtained by multiplying the evaporation rates with the factor 125/200. This gives: For ethyl benzoate: For ethyl salicylate:

300 x 125/200 100 x 125/200

187 microns 82 microns

These pressures are in acceptable agreement with more accurate methods of measurement which will be described in the next chapter. Several remarks should be made about this test: 1. The weight of the filter paper and the weight of the oil (both | g) are not critical since the evaporation rates do not depend on these factors. However, these weights should be observed as closely as possible. The size of the blotter is of course essential for correlating the evaporation rates to the vapor pressures. 2. The evaporation rates increase rapidly with the temperature. Actually the controlling factor is vapor pressure which varies with temperature, roughly doubling for every 10°C increase. 3. The proper air conditioning is of importance, as any variation in the volume displacement of air greatly affects the evaporation rates. If there is no removal of vapor — for instance by sealing the blotter in a cylinder —evaporation does not take place. This fact can be put to use for interrrupting the test overnight. Resuming the test the following day, the maximum rate of the previous day is frequently observed since internal diffusion formed a new free surface of evaporation. 4. Exposing the blotters to a stream of nitrogen increases the evaporation rates considerably. The increase is maximum when the jet of nitrogen is directed perpendicular to the surface of the blotter. 5. Exposing the blotters in a cylinder under vacuum causes a relatively minor increase in the evaporation rates since the removal of vapors is slow. As can be seen from these preliminary findings, the evaporation process is of considerable complexity. Essentially, however, the volatilization depends on three main factors: Vapor pressure of the aromatic Speed of removal of the vapors Speed at which the free surface ternal diffusion of the aromatic evaporation.

chemical at a given temperature. at the surface of evaporation. of evaporation is replenished through insubstance. This factor often controls the

Two modes of evaporation can be observed for the aromatic chemicals. Initially, a constant rate of evaporation is noted which continues as long as sufficient liquid diffuses to the surface. This is followed by a second mode, namely evaporation at a decreasing or falling rate when the internal diffusion of the aromatic is slower than the rate of evaporation. Of these two modes, only the

Physical aspects of odor

233

constant rate is of interest since it is directly related to the vapor pressure. Furthermore, it can be observed that the more volatile aromatics with vapor pressures higher than 70 microns nearly completely evaporate at a constant rate, whereas those below 60 microns evaporate at a falling rate which sets in rather soon after starting the test. In order to minimize these various perturbing factors, the author has devised a special evaporometer that accelerates the evaporation under controlled conditions of reduced pressure and simultaneous vapor removal. The apparatus consists of an evaporation chamber formed by two large tubulated desicator covers set back to back. This chamber is connected to a pressure regulating vacuum system, preferably a Cartesian manostat and a Zimmerly or Dubrovin vacuum gauge. A small disk of filter paper is saturated with the sample and placed centrally. Vacuum is maintained in the chamber at about 13 mm Hg. At the same time a cone of nitrogen is bled into the system through a 2-ml pipette tip centered perpendicularly to the filter disk. This disk should be set entirely within the cone of nitrogen that emerges from the pipette tip, since the stream of gas increases the evaporation rate to a considerable extent. This apparatus cannot be used for substances with vapor pressures above 1 mm Hg because of the rapidity of the evaporation and the accompanying cooling effect. The method is also not suitable, for aromatics of less than 20 microns vapor pressure. Data obtained must be correlated to the evaporation rates of benzyl acetate under similar conditions in order to obtain the vapor pressures at 25°C. The determination is particularly useful when boiling points under reduced pressure are not available, or in the case of mixtures such as the essential oils. {TO MANOSTAT TO

VACUUM

—_—

Evaporometer. Filter disk D is hooked to spiral microscale S to follow the evaporation without dismantling the apparatus. A remote controlled arresting system stabilizes the scale during operation. This construction allows a rapid determination of vapor pressure and volatility index under controlled conditions of temperature, air displacement and vacuum.

234

Physical aspects of odor

Volatility of the Essential Oils

The evaporation and fractionation of mixtures is a subject taken up in physical chemistry. For our part, we are mostly interested in the initial volatil- ity of the essential oils. More precisely, we shall define the volatility index of an oil as the quantity in milligrams evaporated in the first hour in the blotter test. This is a measure of volatility. For instance, oil of bergamot has an index of 450, oil of cloves an index of 20. These indices are the counterpart of the vapor pressures ‘of the aromatic chemicals and will find the same use in practical perfumery.

2. PHYSICAL LAWS IN ODORIMETRY The question of vapor pressure of the aromatic chemicals has been dealt with in considerable detail in Physical Foundations in Perfumery. The precise measurement of these pressures at 25°C is difficult because of the small pressures involved. As is well-known, a practical unit of pressure is the torr (named after Torricelli), the pressure of a column of 1 mm of mercury (Hg) at 0°C. A smaller unit, the micron (), is more convenient in odorimetry. This unit is 107° torr, or 0.001 mm Hg. It is equivalent to 1.36 mg-force per sq. cm which perhaps gives a better representation of the order of magnitude. Most aromatic chemicals fall in the vapor pressure range of | to 1000 microns (0.001 mm to 1 mm Hg) at a temperature of 25°C. Aromatics having pressures above I mm are extremely volatile. For example, limonene (vapor pressure of 1.4mm Hg) evaporates at a rate of 1.4 gram per hour in the blotter test. Several simpie laws of physical chemistry should now be reviewed and adapted to odorimetry. Ideal Gas Law (Gay-Lussac 1805)

The ideal gas law, as is well-known, is closely obeyed at low gas pressures. This is particularly the case of rarefied gases or the vapors of the aromatics at room temperature. The law states that

pv = nRT where p is the pressure in atmosphere, v the volume in cc, n the number of moles (n = m/M, M molecular weight, m mass in gram), R the gas constant, and T the absolute temperature defined as T = 273 + t °C. With these units the gas constant R has the value 82.057. For our purpose, smaller units must be chosen with the pressure p expressed in microns and the mass m in microgram (1 microgram = 0.001 mg, a unit often called Gamma), the other units remaining the same as above. With the new units, the gas constant R has the value 62.3, and the ideal gas law is again written

Physical aspects of odor pe

m mR

235 (1)

where the gas mass m is in microgram, and M is the molecular weight. Example: Determine the weight of 1 cc of saturated vapor of benzyl acetate at 27°C, knowing that the vapor pressure at this temperature is 125 micron. The absolute temperature is T = 273 + 27 = 300°K (degree Kelvin), the molecular weight of benzyl acetate is M = 150. Replacing these values in Equation (1), we obtain m = | microgram per cc. This result gives a good representation of the order of magnitude in odorimetry.

Raoult’s Law (1886)

Raoult’s law gives the partial vapor pressure p of a volatile material in solution in a solvent, knowing its concentration c and the vapor pressure P of the material as a 100% substance. Raoult’s law is widely used in physical chemistry although it is assumed valid only for ideal solutions for which the escaping tendency of each component is proportional to the mole fraction in the solution. It is usually formulated as follows: p = XP

where X is the ratio of moles X, of the solute to moles X, + X, of combined solute and solvent. For solutions of aromatics in a solvent a simple calculation shows that this equation takes the form

) He

70

Butter Flavor No. 1

25 Va 5 Et Va

530

20

350 Water

PG

560

350 T 1000

(1) Givaudan Co. 378

IDA 5 Et Bu 6

Butter Flavor No. 2

3 Bu Acid 2 Co sub 5

4 Va 400 P G Bu (1) 404

585 Corn oil

585 T 1000

(1) Propylene glycol butyrate (di-isobutyrate) 379

20 DA 7 Am Ac 10% 5 Am Bu 10% _5 Am Val 10% 37

1 2 10 150 163

Butter Scotch

Et PhAc Birch 10% (1) Et Va Melilot Tr (2)

300 380 100 _20 800

Van flavor Fng Tr PG Et Alc T 1000

(1) Crude Birch Tar oil 10% (2) Or substitute

380

20 Et Bu 50 Et Val 10% _30 Bu Acid 100 Dilution: 10% in

Caramel Artificial

100 Cognac oil 100 Co sub 200 EMPG 400

200 NoLac 200 Va

100 PG 500 T 1000

PG

5. VANILLA-TYPE FLAVORS 381

260 Rum Ether 20 Et Bu

50 Mace 10%

330

Custard Artificial

20 Lem 2 Org tpl

70 Co sub 560 Va

10 Cognac oil

__8 Rose

32

638 T 1000

Dilution: About 15% in alcohol. Add color 382

300 Crb Tr 30 SgC Tr 12 Lvg Tr

342

1 Et PhAc 10% 6 Fng res

Maple Flavor

15 Co sub 10% 4 Va

2 Ethone 10% (1) 100 Nulomoline (2)

9

(1) Givaudan Co. (2) Invert sugar (Sucrest Corporation)

119

30 Caramel color 500 Water

530 T 1000

345

346

The formulation of flavors

383

Vanilla Flavor No. 1 10 Fold

250 Vanilla oleoresin

640 Vanilla extract

10 Vanillin 100 Glycerin

384

Vanilla Flavor No. 2

20 Fold 5 Heliotropin 25 70 30 770

Coumarin substitute Vanillin Vanilla oleoresin Ethyl alcohol 95% vol

100 Water 1000

6. FLAVORS FOR ALCOHOLIC BEVERAGES 385

20 10 20 _50 100

A 10% Rum Ether Et Ac Fusel oil

Imitation

Whisky

10 Et Lat 45 Fr Ald 30 Fr Alc

2 Creosote 5% 10 Cay 10% 8 Ani 1%

_15 Bu Lat

280 Cider vinegar

100

300

150 Wood extract 200 Crb Tr

150

PG

500 T 1000

This flavor must be heated 36 hrs at 65°C under reflux. Use 2.5 ml for 100 ml Alcohol 50%

by vol. 386 100 Rum Ether

170 Et Ac = /2Cini 277

Imitation Cognac

7 Ci 3 Cin Ald 500 Et Decylate 510

3 Gin olr 7 Cad 10% 100 Mal 1% 110 387

720

100 Et Pr

30

_20 Et Hp

10 Et Pel

400 Crb Tr

120

40

402

150 Lem 240 Org 75 Wormwood

2 Ang 15 SgD 10% 7 Hys

4 Mnt 15 Thy 10%

300 Cognac oil

_2 Com

_4 Melissa

765

26

25

450 Et Pr

110 Mal 1% 130 Va __7 Gin olr 247 388

Am Hx

7 Cad 10%

7 T 1000

Imitation Sherry

2 DM Ant 10%

389

103 T 1000

Imitation Rum

Cine 7c 12 Cin Ald 6

100 Rum Ether 170 Et Ac

3 NoLac 100 Va

438 PG

438 T 1000

Imitation Benedictine

2 Ner

25CiniG 4 Clo 163 Et Alc 95% vol _15 Rose flavor 184 T 1000

The formulation of flavors

7. FLAVORS FOR TOBACCO 390

10 10 10 30

Rum Ether Cel Ori crt 10%

Tobacco Flavor No. 1

10 Lvg Tr 10% 20 Mal

20 Va 360 Fng res 10% in

20 Co 50

540 PG 920 T 1000

391

100 50 100 250

Tobacco Flavor No. 2

Rum imitation 250 Maple 7 fold Coumarin subst 100 Vanilla extract

150 Water

Maple imitation 250 Glycerin

600

150 T 1000

8. MISCELLANEOUS 392 Mnt

Ald C 10,10% _5MNA 10% 10

FLAVOR COMPOUNDS Confectionary Rose Flavor

30 Ger

30 Eu

150 PhEt Alc _70 Pal 250

30 PhEt i-Bu 650 PG 710 T 1000 393

30 30 30 90

PG

Org Mar Lem Cel 10% Cel olr

15 Nut

35 SgD 150 Dil 35 ist

Salad Flavor

DOCK

5 Gin 10 Gin olr 10 Bay

15 Ani

10 Pim 100 Clo 325 Corn oil

_20 Thy

20 Cin C sub

—

255

70

450 T 1000

Dilution: 10% in Corn oil

347

348

The formulation of flavors

9. MEAT FLAVORS 394

Meat Sauce, Type A I Sauce Concentrate

Mix 1 450

Ingredients 4 Caramel color

Soy sauce Vinegar Mix 2 Water, hot Beef extract Gelatin Mix 3

Black strap molasses

Tabasco sauce Salt Powdered spices 5 Crb Tr Sodium benzoate

Water, hot Tamarinds

T 1000 Finished sauce Concentrate Ref 394 Vinegar Water

Powdered spices 5 Onion Garlic Chile Paprika Cloves Lovage roots Allspice Mace

Prepare separately mixtures 1, 2 and 3. Blend these mixtures and add ingredients 4 in the order shown. Mix for two hours and strain through coarse wire mesh. Finished sauce is blended separately. 395

Meat Flavor

Concentrate 90° Diastatic Malt syrup Hydrolyzed Vegetable protein Powdered onion, dehydrated Powdered garlic, dehydrated Powdered chile Powdered lovage roots

Zz 1 50 1 216

Powdered cloves Powdered pepper Vinegar, 4% acetic acid Sodium benzoate Water

T 1000

The formulation of flavors

10.

349

FRUIT FLAVORS FOR COSMETICS

The regular food flavors cannot tile materials are dosified as trace flavor practice. The formulas that Furthermore, the ingredients need 401 2 Am Ac

2 PhEt Ac

5 Bz Ald

25 PhEt Alc

2 AcPh

10 Lin Ac 1

the highly volacase in present these elements. (GRAS).

Apricot Fragrance 25 Hy

25 Bz Sal

7 NoLac 100%

50 Ben 50%

235 UnLac

u2 Co 79

_10 Am Cin Ald 277 402

100 Bz Ald 50 An Ald

be used in cosmetics unless elements which is not the are given here are free of not be approved for food

50 An Ac 50 Me Cin

600 PG

100%

_— 625 T 1000

Cherry Fragrance

50 Am Sal 50 EMP G 100%

$0 UnLac 10% 20 Va

_50 Cin Ald

_50 Me Io

_50 Bz Cin

430 DEP

200

150

150

500 T 1000

403

Coconut Fragrance

50 No Ac 10% Smo 100 NoLac 100% 845 DEP 1000 404

200 Lm 100 Brg _40 Tl Ac 340

Lemon Fragrance No. 1

50 PhEt Alc 75eGi _40 Tl 165

40 An Ald 250 Gl _10 Co 300

405

250 Lm __5 Ald C 8,10% 255

5 100 B90 195

He Rose W DIB b T 1000

Lemon Fragrance No. 2

5 Ald C 9,10% 50 Bz Ac 55 406

150 Lem 10 Org 300 Lim dist 460

130 Lm 50 Brg No. 1 _20 Ptg 200

10 Melonal 10% 50 Ald C 8,10% 60

10MHC10% 180 Cy 190

407

50 PhEt Alc 100 Ci 150

140 Rose W 400 DEP 540 T 1000

Lime Fragrance

$0 Lin 50 Lin Ac _30 Ci 130 Melon Fragrance

350 Hy 400 Herbal base 10 750 T 1000

10 Cin Ald 10% 200 DEP = 210 T 1000

350

The formulation of flavors 408

10 Org

30 MHC1%

10 Al Cap 1%

20 lo

Papaya Fragrance

10 Me Sal 30

300 EMPG10% 350

500 Ben 10%

40 Am Cin Ald 125 Bz Sal 165

50 70 500 620 409

125 Hy 625

5) NoLac 100% 40 UnLac 100% 10 Rasp cryst 55

50 lo 400

Peach 10

5 Mal 120 Hx Cin Ald _5MB 130

411

250 PhEt Alc 100 RI

Peach 5

— 200 UnLac 100% _10 NoLac 10% 210 T 1000 410

10 Clo 45 AmPh Ac 200 Me Io 255

He UnLac 10% Rose flavor T 1000

Raspberry 1

50 50 Ori crt 10% 350 Rasp cryst 10% 50 Mal 5% (1) _50 150 450

_50

Jasmin 50 C Vanilla 10 Bz Bz T 1000

Bz i-Eu UnLac 10% Va T 1000

(1) Maltol (Palatone), 5% solution in Phenylethyl alcohol 412 350 PhEt Alc

_50 RI 400

Raspberry 2

lo 50 Mal 5% (1) Rasp cryst 10% 50 Am Sal 100 400 250

150

50 Am

50

Cin

Et Va 1% 100 T 1000

(1) Maltol. See Ref 411 413 3 Bz Ac

2 Me Sal 40 MHC 10% 45

Strawberry Fragrance

5 Ger 5 PhEt Aic 30 lo

50 EMPG 100% 10 UnLac 100% SMNK 65

40 414

20 Am Ac 10 Am Bu 20 Org

10 Et Cap 60

5 Al Cap 40 Bz Ac 10 Et Oen 5 Et Pel 60

10 y-HpLac (1) 23

2 Et Oen 10 Per 40 An Ald 52

850

T 1000

Tutti Frutti

10 Ci 10%

Hy

10 Gl Ac 10 Gl Bu

10 EMPG 40 415

10 Ci 3 Org

10 Orange Flower 30 840 DEP

UnLac 10% $00 Lilac 50 C oo N

10%

330

DIBIE

840 T 1000

Vanilla 10

160 Va 50 He _15 Mal 225

700 Bz Bz

700

T 1000

(1) y-Heptalactone, Fritzsche Bros. This aromatic chemical is used as a coumarin substitute in

flavors in conjunction with methyl coumarin and other aromatics.

Chapter V Stability of Perfumes and Cosmetics Perfume stability and cosmetic stability should be distinguished. The first implies chemical stability of the aromatic ingredients, the second implies physical stability of the cosmetic system. In the first case there are no odor or color changes, in the second there are no physical changes such as separations, sweatings or other undesirable features. Stability tests can be performed in many different ways. The most reliable and simplest test is the shelf test over a period of one year at ambient temperature. All formulas in this book passed this test, many for periods over one year. In cosmetic practice it is not always possible to conduct stability tests for extended periods. It is then necessary to rely on accelerated oven tests that are often conducted at 42°C for a period of at least one week. These tests are not always realistic since some cosmetic preparations cannot withstand these higher temperatures although they would be perfectly stable on the shelf test. The 8 hour lipstick is an example of the case. However, the test is infallible for determining the stability of perfume compounds in cosmetic media. Table I reports odor quality of single aromatics after a one year shelf test for lipstick and face powder. Concentrations of aromatic product vary, depending on odor intensity. Table glycolate 42°C for tested in

II gives stability data in aluminum chlorhydrate, ammonium thioand calcium thioglycolate. Results are based on accelerated tests at one month. Data reported under calcium thioglycolate was actually Depilatory Ref. No. 7. Some of the aromatic aldehydes were found to be surprisingly stable, possibly due to a stabilizing action of the thioglycolic acid. Results reported should be of value in compounding perfumes for the various cosmetic media. Any element that discolors, fades or alters in odor should not be used.

352

Stability of perfumes and cosmetics

TABLE I. Stability of Aromatic Products in Lipstick and

Face Powder

Lipstick Aromatic chemicals

%

Face powder

Odor

%

Odor

Acetophenone

0.05

Faded

0.25

Bad

Aldehyde C 10 Aldehyde C 11 Methyl nonyl acetaldehyde

0.025 0.025 0.025

OK OK Faded

0.025 0.025 0.025

Weak OK OK

Amyl cinnamic aldehyde Amy] salicylate Anisic aldehyde Anisyl acetate Benzophenone Benzyl acetate Benzyl propionate Benzyl salicylate Bromostyrole Cinnamic alcohol Citral Citronellal

0.25 0.25 0.025 0.025 0.2 O58 0.25

Weak Very good OK OK OK Very good Faded

0.025 O25 0.025 0.1

Weak OK Faded OK

1 1 0.25 0.25 1 1 I 1 0.25 1 0.25 0.25

Good Very good Weak Good WeaO Good Good Good Weak Good Faded Weak

Citronellol

0.25

OK

1

OK

Coumarin p-Cresyl acetate p-Cresyl phenylacetate Cyclamen aldehyde

0.1 0.025 0.025 0.075

Very good OK Weak Weak

0.1 0.05 0.1 1

Dimethyl anthranilate Dimethyl benzyl carbinol acetate Dimethyl hydroquinone Diphenyl oxide Ethyl methyl pheny! glycidate Ethyl vanillin Eugenol Geraniol Geranyl acetate Heliotropine Hydratropic aldehyde Hydroxycitronellal Indol Ionone Isoeugenol Linalool Linalyl acetate Methyl acetophenone Methyl anthranilate Methyl benzoate Methyl eugenol Methyl heptine carbonate Methyl ionone Methyl naphthyl ketone Methyl salicylate

0.05

Weak

0.05 0.1 0.025 0.025 0.1 0.25 0.1 0.1 0.025 0.25 0.01 0.25 0.1 0.25 0.5 0.05 0.05 0.05

Faded Faded Weak OK OK OK Weak OK Faded Weak Weak Good (1) Weak Weak Good OK Weak

1 0.1 0.1 1

Very good OK Good OK OK OK Disagreeable Strong

0.01 0.25 0.1 0.025

Good Good Good Faded

0.25 0.5 1 1 1 0.1 1 0.1 1 0.5 1 ] 0.25 1 0.25 0.5 0.05 1 0.1 0.25

Good Good Terpenic Good Good Fades Fading Poor Good (2) Changed Terpenic Weak (3) OK Weak OK Good OK OK

Stabilility of perfumes and cosmetics

353

TABLE I (Continued) Lipstick

Face powder

Aromatic chemicals

%

Odor

Musk ambrette Musk ketone Musk xylene Musk brassylate Musk pentadecanolid Nerolin Nonalactone Phenylacetaldehyde Phenylacetaldehyde dimethylacetal Phenylacetic acid Phenylethyl acetate Phenylethyl alcohol Phenylpropy! alcohol Rose crystals Skatol Styrallyl acetate Terpineol Terpinyl acetate Vanillin Vetiveryl acetate Undecalactone

0.1 0.1 0.1 0.025

Very good Faded Faded Weak

0.1 0.025 0.025 0.05 0.025 0.05 0.25 0.25 0.1

Faded Weak Faded Faded

Odor Very good Good OK Good Very good Bad OK OK

OK Weak

OK OK OK OK Fading Terpenic Terpenic Good Very good OK

0.075 0.5 0.5 0.1 0.025

Essential oils

Anise Basil

0.05

Bergamot

0.25 0.25 0.25 0.025 0.025 0.025 0.25 0.25 0.25 0.25 0.25 0.5

Cassia Cedarwood Celeri Chamomile Cinnamon Ceylon Cloves Coriander Geranium Guaicwood Lavender Lemon Neroli Orange Olibanum Opoponax Palmarosa Patchouli Petitgrain SA Petitgrain terpeneless Pimenta berries Rosemary

Good Terpenic Terpenic

OK

ws nao

ence

Weak Terpenic Terpenic Bad Bad Terpenic

0.5

0.25 0.25 0.25

Terpenic Terpenic

ws nw Terpenic ee Bo eT

OK o-= wn

Terpenic

354

Stability of perfumes and cosmetics

TABLE I (Continued) Lipstick

Aromatic chemicals

%

Face powder

Odor

Sage Clary

%

Odor

0.05

Weak

Sandelwood Spearmint

0.25

Weak

0.5 0.5

Very good Bad

Tarragon (Estragon) Vetiver

0.025 0.25 0.25

Weak OK Weak

0.05 0.5 1

Terpenic OK Good

Benzoin Castoreum

0.25 0.025

Good Faded

1 0.1

OK OK

Civet

0.025

Faded

0.1

OK

Labdanum Mousse de Chéne (Oak moss) Olibanum Orris Peru Styrax Tolu

0.25 0.1

Weak Faded

0.025 0.25 0.1 0.25

Weak Faded Faded Weak

1 0.25 ] 0.2 1 1 ]

OK Very good Terpenic Weak OK Weak Faded

0.25

Good

0.25

OK

0.1 0.5 0.5 0.5 0.1

OK Bad OK Very good Good

Ylang, extra Resinoids

Absolutes Ambrette Jasmin Rose, Grasse Rose, Bulgarian Violet

(1) Changes to vanillin (2) Changes to vanillin, discolors (3) Turns bad, discolors badly Odor quality reported as OK means that it is true to type.

Stability of perfumes and cosmetics

355

TABLE II. Stability in Reactive Cosmetic Media

Aromatic products Acetophenone Aldehyde C 10, 10%

Aluminum chlorhydrate,

Ammonium thioglycolate,

Calcium thioglycolate

30% solution. 0.5% Perfume

5% solution. 0.5% Perfume

1% Perfume

Good, sl. discol.

OK

Aldehyde C 11, 10%

Methyl nonyl acetaldehyde, 10% Aldehyde C 14, 10%

Amyl salicylate Amyl cinnamic aldehyde Anisic aldehyde Benzaldehyde Benzophenone Benzyl acetate Cinnamic aldehyde Cinnamic alcohol Citral Citronellol Citronellyl acetate Coumarin Cyclamal Diphenyl oxide Eugenol Geraniol Heliotropine Hydroxycitronellal Indol Ionone Isobornyl acetate

Isoeugenol Linalool Linalyl acetate Methyl anthranilate Methyl benzoate Methyl heptine carbonate, 10%

depilatory.

V. good Good

OK

OK OK Good Good Good Good Good, sl. discol.

Weak, brown Fair Weak

Good, sl. discol. Excellent

Good Good Weak

OK V. good, sl. discol. Weak

Good Good, sl. discol.

Weak, discol.

Weak

OK Good V. good

Good OK OK but discol.

Good Good Weak OK OK

Good Good but discol.

OK Bad discol.

OK Weak

Good OK, sl. discol. Weak

356

Stability of perfumes and cosmetics

TABLE II (Continued)

Aromatic products Methyl ionone Methyl salicylate Musk ambrette PCME

Changed Weak

Phenylacetaldehyde 50%

Phenylacetaldehyde Phenylacetic acid Phenylethyl acetate Phenylethyl alcohol Phenylpropyl alcohol Styralyl acetate Terpineol Terpinyl acetate Vanillin Yara yara

Aluminum chlorhydrate, 30% solution. 0.5% Perfume

Ammonium thioglycolate, 5% solution. 0.5% Perfume OK OK OK but yellow OK

Good

Good, sl. discol.

OK

Good, sl. discol. OK

DM A Weak V. good Good

Good V. good OK Good Good

OK OK

Weak Good OK

Terpenic

V. good V. good

Changed Weak Good Good OK Discolored Good, sl. discol. OK Good Good

Sweet orange

Terpenic

Terpenic

Vetiver

Good, sl. discol.

Poor, discol.

Ylang

V. good

Good

Essential oils Bergamot Cloves Geranium Lavandin Lemon Oak moss Patchouli Peppermint Petitgrain Sandelwood

V. good Weak

V. good

Odor quality reported as OK means that it is true to type.

Calcium thioglycollate depilatory. 1% Perfume Good Bad discol.

OK

OK

Poor

Good

OK

Weak

-

Chapter VI Selected Aromatic Syntheses A knowledge of aromatic chemistry is part of the education of the perfumer as well as of the student of organic chemistry. Publications on perfume technology give extensive reviews of the patent and scientific literature and are primarily meant for the research chemist. This text presents only standard processes used in the industry. These were carefully selected and checked for efficient operation and satisfactory yield of olfactory pure product. To complete the review of the important aromatic chemicals, additional workable processes are needed. Hopefully, this could be achieved in part by fulfillment of PhD theses. A perfect example is the thesis of R.O. Meyer, Investigations of the preparation of phenylethyl alcohol, Polytechnic Institute, Zurich, 87 p (1947). Books on synthetic aromatics are published infrequently. One of the earliest was written by René Sornet, Techniques Industrielles des Parfums Synthétiques, Gauthier-Villars, Paris, 123 p (1923). Two books are available for a more recent review of the literature: West, Strausz and Barton, Synthetic Perfumes, Edition Arnold & Co, London, 380 p (1949). P.Z. Bedoukian, Perfumery Synthetics and Isolates, Edition Van Nostrand, New York, 488 p (1951). Reprinted in 1976. The present notes are meant to complete the information that is given in these books.

MEASURES AND UNITS The quantities of chemicals and solvents in the processes are given in pounds and also in gallons for the solvents to conform to American practice. This data could be converted to metric units, but it is simpler to consider the given quantities as metric pounds (1 metric pound = 0.500 kg) and metric gallons (1 metric gallon = 4.000 liter). This preserves both the proportions and round figures, although the batch size is increased by 10%. Incidentally, the metric pound is still widely used in retail trade in continental Europe where it is called libra, livre, Pfund, etc. Note that the process quantities are usually based on the key raw material taken as one mole, or occasionally an integral multiple, that is often expressed in pounds instead of grams. Furthermore, the reactants are shown for a complete processing charge which should be mixed in the order that is given and according to the directions. This presentation will help interpreting the mechanism of the reactions.

358

Selected aromatic syntheses

ABBREVIATIONS l Ib Me Mol Wt MP mm

Ac AcOH BP Et FP g

Acetyl, CH;CO Acetic acid Boiling point Ethyl Freezing point Gram

Gal

U.S. Gallon (3.785 /)

Liter Pound (454 g) Methyl Molecular weight! Melting point mm Hg (pressure)

1. ACETOPHENONE Friedel-Crafts (1857)

Acetophenone is obtained by condensation of benzene and acetic anhydride according to Friedel-Crafts’ reaction: AICI; 2CséHs

Benzene 78

+

(CH;:CO)2.0

Acetic anhydride 102

——~

2Ce6H;.COCH;

+

H20

Acetophenone 120

In a 5 / flask, charge:

1000 g Benzene, thiophene free 750 g Aluminum chloride, anhydrous 200 g Acetic anhydride Add the acetic anhydride while cooling the flask. Keep the temperature under 50°C. After this addition, continue stirring for 2 hours. Let stand overnight. Add water through a dropping funnel while cooling the flask with cold water. This causes the benzene to reflux. Wash and distill as usual. The yield is 210g, or 87% of theory. p-Methyl Acetophenone The procedure is the same as for acetophenone, except that the condensation is made with toluene and acetic anhydride. The charge is: 1000 g Toluene 750 g Aluminum chloride, anhydrous 200 g Acetic anhydride

The yield is 245 g, or 90% of theory. ‘Numbers below chemical names also indicate the molecular weight.

Selected aromatic syntheses

359

2. AMYL CINNAMIC ALDEHYDE Le Sech, Descollonges Fréres (1923)

Amyl cinnamic aldehyde is obtained by condensation of benzaldehyde with heptaldehyde: CsHs.CHO

+

wos CHO

— > CcHs.CH=C.(CH2)sCH3

|

CHO

Benzaldehyde

Heptaldehyde

Amyl cinnamic aldehyde

106

114

202

Some amyl] nonenealdehyde is also formed as a side reaction when heptaldehyde condenses on itself. Since this product has a somewhat rancid odor and is not easy to separate by vacuum distillation (the boiling points are only 10° apart), special methods have been proposed to minimize its formation. U.S. Patent 2 102 965 by W.C. Meuly uses the bisulfite of heptaldehyde in the condensation. As the aldehyde is liberated by the alkali it reacts with an excess benzaldehyde. Bisulfite Compound In a 1 / flask, charge:

310 150 40 150

g Methanol g NaHSO; g Water g Heptaldehyde

After addition of the heptaldehyde reflux for 1 hour. Filter cold, wash and resludge with methanol. The cake weighs 230 g.

Condensation In a 1 / flask, charge:

18 32 150 212 220

g KOH g Water g Methanol g Benzaldehyde, 2 moles g Heptaldehyde bisulfite compound, | mole = 217

After the benzaldehyde has been added, charge the bisulfite compound over a period of 2% hours at 20-25°C. Hold for half an hour. Isolate the reaction product and fractionate as usual. The yield is 128 g.

360

Selected aromatic syntheses

Recapitulation

Benzaldehyde recovered Benzaldehyde used

118g 94 g, or 94/106 = 0.88 mole

Yield based on heptaldehyde Yield based on benzaldehyde

128/202 = 0.63, or 63% of theory 0.63/0.88 = 0.72, or 72% of theory

Second Procedure In a 1 / flask, charge: 300 g Ethanol 200 g Water

11 g KOH 212 g Benzaldehyde, 2 moles © 134 g Heptaldehyde, 0.9 mole of 100% aldehyde Add the heptaldehyde last over a period of 2 hours at 25°C. Separate the oil layer, neutralize with acetic acid 30% solution, wash and fractionate. The yield is 134 g based on heptaldehyde, or 74% of theory. Amylcinnamic aldehyde should be stabilized since it gradually oxidizes. BHA is widely used as an antioxidant to preserve aromatic chemicals. 3. ANISIC ALDEHYDE

H. Labbé (1899) Anisic aldehyde is obtained by oxidation of p-cresyl methyl ether with active manganese dioxide paste: CH;

CHO

+ 2MnO,

=

OCH;

+ 2MnO

+ H,20

OCH;

p-Cresyl methyl ether

Anisic aldehyde

In a 5 / flask, charge:

A 2700 g 290 g B_ 122 g C 330g

MnO; sludge 5.4%, 1.7 moles Sulfuric acid 66°Bé (92%), 2.8 moles p-Cresyl methyl ether, 1 mole Sulfuric acid 50°Bé (62%), 2 moles

After part A is mixed, add B over 30 minutes and C over 3 hours. Keep temperature at 30-35°C during these additions while agitating continuously. Then, filter the reaction mass on a stoneware filter after addition of 10 g filtercel.

Selected aromatic syntheses

361

Wash cake with 200 ml toluene. Stir and separate. Extract aqueous layer with 150 ml toluene, verify that extraction is complete. The combined toluene solutions are now washed with 200 ml 10% sodium carbonate solution in order to extract the small amount of anisic acid that is formed in the reaction. On acidification, 5 g of anisic acid is obtained. Wash the toluene extracts with 2 x 5 g of bisulfite solution 38°Bé (42%) to decolorize. This washing must be done quickly to prevent formation of bisulfite compound. Then wash with water until neutral and distill off the toluene under atmospheric pressure. Vacuum distillation of the crude (120 g), yields 35 g unreacted p-cresyl methyl ether, 75 g anisic aldehyde, and 10 g residue. The yield is 78% of theory. The boiling point of anisic aldehyde is 91°C at 4mm. Refractive index nD/20° 1.5700. The percent p-cresyl methyl ether converted is 71%. The manganese oxide MnO in the mother liquors can be regenerated to active MnO, paste by addition of a solution of potassium permanganate: 2KMnO,

+

MnO

H2SO,

+

O

2MnO,

=

+

K»SO,

+

H.O0

+

30

MnO,

Theoretically, 316 g KMnOa,, 2 moles, is needed to oxidize 3 moles of MnO with formation of a total of 5 moles MnO2. To the mother liquors of the reaction, which contains 1.7 moles MnO, add 2100 g of a 10% solution of KMnO, over a period of 15 minutes. This is left to settle for 4 hours. After decantation of about 2100 g, an equal amount of water was replaced. The next day this was decanted and filtered repeatedly, yielding 3000 g paste titrating 7.8% MnOn, or a total of 2.7 moles. The reoxidized paste was tested against regular paste as an oxidizing agent, using 1.7 moles MnO; as previously. The conversion of p-cresyl methyl ether was 70% of theory, against 62% with regular commercial paste. An experimental batch using KMnO, as an oxidizing agent gave a somewhat lower yield of anisic aldehyde and an increase of anisic acid that forms in the reaction. Preparation of p-Cresyl Methyl Ether p-Cresyl methyl ether is prepared by methylation of p-cresol by means of dimethyl sulfate: CH;

CH; SF Me2SO,4

2

OH 108

+

2NaOH

=

+

7

OCH; 126

122

Na2SO,4

ta 2H20

362

Selected aromatic syntheses

Transfer of the first methyl group is quantitative, but conversion of the second methyl group requires a higher temperature. In a 5 / flask, charge: 865 g p-Cresol, purity 98/100%, 8 moles 1075 g Caustic soda 30% 693 g Dimethyl sulfate, 5.5 moles

Add the caustic soda to the p-cresol over half an hour, keeping the temperature between 30 and 33°C. Then add the dimethyl sulfate over 2 hours at 34-36°C. Hold at that temperature for another half hour and then heat the batch to 95°C over a period of 2 hours. Hold at 95°C for 3 hours. Let stand, separate and wash until neutral. Fractionate under vacuum. BP 75°C at 20mm. Refractive index nD/20° 1.5125. The yield is 976g, or 80% of theory based on dimethyl sulfate. Caution: Extreme care is needed in handling dimethyl sulfate. Vapors are odorless and extremely toxic. Follow safety instructions of the supplier. 4. BENZOPHENONE Friedel-Crafts (1877)

Benzophenone is obtained by condensing benzene and carbon tetrachloride in the presence of aluminum chloride according to the reaction of FriedelCrafts. The chloride that is formed is hydrolyzed to benzophenone: 2CeHe

Benzene 78

+

CCl,

Carbon tetrachloride

AICI; —>

(CoHs)2CCl,

H20 — >

Benzophenone dichloride

(CeHs),CO

+

2HC

Benzophenone

In a 400 Gal glass lined reaction kettle with jacket for brine circulation, charge: 1150 lbs Carbon tetrachloride 325 Ibs Aluminum chloride, anhydrous In a 150 Gal mixing tank for the reactants, charge:

616 lbs Carbon tetrachloride, 4 moles = 616 390 Ibs Benzene, thiophene free, 5 moles = 390

The first mixture should be considered as the reaction medium since all of the carbon tetrachloride is recovered. In the second mixture only 2 moles of carbon tetrachloride react with the benzene. The detailed operation is as follows: In the reaction kettle, with stirrer running, charge the carbon tetrachloride and the technical anhydrous aluminum chloride. Circulate the cooling brine in

Selected aromatic syntheses

363

the jacket until the temperature of the mixture is 0° to 5°C. Then add 100 lbs of the benzene mixture and the reaction begins immediately. The water spray is opened in the hydrochloric acid absorber. The mixture of the balance of the reactants is added over a period of 12 hours under continuous cooling. The temperature rises, but should be kept below 10°C. After all is added, continue cooling and stirring for 2 hours.

The brine is now pumped out of the jacket and stirring is continued for at least 12 hours. After that period, add cautiously 100 Gal water. As the water is being added, the reaction mixture must be constantly watched since frothing occurs. If not controlled by stopping the flow of water, a considerable loss occurs through the condenser. Cooling water is run through the jacket during the addition of water, but towards the end the temperature is allowed to rise close to the boiling point of carbon tetrachloride TEC): Steam at 2-3 lbs pressure per sq. in. is now admitted into the jacket and the carbon tetrachloride is distilled off as fast as possible without loss in the condenser. The distillation takes about 10 hours. The recovered carbon tetrachloride amounts to nearly 1200 lbs and is treated as shown further below. The content of the reaction kettle is allowed to settle, and the lower layer of aluminum chloride is separated. The crude benzophenone is washed first with 50 Gal water, then with 50 Gal water and sodium carbonate to neutralize completely the excess acidity. The washed benzophenone is distilled in a copper still at a pressure not exceeding 10 mm. The main fraction consists of 350 lbs of material that is water white. First and last fractions are redistilled. Crystallization

The distilled benzophenone is dissolved in twice its volume of methanol, filtered and run into the crystallizer. While stirring, the temperature is slowly lowered to 5°C. The crystals are centrifuged and dried with warm air in a shelf drier. The mother liquor is distilled to recover the methanol, and the residue is vacuum distilled with the next batch of crude benzophenone. Taking into account all recoveries, the yield is approximately 375 lbs. This is 50% of theory based on the carbon tetrachloride used up in the reaction. The yield based on the benzene is high. Recovery of Carbon Tetrachioride

The carbon tetrachloride that is recovered in the distillation must first be separated from the water and neutralized with soda ash. It is then distilled under atmospheric pressure and dried with 10 lbs of calcium chloride. It is used for subsequent batches.

364

Selected aromatic syntheses 5. CINNAMIC

ALDEHYDE

Schimmel & Co, Leipzig (1893)

Cinnamic aldehyde is obtained by condensation of benzaldehyde and acetaldehyde with dilute caustic soda: NaOH

CsHs.CHO

+

CH;.CHO

——~

CoH;.CH:CH.CHO

Benzaldehyde

Acetaldehyde

Cinnamic aldehyde

106

44

132

+

H.20

A secondary reaction, the condensation of acetaldehyde on itself with formation of aldol and higher polymers proceeds at the same time and cannot be avoided. The concentration of the caustic solution may vary between 2 and 4% without affecting the yield. The acetaldehyde must be added slowly or the yield is impaired. The temperature of the reaction should be kept at about 10°C, although no decrease in yield was observed with temperatures up to 20°C. Contact with iron should be reduced to a minimum to avoid discolorations and polymerizations. In a 100 Gal copper kettle equipped with agitator and condenser, charge: 490 11 50 65

lbs Ibs lbs lbs

Water Caustic soda, NaOH Benzaldehyde Acetaldehyde

flakes

After addition of the caustic soda, cool to 14°C, and add the benzaldehyde. The acetaldehyde then is added over 2 hours, keeping the temperature below 16°C; this is fed by gravity from a cooled drum, the feed line extending well below the surface of the liquid to reduce the loss of acetaldehyde to minimum. After all the acetaldehyde is introduced, the mixture is extracted twice with 35 lbs benzene. The extracts are combined and washed neutral with water. Should layers prove difficult to separate, add dilute acetic acid until just acid to litmus. The benzene (60 lbs) is distilled off, and the residue (77 Ibs) is fractionated under vacuum in an aluminum still. The following fractions are obtained: 10 40 5 20 15)

Ibs lbs lbs Ibs

Heads, mostly benzaldehyde for re-use Good material, BP 139°C at 15 mm Heavy intermediates for redistillation Residue

The yield is 62% of theory.

Refractive index nD/20° 1.6160 Specific gravity 20°C 1.041 Cinnamic aldehyde 97.8%

Selected aromatic syntheses

365

6. CITRAL F.D. Dodge. Isolation from lemongrass oil (1890)

ye HC” “CH, Citral

Although citral is now produced synthetically, its extraction from lemongrass oil is still of importance. This is achieved by means of the bisulfite compound. Since citral has two double bonds and one aldehyde group there are several bisulfite compounds. At room temperature and under weak acidic conditions, the so-called labile bisulfite is formed which can be hydrolized with caustic soda to regenerate the citral. If the solution is heated, a stable bisulfite is formed that cannot be hydrolyzed. For practical purpose, one mole of citral, or its equivalent content in lemongrass oil, is reacted with 2 moles of sodium sulfite in the presence of 2 moles of sodium bicarbonate: Na2SO;

+

Sodium sulfite

126

NaHCO;

==

Sodium bicarbonate 84

NaHSO;

Sodium bisulfite 104

+

Na2CO;

Sodium carbonate 106

Na.2CO;

CsHis,;CHO

+

Citral 152

2NaHSO;

CyH5(H.SO3;Na).CHOH.SO3Na Bisulfite compound 256

After extraction of the terpenes, the citral is liberated with caustic soda, washed and vacuum distilled as usual. In a 500 Gal reaction kettle, charge:

1650 252 170 195

Ibs lbs lbs Ibs

Water Sodium sulfite, anhydrous, 2 moles = 252 Sodium bicarbonate, 2 moles = 168 Lemongrass 75% = 145 Ibs 100%, 0.95 mole = 145

After the sodium sulfite is in solution, add the bicarbonate and heat slightly to complete the solution. Cool to 30°C and add the lemongrass oil. Stir for 4 hours, keeping the temperature at 30°C. Let stand overnight.

366

Selected aromatic syntheses

The following day, after separation of the terpenes, add 150 lbs benzene. Liberate the citral with about 200 lbs of a 50% solution of caustic soda NaOH. The temperature should not exceed 25°C. Stir for 2 hours and allow to settle for 16 hours. Discard the aqueous layer and wash the benzene solution in succession with 60 lbs Water containing 10 lbs of NaCl 75 lbs Water containing 10 lbs glacial acetic acid 150 lbs Water

The benzene is distilled off and the citral is fractionated under vacuum. The yield is 130 lbs citral, or 90% of theory. This yield could be improved with a better method of extraction to minimize polymerization of citral in contact with caustic. 7. CITRONELLYL

OXYACETALDEHYDE

S. Sabetay (1929)

Citronellyl oxyacetaldehyde is obtained by condensation of citronellol and

ethyl chloroacetal with subsequent de-acetalization of the acetal that is formed: Na

CoHi7.CH20OH

+

Citronellol

Acetal + 2AcOH

Cl.CH2CH(OEt)2

-——>»

CosHi7.CH2.0.CH2CH(OEt)2

Ethyl chloroacetal

Citronellyl oxyacetaldehyde diethyl acetal

152.5

Ia

H.2SO

——>=~CoHi7.CHi.0:CH,CHO®

40 2/AcOEt: +) HsO

Citronellyl oxyacetaldehyde

Citronellyl oxyacetaldehyde is an important aromatic chemical, although it can be used only sparingly because of its powerful muguet-rose odor. Procedure!

In a 12 / flask fitted with agitator, nitrogen inlet tube and reflux condenser, charge: 6500 g Citronellol extra 320 g Sodium cut in small pieces 2120 g Ethyl chloroacetal

After the sodium is added, introduce nitrogen and slowly raise the temperature of the oil bath to 106°C to melt the sodium. When the sodium is melted, turn off the heat and the temperature rises spontaneously to 130°C. After the reaction subsides the oil bath is raised to 140°C. After 2 to 3 hours the sodium is 'Private communication of Dr. Sabetay (1939).

Selected aromatic syntheses

367

completely dissolved. Add about 200 g ethyl chloroacetate to the mixture kept at 140°C with the flow of nitrogen and the agitator running. After 45 minutes a precipitate of sodium chloride forms and the balance of the chloroacetal is then added over a period of 2 hours. The precipitate becomes considerably heavier. If an exothermic reaction is not noticed, the temperature is raised to 150°C. Stirring is continued for 2 hours. The reaction mass is now tested by filtering a small sample and heating the filtered solution to boiling. If no precipitate forms after several minutes the reaction is considered complete. When the reaction mixture has cooled, add about 3000 ml water while stirring. The precipitated sodium chloride dissolves and the solution is separated. About 5 more washings are required until the oil is neutral. The crude reaction product (7800 g) is distilled under vacuum in a flask fitted with a 50 cm packed column. After the citronellol is distilled off, the column is replaced with a Claisen head and the citronellyl oxyacetal is rapidly distilled over. The following fractions are obtained in the distillation: 200 400 4500 50 2500 50 100

g g g g g g g

Water Ethyl chloracetal, unchanged Citronellol Acetal, heads Acetal, good material Acetal, tails Residue

The acetal has the following characteristics: Boiling point 115°C at 1 mm Refractive index nD/20° 1.4395 Specific gravity 0.8800

De-Acetalization In a 5 / flask fitted with stirrer and air condenser, charge: 1970 700 700 170

g g g g

Citronellyl acetal Water Glacial acetic acid Sulfuric acid 66°Bé

While stirring, heat to 50°C for 4 hours. Cool and dissolve the yellow oil in benzene. The benzene solution is then washed until absolutely neutral. Extract the washings with benzene and add to the main solution. Distill off the benzene and fractionate using a 50 cm packed column. About 1000 g citronellyl oxyacetaldehyde (92%) is obtained. BP 98°C at 2 mm. Refractive index nD/20° 1.4500. A last fraction (about 175 g) is returned for de-acetalization. The yield is 65% of theory. The reaction can also

368

Selected aromatic syntheses

be run with ethyl bromacetal that is now available commercially. This increases the yield 10%. Citronellyl oxyacetaldehyde should be kept as a 50% solution in ethyl alcohol.

8. CUMINIC ALDEHYDE Cuminic aldehyde occurs in several essential oils, particularly in oil of cumin (25%). However, synthetic cuminic aldehyde is more economical as a raw material for the preparation of cyclamen aldehyde. Two manufacturing methods can be used. In the first method, cuminic aldehyde is obtained by means of the Gatterman-Koch reaction from benzene in a single condensation with carbon monoxide and isopropyl chloride: CHO AlCl; 5s Cu,Cl,

Fi

on

+

HCl

CO + Cl.CH(CHs)2 CH(CH:;)2 Benzene 78

Cuminic aldehyde 148

Another method is based on the Sommelet reaction. The basic material is commercial cumene which is first converted into chlormethy! cumene by means of paraformaldehyde and hydrogen chloride (HCI gas) in the presence of zinc chloride ZnCl2. An intermediate theoretical compound HO.CH>Cl of formaldehyde and hydrochloric acid may be assumed to react with the cumene: CHCl + HO.CH,Cl

Cumene

ZnCl.

—~>

+ H.,0

Chlormethyl

cumene

Selected aromatic syntheses

369

Chlormethyl cumene is then oxidized to cuminic aldehyde by means of the sodium salt of 2-nitropropane:

+ fips

ae

as

+ Naame

CH;

Chlormethyl cumene

+ NaCl

CH;

2-Nitropropane Sodium salt

Cuminic aldehyde

Acetoxime

The hydrogen chloride (HCI gas) needed for this reaction can be produced by reacting chlorosulfonic acid with HCl 20°Bé (35%): HSO;Cl

+

HCl

+

H.,0

=

H.2SO,4

+

2HCl

Hydrogen chloride is also needed for the Gattermann-Koch synthesis. It can be produced together with carbon monoxide by running formic acid and HCI 20°Bé into concentrated sulfuric acid. The evolving gas mixture must be washed with concentrated sulfuric acid.

Gattermann-Koch Reaction (1906) Equipment 300 Gal glass lined kettle with stirrer and jacket. Aturbo mixer for efficient gas absorption is desirable. A cylindrical reactor provided at the bottom witha porous or sintered plate is used for introduction and absorption of the carbon monoxide. The reactor should be vented by means of a | in. pipe connected to a 10 Gal carboy half filled with water for absorbing the HCI evolved in the reaction. In order to follow the absorption of the carbon monoxide during the reaction, the gas should be vented through a carboy containing sulfuric acid; a safety tank should be added to prevent back-suction into the reaction mass. Carbon monoxide generator. A 100 Gal lead lined jacketed kettle is suitable. This is half filled with concentrated sulfuric acid and kept at 90°C. Formic acid is fed into the generator at the rate of 4 lbs every half hour. Or preferably use CO gas from cylinder containers. Quenching tank. Capacity 1000 Gal, lead lined. Still for evaporating the solvent and vacuum distillation of the cuminic aldehyde. The reaction should be conducted in a completely enclosed system. Leaks of HCl can be readily detected with ammonia, but there are no good methods to show the presence of carbon monoxide.

370

Selected aromatic syntheses

Procedure

In a glass lined kettle fitted with cooling jacket, charge: A 780 500 50 B 236 140

lbs lbs lbs lbs lbs

Benzene, thiophene free, 10 moles = 780 Aluminum chloride, anhydrous Cuprous chloride, anhydrous Isopropyl chloride, 3 moles = 235.5 Carbon monoxide CO gas, 5 moles

Mix the ingredients A and add ingredients B over a period of 20 hours, keeping the temperature at 20-25°C. For best absorption of the carbon monoxide, the reaction should not be run for a shorter period, except when using a turbo mixer. ‘ After the reaction is completed, the batch is quenched on ice. The amount of ice required is about four times the amount of aluminum chloride used in the reaction. Wash and separate. Benzene (500 lbs) is recovered by distillation, the aldehyde being fractionated under vacuum. The yield is 200 Ibs cuminic aldehyde 90-100%. This is 45% of theory calculated on the isopropyl. chloride. Benzaldehyde (4%) and a few percent of higher boiling diisopropyl compounds form in the reaction. Satisfactory results were also obtained in a reaction with isopropyl ether instead of isopropyl chloride. This requires the introduction of both HCl and CO gas. The following is an example: In a 5 / flask fitted with good agitation, charge: A 860 650 65 B 312g 140 85

g Benzene thiophene free, 11 moles g Aluminum chloride, anhydrous, 5 moles g Cuprous chloride, anhydrous Isopropyl ether, 3 moles g Carbon monoxide, 5 moles g Hydrogen chloride HCI gas, 2.3 moles

Mix the ingredients A and introduce simultaneously the ingredients B over a period of 7% hours, maintaining the temperature at 27°C. After the reaction stops, as can be seen by poor absorption of the carbon monoxide, pour the mass slowly on ice, separate the oil and wash to neutral. Recover the benzene and fractionate under vacuum. The yield is 180 g of cuminic aldehyde. Note. HCl and CO gas can also be generated tegether by means of the following reagents:

255 g Formic acid 90%, 5 moles 275 g Hydrochloric acid 20°Bé (31%), 2.3 moles

Add these acids separately to 1100 ml sulfuric acid 66°Bé over a period of 7% hours. The evolving gas mixture must be dried.

Selected aromatic syntheses

371

Sommelet Reaction (1914) Generation of HCI Gas

For the procedure given below, place 140 g chlorosulfonic in a flask provided with agitation. Over three hours add slowly 44 g HCI 20°Bé by using 1 Ib pressure to overcome the pressure in the flask. Place the HCI admission tube just below the surface of the liquid. Temperature of the liquid is 50°C. Chlormethylation

In a 1 / flask fitted with agitator, charge: 120 180 34 24

g g g g

Cumene, reactant, dry; 1 mole Cumene, solvent, dry Paraformaldehyde Zinc chloride, anhydrous

Over 3 hours, introduce HCl gas at the rate mentioned above. Temperature rises to 65-70°C in the reaction. In the last hour, the temperature drops and HCl is released. Agitate another half hour at 65-75°C. Cool to 30°C and allow to stand for 2 hours. Separate small residue, wash with 300 ml water containing 5 g salt and 0.3 g tergitol. Actually wash 4 times with 75 ml, with little agitation to prevent emulsification. Finish washing rapidly with 80 ml water and 2 g soda ash. Separate and distill under vacuum. Cumene (180 g) is recovered and the yield of chlormethyl cumene is 120 g, or 70% of theory. BP 90-95°C at 4mm. Distillation must be rapid to prevent hydrolysis. Use short column. Oxidation In a 1 / flask fitted with agitation and reflux condenser, charge: 41 350 90 170

g g g g

Sodium hydroxide, flakes 98% Methanol 100% 2-Nitropropane, (CH;)2CH.NO2, 1 mole = 89 Chlormethyl cumene, 1 mole = 168.5

Add the 2-nitropropane at such a rate that reflux continues while stirring and applying heat. After addition is complete, continue stirring for 15 minutes. Then add the chlormethyl cumene over a period of one hour. Distill off the methanol under atmospheric pressure or poor vacuum. Cool the reaction mixture and add 450 ml water. Stir to dissolve the precipitated sodium chloride, separate any insoluble oil and extract with 3 portions of 70 ml each of benzene. Combine the separated oils and the 3 extracts and wash with 100 ml water. Extract 3 times with 70 ml each of NaOH 20% solution to remove the acetoxime formed in the reaction. This must be completely removed, or it will spoil the final product. Wash with water until neutral, about 3 times with 70 ml each. Distill off the benzene at atmospheric pressure and the cuminic aldehyde under vacuum. The yield is 115 g, or 78% of theory.

Boiling range: 83-90°C at3mm__

Refractive index: nD/20° 1.5290-1.5300

372

Selected aromatic syntheses 9. CYCLAMEN

ALDEHYDE

(CYCLAMAL)

A. Knorr and A. Weissenberger, Industrial process (1929)

Cyclamen aldehyde is obtained by condensation of cuminic aldehyde and propionaldehyde, and subsequent selective hydrogenation of the double bond of the condensation product:

CH, CHO

CH;

jG

|

CH;

athere

GHOL Ss

CH,

H.CHO

eee

CH(CHs).

CH(CHs).

Cuminic

Procyclamal

aldehyde 148

CH(CHs). Cyclamal 190

Condensation

The condensation agent that is generally used for the production of procyclamal is sodium hydroxide. However, laboratory tests showed that sodium methylate gave better results. The procedure is as follows: In a 1 / flask, charge: 300 4 148 58

g g g g

Methanol 100% Sodium, metallic Cuminic aldehyde 100%, 1 mole Propionaldehyde, freshly distilled, 1 mole

Add the sodium slowly, cooling to 25°C. When in solution, add rapidly the cuminic aldehyde. Then, over a period of 6 hours, add the propionaldehyde, keeping the temperature at 25°C. After the final addition, stir for 1 hour. Acidify with glacial acetic acid, using litmus as indicator. Distill off the methanol at atmospheric pressure (Column 74°C, liquid 84°C max). Proceed carefully since some foaming takes place at the end of the distillation. Add 100 ml water and 100 m! hexane; stir for several minutes and place in separatory funnel. Wash the oil layer until neutral, distill off the hexane, and fractionate the residue.

Distillation Heads Intermediates Procyclamal Residue

19g 8g 134g 13 g

60to 93°Cat3mm nD/20° 1.5289-1.5335 93to 95°C at3mm nD/20° 1.5657 95to 125°C at3mm _ nD/20° 1.5745-1.5840

The yield is 74% of theory.

Selected aromatic syntheses

373

Hydrogenation The hydrogenation is the most critical step in the manufacturing procedure. It hinges on the development of a catalyst that will allow saturation of double bond without reducing the aldehyde group. Raney catalyst and other nickel catalysts were unsatisfactory although the newer Ni-K catalysts were not tested. Most consistent results were obtained with palladium catalysts deposited on carbon in the presence of K2CO; as an inhibitor. Depending on the activity of the catalyst, 1 to 2% must be used based on the weight of procyclamal. The reduction proceeds slowly, 8 to 12 hours at 60 to 70°C at a pressure of 65 psi. After filtration of the catalyst (which is non-pyrophoric), remove the solvent and fractionate the residue. The yield is 80% or better. A typical procedure is as follows: In a small autoclave, charge:

160 180 1.2 0.15

g Procyclamal 99% aldehyde, nD/20° 1.5840 ml Isopropanol 99% g Palladium catalyst (Baker Platinum Co) g Potassium carbonate anhydrous

Reduction at 65°C and 60 psi is allowed to proceed overnight. The catalyst is filtered out and washed with 50 ml isopropanol and the solvent is removed. Fractionation yields 127 g aldehyde (92%). Refractive index nD/20° 1.5069. Boiling point range 115-125°C at 3 mm.

10. ESTERS Allyl Caproate (Hexanoate) In a 12/ flask equipped with Bidwell! tube and a large reflux condenser with six or more bulbs, charge:

7lbs_ 7 lbs 7lbs 5ml

Allyl alcohol 68-70% hexanoic acid Benzene Sulfuric acid CP Pumice stones

Reflux until no more water separates. This takes approximately 40 hours. Change Bidwell tube to a long direct condenser and distill off the benzene and excess allyl alcohol. Distillation is stopped when the temperature of the vapors reaches 110°C. The residue is cooled and 4 / of water is added. Neutralize with powdered soda under good stirring. Separate the top layer, wash with water and transfer to a 12/ flask for vacuum distillation. The yield is 8 lbs. BP 75°C at 15 mm. Bidwell-Sterling or Dean-Stark distilling receiver with solvent return tube and stopcock for water release. SGA Scientific Co, Bloomfield, N.J. Cat. No. 8040.

374

Selected aromatic syntheses

Amyl Caproate (Hexanoate)

In a 12 / flask fitted with Bidwell tube and reflux condenser, charge: 11 Ibs Amy! alcohol (Fusel oil) 8 lbs Hexanoic acid Pumice stones

Reflux until no more water separates. This takes approximately 40 hours at which time the content of hexanoic acid should be less than 3%. Change reflux condenser and Bidwell tube to straight condenser. Distill excess fusel oil under atmospheric pressure. Cool the flask and neutralize with soda ash solution. Separate, wash with water and fractionate under vacuum.

First fractions with amyl alcohol odor are returned to the next distillation. The yield is 111% lbs. Phenylethyl Formate

In a 12 / flask equipped with Bidwell tube and condenser, charge: 9lbs_ 6 lbs 6lbs S5ml

Phenylethyl alcohol Formic acid Benzene H2SO, 100% Pumice stones

Reflux until no more water separates. Wash and distill as shown in the procedure for allyl caproate. The yield is 10 lbs, or 90% of theory. Note that the quantity of formic acid used is about 50% in excess of theory. A similar procedure is used for cinnamyl formate. The yield is 85-90% of theory. Phenylethyl Acetate

In a 12/ flask equipped with a 35 in. column and a 18 in. downward condenser, charge: 12 lbs Phenylethyl alcohol 9 lbs Glacial acetic acid Pumice stones

Esterification is accomplished directly without catalyst. The water is distilled off together with a small amount of acid. The vapor temperature should not exceed 100°C. After the esterification is completed (about 20 hours), distill off the excess acid using a shorter column. Wash and distill under vacuum as usual. BP 58°C at 3 mm. The yield is 13.7 lbs, or 85% of theory. A similar procedure is used for phenylethyl propionate, cinnamy] acetate and propionate. The yield is 85% of theory in all cases. The esterification in presence of benzene as in the first example could also be used. However, benzene cuts down on the capacity of the run and is also a fire hazard. Since the boiling points of acetic and propionic acids are well over

Selected aromatic syntheses

375

100°C, the water easily separates without benzene. In the case of formic acid, the boiling point is near to that of water and therefore this method is not indicated. Cinnamy! Isobutyrate

In a 12 / flask equipped with Bidwell tube and condenser, charge: 11 lbs Cinnamy]l alcohol 11 lbs Isobutyric acid Pumice stones The mixture is refluxed until water no longer separates. The Bidwell tube is replaced by a Vigreux head and the excess acid is distilled off with poor vacuum. The mass is allowed to cool and 2 / of water is added. Neutralize with soda ash and wash with water. The crude oil is fractionated under vacuum. The yield is over 90%.

Geranyl Acetate In a 5 / flask, charge:

2000 g Geraniol crude, alkali treated 1400 g Acetic anhydride 25 g Phosphoric acid Keep for 20 hours at room temperature. Ester content should be 87%. Drown in 2000 g crushed ice and 2000 g water. Agitate for 24 hours to decompose excess anhydride. Separate, wash with a solution of 3000 g water and 200 g sodium carbonate. Separate, wash with 2000 g hot water. The yield of crude oil is 2400 g. Charge in still and fractionate under vacuum. BP 96°C at 3 mm. The yield is 1600 g geranyl acetate 94% ester, and 300 g geranyl acetate of somewhat lower ester content. Linalyl Acetate! In a 5 / flask, charge:

370 g Linalool, 2.4 moles 357 g Acetic anhydride, 3.5 moles 12 g Catalyst, 10% H3POs in acetic anhydride Keep one week at 5°C. Take up with 800 Wash the benzene layer with a saturated neutral to litmus. Distill off the benzene. ester. After distillation, a water white 72°C at 3 mm.

g benzene and wash with 300 g water. solution of sodium bicarbonate until The weight of crude oil is 420 g, 84% product is obtained, 90% ester. BP

‘Acetylation according to Isagulyants, Riechstoff Ind. & Kosmetik Bedoukian, Perfumery Synthetics and Isolates, p 293.

8, 194 (1933). See also

376

Selected aromatic syntheses

Menthyi Acetate

In a 5 / flask fitted with stirrer, charge:

408 468

g Acetic anhydride, 4 moles g Menthol, 3 moles

1.9 g H3PO,

Add the phosphoric acid last. The reaction is exothermic, therefore cooling may be necessary at start. Raise the temperature to 125°C and hold 4 hours. Add water to decompose the excess acetic anhydride. Proceed slowly as the reaction is violent. Wash with sodium bicarbonate until aqueous layer is alkaline to litmus. Drain off the water, dry over anhydrous sodium sulfate and distill under vacuum. Take off first 3 to 5%. Residue is negligible. BP 84°C at 3 mm. Ester Interchange Ester interchange is useful for the preparation of some of the higher alcohol esters. In consists in replacing the volatile alcohol component of an ester with an alcohol of higher molecular weight. This is easily achieved by heating the reactants in the presence of the sodium derivative of the volatile alcohol. The volatile alcohol of the basic ester distills off as it is replaced by the alcohol of higher molecular weight. The following examples illustrate the reaction: BuONa

Butyl phenylacetate

Butyl isobutyrate

+

+

Geraniol

Geraniol

———~> BuONa

———>

Geranyl phenylacetate

Geranyl isobutyrate

+

+

BuOH

BuOH

Procedure. In a distilling flask, charge the ester and the alcohol, using a 10% excess of the material that is cheapest. Add 10% by weight of sodium methylate (or butylate), 6% concentration. Distill off the volatile alcohol at atmospheric pressure. The temperature in the liquid slowly rises to 150°C, as about 2/3 of the theoretical quantity of volatile alcohol is collected. Example:

Geranyl phenylacetate

In a 5 / flask fitted with descending condenser, charge: 2000 g Butyl phenylacetate 1200 g Geraniol 300 g Sodium butylate, 6% in butyl alcohol

Selected aromatic syntheses

377

All material must be perfectly dry. Heat slowly to 150°C, vapor temperature

staying at 115°C. About 700g butyl alcohol is collected in 10 hours. Wash the residue with very little water, dry and distill under vacuum. Heads consist of about 1000 g geraniol and butyl phenylacetate. The yield of geranyl phenylacetate is 1500 g, distilling at 150-160°C, 4-7 mm. The residue is 50 g. Some esters such as geranyl salicylate, linalyl cinnamate and a few others cannot be distilled because of decomposition. Only the head fractions can be removed. Vetiverol

In a 50 Gal jacketed kettle, charge: 110 lbs Water 10 lbs KOH, flakes 75 lbs Vetiver oil

Reflux for 3 hours. Separate and wash with warm water until neutral to litmus. The yield is 70 lbs of crude vetiverol. Distill under vacuum. The fractions obtained over a range of 130-165°C at 10 mm are as follows: 8 lbs Heads 55 lbs Main fraction 7 lbs Residue

70 Redistilling the heads yields about 6 lbs of vetiverol. Vetiveryl Acetate

In a 50 Gal jacketed kettle, charge: 61 lbs Vetiverol, Mol Wt 220

63 lbs Acetic anhydride 90% Reflux for 3 hours. Decompose the excess anhydride slowly with warm water. Separate, wash with water, neutralize with sodium bicarbonate and wash

again with water. Fractionate under vacuum. The yield is 55 Ibs of vetiveryl acetate. Vetiver oil can also be acetylated directly since its saponification value is low.

378

Selected aromatic syntheses

11. ETHYL METHYL PHENYL GLYCIDATE So-called Aldehyde C 16, Strawberry aldehyde G. Darzens (1903)

Ethyl methyl phenyl glycidate is obtained by condensing acetophenone and ethyl chloroacetate in the presence of sodium methylate as condensation agent: CsHsCO.CH;

+

CH;ONa

CICH2,COOEt

ee

CH

CeHs.

i, ;

BAT ERO

CL

O Acetophenone

Ethyl

Sodium

Ethyl methyl phenyl

120

chloroacetate

methylate

glycidate

54

206

12285

;

The raw materials for this reaction are industrial chemicals. The processes for ethyl chloroacetate and sodium methylate are outlined below, but it is best to use the commercial products since ethyl chloroacetate is an eye irritant, whereas sodium methylate requires specialized equipment for efficient production. In a 150 Gal vertical reaction kettle, tightly closed, fitted with a cooling jacket extending the full length, and a high speed stirrer, charge: 120 Ibs Acetophenone, 1 mole = 120 120 lbs Ethyl chloroacetate, 1 mole = 122.5 164 Ibs (22.5 Gal) xylene. Note 1 In a separate 60 Gal kettle, tightly closed, fitted with stirrer, charge:

54 lbs Sodium methylate (100%), 1 mole = 54. Note 2 327 lbs (45 Gal) xylene, sp gr 0.870 A slow stream of dry nitrogen (passed through H2SO, and CaCl.) is run into the reactants. The stirrer is started in the reaction kettle and brine is circulated through the jacket. When the temperature is — 10°C, the sodium methylate that is suspended in xylene is cautiously added since the temperature should not be allowed to rise above — 5°C. The addition requires about 12 hours, but it can be shortened with effective cooling. Before each addition, the sodium methylate is agitated to disperse the powder that settled. Stirring and cooling are continued for several hours after the addition is completed. The mixture is then allowed to stand. After 2 days, wash the reaction mixture twice with water. Distill off the xylene at about 50 mm. The recovered xylene cannot be used again for the re-

action. Rectification is not economical.

Selected aromatic syntheses

379

The residue, distilled under high vacuum, gives the following fractions: 15 18 113 5

lbs lbs lbs lbs

Acetophenone. Refractive index nD/20° 1.5200 Acetophenone + glycidate, nD/20° 1.5200-1.5100 Glycidate, BP 132-134°C at 5 mm, nD/20° 1.5100. Residue

151 After redistillation of the intermediates, the yield is about 122 lbs, or about 80% of theory based on reacted acetophenone. The distilled product may have a slight off odor. It is treated with 1% Norit A and 20% water. This is kept boiling in a stream of air under slight vacuum. After about 2 hours the water has vaporized and the Norit is filtered out. This is the finished product. The odor may still be slightly off but after 2 weeks ageing it is entirely satisfactory. Specifications

Refractive index nD/20° 1.5050 Specific gravity 20°C 1.090 Saponification number 275 (Theory 272) Acid number 1.7

See also procedure by C.F. Allen and J. Van Allen in Organic Syntheses, 24, p 82 (1944). Notes

1. The xylene that is used is “Nitration” grade. This distills within three degrees and does not require any preliminary drying or distilling. 2. The sodium methylate is available as a fine powder CH3ONa.CH;30H, or as a suspension in xylene. Suspensions in benzene or toluene are also satisfactory; the concentration of CH3;ONa is usually 25%. In the process, 1 mole acetophenone requires 1 mole CH3;ONa; the quantities of solutions should be adjusted accordingly. The above process was successfully used for preparing several other glycidates, for instance:

Methyl methyl phenyl glycidate prepared from acetophenone and methyl chloroacetate. Ethyl dimethyl glycidate prepared from acetone and ethyl chloroacetate. Ethyl dipropyl glycidate prepared from dipropyl ketone and ethyl chloroacetate. Phenylethyl dimethyl glycidate prepared from acetone and phenylethyl chloroacetate.

380

Selected aromatic syntheses The following two glycidates are important as aromatic intermediates: Ethyl phenyl glycidate obtained from benzaldehyde and ethyl chloroacetate. This can be used as an intermediate for producing phenylacetic aldehyde. Ethyl methyl monyl glycidate obtained from methyl nonyl ketone and ethyl chloroacetate. This is used for producing methyl nonyl acetaldehyde.

Furthermore, the standard glycidate is used to prepare hydratropic aldehyde. This glycidate is easily hydrolyzed to the aldehyde, but the method given in the text failed to split the two glycidates mentioned above. More drastic conditions are required. See methyl nonyl acetaldehyde. Ethyl Chloroacetate

In a 100 Gal glass lined kettle, with steam jacket and reflux condenser, charge: 237 lbs Monochloroacetic acid, 2.5 moles = 236 168 lbs (26 Gal), ethyl alcohol 95%. Note 1

33 lbs Sulfuric acid 66°Bé (97%) Reflux for 9 hours. Cool, pour on 4 to 5 times the volume of water. Separate, dilute the water layer to make certain it does not retain some ester. Repeat the washing to remove the sulfuric acid as much as possible. This also removes the excess alcohol which is discarded. Neutralize the oil layer with a solution of soda ash and wash again with water. Some CO, evolves in the washing and carries over traces of strongly lachrymatory ethyl chloroacetate. This is minimized with the previous water washing. The washed ester is distilled under atmospheric pressure. The first fraction is a mixture of water and ester. The fraction between 142 and 146°C is finished ethyl chloroacetate. First and last fractions are usually very small and are redistilled in the next batch. The yield is 230 lbs, or about 75% of theory.

Note 1

Specially denatured alcohol 2-B is used. This contains 0.5% benzene. There is no advantage in using absolute alcohol. Sodium Ethylate

In a 60 Gal jacketed iron kettle! equipped with a high speed stirrer (preferably a turbo-mixer), charge:

30 Gal Xylene 15 lbs

Sodium metallic. Note 1

Heat to about 105°C to melt the sodium, while introducing a steady stream of dry nitrogen through the mixture. Start the stirrer and disperse the sodium. 'The outlet must be sealed off securely to prevent sodium from entering the pipe.

Selected aromatic syntheses

381

Stop heating. Stop stirring before the sodium is due to solidify. A fine suspended powder must be obtained that reacts completely when mixed with alcohol. When the temperature in the kettle is 95°C, the condition of the sodium must be checked to make sure all has been powdered. This is done by probing with a 1/4 in. iron rod threaded at one end. If any caked sodium is present, this is detected between the threads. In this case the operation must be repeated until the proper mixing conditions are determined. When the sodium is powdered, reduce the temperature somewhat below 45°C, and slowly add 30 lbs ethyl alcohol, absolute. Note 2. Continue cooling to keep the temperature not higher than 45°C, leading the hydrogen formed to the outside. Do not allow the temperature to rise 5°C at any time of the addition, or the mass is liable to froth over. At the end of the addition the temperature should not exceed 50°C. Heat is then applied, keeping the batch at 75°C for 2 hours. After cooling to 25°C, the mixture is ready for the glycidate condensation. Notes

1. Only clean, bright sodium is used. All oxide is cut off before weighing. This entails a loss of about 20%, particularly in small scale operation. 2. Specially denatured alcohol 2-B, anhydrous, is used. This contains 0.5% benzene. It should be tested with anhydrous copper sulfate to make certain it is absolute alcohol. 12. EUGENOL M.

Wasserman

(1876)

CH.2CH:CH,

OCH; OH Eugenol

Eugenol is present in various essential oils such as bay, clove, pimento and cinnamon leaf. Since these oils contain from 60 to 80% eugenol, any could be used for extraction of eugenol by means of caustic soda. After the solution of sodium eugenolate that is formed in this operation is washed free of terpenes, the eugenol is liberated with sodium bicarbonate and taken up with a solvent. In a 100 Gal copper vessel, charge: 200 lbs Caustic soda, 10% solution 100 Ibs Oil of clove, 82% phenols

382

Selected aromatic syntheses

Heat the caustic solution to 40°C, and add the oil over 1% hour. Stir for 3 hours, keeping the temperature below 40°C. Let settle and separate the terpenes. Wash the aqueous layer twice with 25 Ibs benzene to remove all traces : of caryophyllene. To the solution, add: 25 lbs benzene 75 lbs Sodium bicarbonate NaHCO; 75 lbs Water

Stir for 1 hour. Let settle and draw off the benzene layer. Wash the aqueous layer with benzene to recover all eugenol and combine the benzene extracts. Distill off the benzene and fractionate under vacuum. The yield is 75 lbs. A second fractionation may be necessary and somewhat lowers the yield. Note. 1. The benzene extractions containing the terpenes are washed with water. The benzene is distilled off and the residue is rectified to get pure caryophyllene. From 100 lbs of oil of clove, up to 10 lbs of caryophyllene is obtained. Note 1

This redistillation may not be necessary if isopropyl ether instead of benzene is used as a solvent. 13. ISQOQEUGENOL W. Haarmann

and K. Reimer (1890)

Isoeugenol is prepared by isomerization of eugenol with caustic potash at 140°C: CH2CH

=CH),

CH=CH.CH3 KOH

—> OCH; OH

{

OCH; OH

Eugenol

Isoeugenol

164

164

In the example given below, the reaction is made in isoamyl alcohol according to German Patent 57 808 (1890) by Haarmann & Reimer. Ina 5 / flask fitted with agitator, Bidwell tube and reflux condenser, charge: 900 g Isoamyl alcohol 600 g Potassium hydroxide, flakes 90% 1000 g Oil of clove, 82% phenols Heat the isoamyl alcohol and caustic flakes to 160°C to keep the mass homogeneous and add the oil over 30 minutes. Reflux for 5 hours at 135140°C while separating the water that accumulates in the Bidwell tube. Note 1.

Selected aromatic syntheses

383

Cool to 100°C, adding 200 ml boiling water to dissolve the crystalline mass. Steam distill off the amyl alcohol. This is best done by producing the steam directly in the reaction flask under agitation, adding water when necessary. The distillation should be completed in 1 hour, giving 1000 g of steam distilled oil (isoamyl alcohol and terpenes). Note 2. After cooling, extract twice with a total of 1000 g benzene for complete removal of the terpenes. The potassium isoeugenolate is transferred to a flask set in a cooling bath and fitted with a stirrer. In order to neutralize the excess KOH, not including the potassium isoeugenolate, add a solution of 250 g sulfuric acid 66°Bé in 700 g of water. This solution is added slowly under agitation, the temperature not exceeding 35°C. The exact amount of solution will depend on the activity of the potassium hydroxide (90% or more) and the exact phenol content of the oil of clove. To liberate the isoeugenol, add

1000 g Sodium bicarbonate NaHCO; 1500 g Water 1000 g Benzene Agitate for 1% hours. After standing, two layers separate, a dark oil upper layer and a clear lower aqueous layer. Extract the water layer twice with 500 ml benzene, combine the extracts, wash neutral with water and distill off the benzene. Remove the last traces of benzene under vacuum. The crude isoeugenol (850 g) is fractionated under vacuum. The yield is 700 g, the residue 150 g. The entire distillate is yellow in color and poor in odor, although the various fractions show a correct refractive index. A redistillation is necessary. The yield is 650 g of good material. Refractive index nD/20° 1.5736. Specific gravity 20°C, 1.084. Notes

1. The quantity of water obtained in the isomerization varies. It is considerably more than the theoretical quantity because of the formation of potassium amylate. 2. The steam distillatiion should proceed as quickly as possible, as long distilling time causes polymerization.

384

Selected aromatic syntheses

14. GERANIOL AND CITRONELLAL O. Jacobsen, Isolation of Geraniol from Palmarosa Oil (1871)

The essential oils are still a principal source for geraniol and citronellal. Oil of citronella Java is the main raw material for these aromatics. The composition of this oil, in the order of a large scale distillation, is as follows: Boiling Point at 15 mm

Component Terpenes Citronellal Citral Citronellol Geraniol Nerol Alcohols Citronellyl acetate Gerany]l acetate Phenols Sesquiterpenes Sesquiterpene alcohols Residue

to

i

90°C 91 114 115 119 120 120 121 127 134 147 153

Quantity 5 % 40 Or2 4 19 5 3 6 8 1 4 3 2

The crude geraniol (Fractions 4-9) contains about 90% of alcohols and traces of citronellal. Citronellol need not be separated since it has a rose odor similar to geraniol, but citronellal must be eliminated by means of a treatment

with alkali. Distillation of Citronella Oil

About 400 lbs citronella Java are charged in a 70 Gal copper or preferably nickel vacuum still equipped with a 10 ft column filled with 1 in. porcelain Raschig rings. The distillation at 10 mm proceeds as follows: Temperature

Weight

Product

Refractive index nD/20°

to 90°C 91-116 116-138

25 Ibs 200 190

Terpenes Citronellal 85% Geraniol distilled

< 1.4565 1.4565-1.4700

The distillation is stopped when the index reaches 1.4700. The complete distillation takes about 40 hours. Since citronellal polymerizes very easily, it is best to utilize this material immediately. If stored, drums should be filled completely.

Selected aromatic syntheses

385

Geraniol Extra. Purification

About 1000 lbs of distilled geraniol is charged into a 300 Gal glass lined still with 40 lbs of sodium methylate (25% solution in methanol). Stir until solution is complete. Then add 150 Gal water, stir for one hour and separate. Wash with 100 Gal water containing 5 lbs of concentrated hydrochloric acid and finally with another 100 Gal of water. Charge 500 Ibs in an aluminum vacuum still and distill over. A first fraction of about 40 lbs and a last fraction of about 20 lbs are kept apart and added to the next batch. The middle fraction should be practically colorless and with no off odor. The yield is approximately 80% of the material used. Geraniol could also be extracted from oil of palmarosa (90% geraniol) or from oil of geranium (40-50% geraniol), but of course geraniol from these sources is very expensive. Citronellal

Citronellal is usually obtained from citronella Java. Eucalyptus citriodora is also a good source since it contains 80-90% citronellal. At times, citronellal has been produced by selective hydrogenation of citral:

fran

aces

Hz

CHO

cu H;C

S:~

CH;

Citral alpha (Geranial)

montane H,

f=

H.C

H2C

fe

CH

ol

CHO

en H;3C

~*~

CH:

CH;

Citronellal alpha

Lemongrass oil (75% citral content) is usually hydrogenated for this purpose without first extracting the citral. Hydrogenation Charge 100 Ibs lemongrass oil and 4 lbs Raney catalyst in an autoclave. Admit hydrogen at 125 psi and gradually raise the temperature to 100°C. Absorption of hydrogen starts at 80°C. Stop heating at this point, since the reaction heat is sufficient to raise the temperature. Do not exceed 105°C as higher temperature favors terpene formation. The reaction is considered to be complete when the theoretical amount of hydrogen has been absorbed. The reaction time is about 12 hours. This reaction has also been carried out at high pressure in small autoclaves.

The reaction time is cut to 15-30 minutes.

386

Selected aromatic syntheses

15. HYDRATROPIC

ALDEHYDE

Hydratropic aldehyde is obtained by saponification of ethyl methyl phenyl glycidate. The sodium glycidate that is obtained liberates hydratropic aldehyde on heating with dilute acid: CH;

EtONa

Cis

Dilute

acid

7 CH.COONa ——> CsHsC—CH.COOEt ——> CsHsC O Ethyl methyl phenyl glycidate 206

CH;

CeHsCH.CHO

O Glycidic acid sodium salt

Hydratropic aldehyde 134

In a 5 / flask fitted with stirrer, charge:

1600 ml Ethyl alcohol, absolute 92 g Sodium metallic, 4 moles 824g Ethyl methyl phenyl glycidate, 4 moles Add the sodium as rapidly as possible without causing the alcohol to boil. After addition, heat under reflux for a short time to complete the solution. Add the ethyl methyl phenyl glycidate in six equal amounts over a period of 1 hour. After the last addition, the mass becomes solid. Let stand overnight. The following day, the mass is broken up and filtered. It is charged ina 5 / flask with a small amount of water and steam distilled while adding 1800 ml of a 25% solution of tartaric acid. Continue the distillation until no more oil distills over. Saturate the distillate with sodium chloride and extract with about 1200 ml isopropyl ether. The filtrate from the glycidate must be treated to recover all the glycidic acid. It is evaporated almost to dryness under reduced pressure and poured into the residue from the steam distillation. This is again steam distilled and extracted as before. The ether extracts are combined, the ether is recovered and the residue is vacuum distilled. The hydratropic aldehyde distills at 92°C at 14mm. Refractive index nD/20° 1.5164. The yield is 430 g, or 80% of theory. Note. Instead of sodium ethylate, it is more practical to use commercial sodium methylate 25% solution. Acetic acid can also be used for the decomposition of the glycidic acid, but tartaric acid is preferred since it is not volatile. See also Organic Syntheses, 24, 87 (1944).

Selected aromatic syntheses

387

16. HYDROXYCITRONELLAL First Produced by Knoll & Co in 1905 New Manufacturing Process L. Appell and J. Wenneis (1940)

Hydroxycitronellal is normally made from citronellal by means of the bisulfite compound which can be separated as a thick paste. This paste must be filtered and washed, two very troublesome operations. The paste is then hydrated below 0°C with a solution of H2SO, 50%. Neutralization with NaOH 10% solution liberates the hydroxycitronellal. This reaction requires special refrigeration and filtering equipment and very careful operation. See U.S. Pat 2 235 840 (1941) by W.C. Meuly. The new process is in part based on the Japanese Patent 109 568 (1934) by J. and M. Haneda. This patent claims the production of hydroxycitronellal by decomposition of its bisulfite compound by means of formaldehyde in order ‘to prevent polymerization by the alkalies that are normally used for this purpose An example quoted from the patent is as follows: “100 parts of citronella bisulfite compound are dissolved in 300 parts of 60% sulfuric acid, which is cooled and agitated for 2 to 3 hours. The solution is saturated with sodium bicarbonate to neutralize the sulfuric acid. On standing, the impurities float on the surface. After removing these impurities, 35 parts of 40% formaldehyde solution is added. The bisulfite is fully decomposed and the hydroxycitronellal floats on the surface. The latter is separated and distilled under vacuum.”

In the new process, the bisulfite compound is not filtered and the subsequent reactions are carried out in the same kettle at ordinary temperature, and without special precautions. When citronellal is added to a solution of sodium bisulfite, the normal compound is obtained. However, in the presence of even dilute strong acid, a cyclic sulfonic acid is formed which does not separate on addition of alkali. To prevent this undesirable reaction, the bisulfite compound is prepared in the presence of an excess of boric acid. The steps required are the following:

1. Formation of the bisulfite compound of citronellal in the presence of boric acid 2. Acidification with hydrochloric acid to form disulfonic acid 3. Neutralization of the disulfonic acid with sodium carbonate 4. Liberation of hydroxycitronellal by the addition of formaldehyde 40% solution

388

Selected aromatic syntheses

The process is summarized in the following reactions: 2 Na2SO;3

NaHSO;

+

H;BO;

+

=

2 NaHSO;

CHO

+

Na2HBO;

=

CHOH.SO;Na

CH

CH

Cc

Cc

II

|

AX

OS

Citronellal

HCl

Bisulfite compound

CHOH.SO3H_

—_—_

Na2CO;

CHOH.SO;Na

——

NaHSO; adele

CH.SO;Na

CH

H

a

MaRS

Disulfonic acid

Disulfonic acid sodium salt

CHO + 2CH,0

=

2 CH,20H.SO;Na

Acet-

Bisulfite

aldehyde

compound of

+

HOH

I

acetaldehyde

H

VAN Hydroxycitronellal

According to a second theory, the addition of HCl shifts the bisulfite group to the double bond:

CHOH.SO;Na o) H

¢

Pes

=, (ee ae SO3H

cu

ZN

Selected aromatic syntheses

389

The new bisulfite compound that is formed is neutralized with sodium carbonate and the hydroxycitronellal is liberated with formaldehyde as in the first case. As can be seen only one mole of bisulfite and one mole of formaldehyde are needed for the reaction instead of two moles in the first theory. This is of course a minimum; actually the process calls for larger quantities. Equipment 650 Gal glass lined reaction tank with 3 H.P. high speed propeller agitator, rubber lined. Equipped with a large exhaust fan placed directly above the tank. 800 Gal glass lined extraction tank with stirrer and bottom outlet. Rotary suction pump for ether extraction. 250 Gal glass lined storage tank for ether extracts. 40 Gal aluminum or glass lined still with 8 ft high, 8 in. wide column filled one quarter high with small Raschig rings. Two condensors connected to the still, one for the recovery of ether, another, preferably glass lined, for hydroxycitronellal. Two vacuum pumps. A piston pump to take out water and ether. A rotary oil sealed pump for the distillation of hydroxycitronellal; this pump should be capable of giving 0.5 mm vacuum. Bisulfite Compound In a 650 Gal glass lined tank, charge:

2677 540 114 180

lbs lbs Ibs Ibs

(321 Gal) Water Na2SO; anhydrous, 4.3 moles = 542 H3BOs3, 1.8 moles = 112 Citronellal 85% = 153 Ibs 100%, 1 mole = 154

3511 The detailed operation is as follows: After the water has been metered out, add the sodium sulfite and dissolve with stirring. Note 1. When solution is complete, add the boric acid. Stir until dissolved. The temperature of the solution should be between 20 and 30°C. Note 2. Add the citronellal all at one time, using vigorous continuous agitation. Note 3. After 15 minutes the stirrer is stopped and the mass is allowed to stand for at least 2 hours. Note 4. Acidification The stirrer is started to break up the bisulfite compound into a thin slurry. With the stirrer and the exhaust fan running add:

1200 lbs HCI 20°Bé (31%) = 370 lbs HCI 100%, 10 moles = 365

390

Selected aromatic syntheses

On adding the hydrochloric acid, there is a strong evolution of sulfur dioxide. Stirring is continued until the bisulfite is in solution which normally takes from 5 to 7 hours. Temperature plays an important part in solubilizing the bisulfite compound. Cold weather and cold acid will make this much slower unless the water has been warmed slightly. Note 5. Neutralization

When the solution is completed, soda ash is carefully added until the solution is neutral. This requires about: 300 lbs Na2CO; anhydrous, 2.8 moles = 297

The end point is reached with litmus paper (both red and blue) turns purple (pH = 8.3). Note 6. i On standing a short time an insoluble oil comes to the surface of the neutralized solution. This is skimmed off as carefully as possible and separated in a 5 Gal separatory funnel, the lower layer being returned to the batch. Note 7. The aqueous solution is then washed 3 times with 90 Ibs (15 Gal) isopropyl ether. These extracts are distilled to recover the ether. The residue, about 3 to 4 lbs per batch, is discarded. Hydroxycitronellal Extraction

The washed reaction solution is pumped into a 800 Gal glass lined extraction tank. It is extracted several times with isopropyl ether immediately after the hydroxycitronellal has been liberated by addition of formaldehyde. The quantities for the various extractions are as follows:

ib

5018 312 180 2,3. 2X 132 4. 180 75 5,6,7.3 x 132

lbs Reaction solution, washed lbs i.e. 52 Gal Isopropyl ether lbs Formaldehyde 40% = 72 lbs 100%, 2.4 moles = 72 lbsi.e. 2 x 22 Gal Isopropyl ether lbs i.e. 30 Gal Isopropyl ether lbs Formaldehyde 40% = 30 lbs 100%, 1 mole = 30 lbsi.e. 3 x 22 Gal Isopropyl ether

All extractions are made under agitation, the hydroxycitronellal being immediately taken up with ether. Notes 8 & 9. Stirring is continued for about one minute after the ether layer is thoroughly mixed with the solution. The ether is allowed to separate and is pumped into the storage tank. Note that the fourth extraction is again made after addition of formaldehyde. In total, the extractions use 192 Gal of ether and 255 lbs of formaldehyde. Notes 10 & 11. Distillation

The combined ether extracts are distilled in a glass lined still heated by means of circulating oil. A few ounces of soda ash are put in the still to neutralize any acidity caused by oxidation of the hydroxycitronellal. When ether

Selected aromatic syntheses

391

has stopped distilling, change condensers and apply vacuum from a piston pump to eliminate the last traces of ether and water. Note 12. The oil temperature is then raised to 150-160°C and high vacuum from an oil sealed pump is applied. Note 13. With a vacuum of 5 mm, a first fraction of 23 lbs is collected. As the distillation proceeds, several fractions of good material distill over at 2mm and give a clear bisulfite test. Altogether 105 lbs are collected. As the rate of distillation slows down, the temperature of the oil is increased to 200°C with an additional 5 lbs collecting. A residue of 6 lbs is left in the still. The 5 lb fraction is added to the first 23 lbs and redistilled after sufficient material has accumulated from subsequent batches. This redistillation yields the following fractions:

10% Terpenes A. Showing an insoluble bisulfite test 25% Returned for redistillation. Cloudy bisulfite test 60% Good material. Clear bisulfite test __5% Residue and loss 100 The redistillations yield altogether 80% of good material, or 23 Ibs per batch. The total yield is therefore 128 lbs. Notes

1. Sodium sulfite, anhydrous, U.S.P. is used. This is a high quality photographic grade. 2. Temperature of this reaction does not effect the yield but it makes considerable difference in time of solution in the next operation. 3. The citronellal used is obtained by fractionation of citronella Java. As it deteriorates rather quickly it should be used as soon as possible after distillation. It should not be allowed to stand for any length of time, especially in partly filled drums. 4. Originally the bisulfite compound was allowed to stand for two days. This was necessary when the bisulfite compound was obtained in presence of hydrochloric acid. After boric acid was substituted the time was steadily cut down. Standing for two hours does not lower the yield. 5. It should not be too warm or the bisulfite compound will not precipitate properly. In this case ice is added until precipitation is complete. 6. The shorter the time required for solution the more soda ash is required for neutralization. The neutralized solution does not deteriorate and standing for a long time does not affect the yield. 7. The amount of this skimmed material ranges from ten to twenty-two pounds depending on the quality of the citronellal used. 8. Isopropyl ether rather than ethyl ether is used because of its lower solubility in water and its higher boiling point making for smaller vaporazation losses. It is also cheaper.

392

Selected aromatic syntheses

9. Originally 50 Gal of 25% caustic soda were used instead of formaidehyde. This had the following disadvantages: The extraction had to be done as cold as possible. The ether and caustic soda solution were always cooled to about 0°C. The separation of the ether layer was much slower. As hydroxycitronellal is very sensitive to strong alkali the extraction had to be carried out in the least possible time. 10. With a more efficient extraction method the ether used and the number of extractions made could probably be reduced considerably. Also the quantity of formaldehyde is more than is necessary. 11. The addition of formaldehyde produces a strongly alkaline solution. It is almost impossible to prevent some of this alkaline solution from getting into the ether extract. This is liable to cause some polymerization of the hydroxycitronellal and also corrosion in the aluminum still. It is therefore advisable to have a stirrer in the ether storage tank and stir the ether extracts thoroughly with a small quantity of sodium bicarbonate (about a half pound), to neutralize any free alkali. 12. A piston vacuum pump is used at the beginning as considerable ether vaporizes and would dilute the oil very quickly if an oil sealed pump were used. 13. An oil sealed pump giving a vacuum of 0.5 mm should be used. At this pressure hydroxycitronellal distills at 95°C. Remarks

The total yield of good hydroxycitronellal from 120 lbs of citronellal 85%, averages 85 Ibs. This corresponds to 300 lbs of citronella Java with a content of 40% citronellal. With a more efficient extraction method the yield can be brought to 90 lbs, or 81% of theory. Attempts to improve this yield were unsuccessful. More specifically the formation of terpenes B could not be lowered by changing process conditions. Using sulfuric acid for the hydration instead of hydrochloric acid was also unsuccessful. There are no objections in using hydrochloric acid, except that glass lined rather than stainless steel equipment must be used. On the other hand, the production cost can be somewhat reduced by lowering the percentage of reagents used in excess. Also boric acid can be formed in the reaction from cheaper borax. In making these changes it is important to maintain the same pH (7.5-8.5) and the same specific gravity as in the original process. Assuming the quantities of bisulfite and hydrochloric acid are reduced to half or more, sodium chloride must be added to compensate for the lower specific gravity. An important question is whether the hydration process can be applied to other unsaturated aromatic chemicals. An attempt was made to prepare

hydroxycitral. A first test gave a low yield of an oil of powerful odor similar to irone. This is interesting since the odor of irone has not been duplicated chemically although its constitution was established. Unfortunately, the new material was not isolated.

Selected aromatic syntheses

i] [55]fo] [Se

=

HYDROXYCITRONELLAL

Isopropyl ether

ether

Formaldehyde

«p» Ss

Finished product

Last fraction

Raw Materials for 300 Ibs Citronella Java 40%

Mol Wt 120 360

Ibs

716

Citronellal 85% Na2SO;3

154 126

H;BO;

62

805

HCI 20°Bé

36.5

200

Na2CO;

170 65

Formaldehyde 40% soln Isopropyl ether, loss

Yields 85 lbs is 4 100 50

Hydroxycitronellal Terpenes A Hydroxycitronellal residue Geraniol extra Geraniol for soap

Process Mole ratio

1 4.3 1.8

10

106

2.8

30

3.4

393

394

Selected aromatic syntheses 17. IONONE F. Tiemann and Krueger (1893)

As is well-known, ionone AB is obtained by condensation of citral and acetone. The condensation product (pseudoionone) yields a mixture of w and 6 ionones after cyclization with phosphoric acid:

“SC.CH==CH CO CH; C (CH3)2 Condensation

‘SCH.CHO

ZC (CHs)2

with acetone

ve

eS

Cyclization

Citral (Geranial) cis-form

~

B-lonone

DG Zee

152

aes

— CH CO CH;

C (CHs)2 a-lonone

192

Lemongrass oil, which contains 75% citral, is used for the reaction since

there is no advantage in isolating the citral first. Condensation In a 2 / flask, charge:

310 g Lemongrass oil 73.5% citral = 228 g citral, 1.5 moles 750 g Acetone 100 g Ba(OH)2 10% solution Reflux for 10% acetic NaCl 10% theory. BP

2 hours, maintaining the pH at 8.5. Neutralize with a solution of acid and remove the acetone by distillation. Wash with 3 x 500 ml solution. Vacuum distillation gave 227 g pseudoionone, or 80% of 143-145°C at 12 mm, nD/20°C 1.5334.

Cyclization (Isomerization)

In a 1 / flask, charge: 300 g Pseudoionone, distilled 30 g Phosphoric acid 78% Heat the pseudoionone to 90°C, interrupt heating, and add the phosphoric acid. Reaction sets in at once as indicated by the rise of temperature to 105°C. Maintain at 105-110°C for 2 hours. Cool, let settle for 15 minutes, draw off the acid layer. Wash with dilute soda ash, and fractionate under vacuum. The yield is 250 g ionone AB, or 83% of theory. BP 126-128°C at 10 mm, nD/20°C 1.5050.

Selected aromatic syntheses

395

Notes on Isomerization

1. The isomerization of pseudoionone is very slow below 70°C, and rapid at 150°C. Up to 110°C, the product is very rich in alpha isomer. At 125°C, the content of beta isomer increases noticeably. 2. The reaction proceeds well with 5 lbs phosphoric acid and even with 2 lbs per 1001bs of pseudoionone. A plant batch of 100 lbs was isomerized in half an hour with 2 lbs of H3POx4, 78% at 150°C. 3. Best results are obtained with phosphoric acid. Fair results were obtained with sulfuric acid at 100°C; the product was unexpectedly rich in alpha isomer. 4. The resinification with H3POs, is particularly low when compared to the usual isomerization process with ZnCl,. 5. The duration of the isomerization depends on the temperature. At 150°C half an hour is sufficient, while at 80°C, about five hours are required. Alpha Ionone (White)

Ionone alpha is isolated from the light ionone intermediates which are rich in the alpha isomer. It is valued because it has a finer odor than the beta isomer. The preparation consists in crystallizing the bisulfite compound in a saturated solution of sodium chloride, the beta ionone remaining in the mother liquors. The bisulfite compound is decomposed with sodium hydroxide and the ionone is isolated by extraction or steam distillation. This procedure is identical to the analytical separation of the two isomers. 18. METHYL

IONONE

Haarmann & Reimer (1893)

The reactions involved in the synthesis of methyl ionone are similar to those for ionone AB. These are: 1. Preparation of methyl pseudoionone by condensation of citral and methyl ethyl ketone. 2. Cyclization to form mixtures of methyl ionone isomers. In a 1 / flask, charge:

100 g Lemongrass oil 75%, 0.5 mole 350 g Methyl ethyl ketone 200 g Ba(OH)2 5% aq. solution Heat under gentle reflux for 5 hours. Distill off the excess ketone to 93°C. About 290 g are recovered. Allow the layers to separate and draw off the water. Wash with AcOH 10% solution and water. Vacuum distillation gave 82 g methyl pseudoionone, or 80% of theory. BP 145-180°C at 10mm, nD/20°C 1.5220.

396

Selected aromatic syntheses

The isomerization of methyl pseudoionone follows exactly the same procedure as given for ionone AB. The yield is 83-85% of theory. Four isomers are formed with the main constituent a-n methyl ionone BP 125-126°C at 9mm. 19. JASMYL ACETATE! NONANEDIOL ACETATE E. Fourneau (1932)

Jasmyl acetate is obtained by condensation of 1-octene and formaldehyde according to the reaction of H.J. Prins (1919). Reacting 1-octene, glacial acetic acid, paraformaldehyde in the presence of sulfuric acid yields acetylated 1,3-nonanediol: é CH;3(CH2)s.CH:CH2

+

HO.CH2OH

—> CH;3(CH2)s.CHOH.CH2CH20H

Actually the reaction gives a mixture of acetates. Because of its powerful jasmone-like odor, this product must be used sparingly. The synthesis is accomplished in two steps: 1. Preparation of l-octene by catalytic dehydration of secondary octyl alcohol or 2-octanol:? CH;3(CH2)s;CHOH.CH;

Al,0

——>

CH;(CH2)s;CH:CH,

2-octanol

+

H2O

l-octene

The catalyst used is active anhydrous aluminum oxide, cylindrical pellets 3 x 3 mm for vapor phase reactions. The reaction is carried out at 400°C and is continuous. The yield is 90% of theory. 2. The second step is the condensation mentioned above. It can be assumed that paraformaldehyde in this condensation reacts as an intermediate of formula HO.CH2.SO3H.* After formation of nonanediol, acetylation takes place. Dehydration of 2-Octanol Equipment a) Reaction chamber. The reaction chamber is a vertical stainless steel tube, 10 cm in diameter and 240 cm in length. The tube is filled with the active ‘Remsen Chemical trade name. Better known as Jasmonyl (LG).

2An inexpensive alcohol that is available commercially. 3Supplied by Harshaw Chemical Co, Cleveland, Ohio. 4As in Sommelet reaction for cuminic aldehyde.

Selected aromatic syntheses

397

alumina and is heated to 400°C by means of strip heaters. There are two automatic control thermometers in the tube and the temperature should not vary more than 10°C. The tube is connected to a preheater for the octyl alcohol so that it enters the tube in vapor form. The octyl alcohol is fed by gravity at the rate of 50 ml per minute, controlled with a flow meter. The tube will produce 75 kg of 1-octene in 24 hours. b) Condenser. The 1-octene is condensed in a tubular copper condenser with about fifteen 20 mm tubes, 90 cm long. c) Fractionation still. The fractionation still should have a capacity of 75 Gal, fabricated of aluminum or copper, steam jacketed and fitted with a 35cm diameter packed column 360 cm high. It should be packed with earthernware saddles, or preferably Corning spun glass tower packing. Procedure

Octyl alcohol is run through the tube at the specified rate and the crude octene is collected at the condenser. The crude product is washed and then fractionated under atmospheric pressure. A small fraction of water and light boiling material is obtained up to 115°C (column temperature). The principal fraction boils between 123 and 126°C, nD/20° 1.4135. The yield averages 77 kg from 100 kg octyl alcohol or about 90% of theory. Condensation

In a 125 Gal glass lined jacketed kettle equipped with stirrer and a small reflux condenser, charge:

33 kg Sulfuric acid 66°Bé 220 kg Glacial acetic acid 42.5 kg Paraformaldehyde Mix under agitation until a clear solution is obtained while heating at a temperature not over 100°C. It is important at this point to be certain that there is no undissolved paraformaldehyde at the bottom of the kettle which could cause a violent reaction when the octene is added. Cool the solution to 55°C and slowly add: 110

kg 1-Octene, 1 mole

=

112

This addition takes about one and a half hours, the temperature being kept at 60°C. As soon as the last octene has been added the temperature is increasd to 100°C and kept there for 15 minutes. The reaction is then allowed to cool to room temperature. Two layers will form but both are so dark that it is almost impossible to separate them. It is therefore necessary to add water until the separation can be made. The oil is then washed with water and finally with dilute sodium carbonate until neutral. The crude product should weigh 184 kg.

398

Selected aromatic syntheses

Distillation

The crude jasmy] acetate is fractionated under a vacuum of 2mm or better. This distillation should be done very carefully to obtain a product of highest purity. An efficient column should be used, equipped with a small dephlegmator to provide a reflux ratio of 2 to 1. There is a small fraction of recovered octene, then a fraction of octyl acetate. Intermediate fractions are returned for subsequent distillations. Octyl acetate can be used as such and octene fractions are used in later condensations. As the distillation proceeds, refractive indices are taken as shown in the following typical distillation. Distillation charge: 100 kg

Fraction Fraction Fraction Fraction Fraction Fraction Fraction Fraction Fraction Residue

1 2 3 4 5 6 7 8 9

Column temperature

Vacuum

kg

nD/20°C

Ester value

63°C 76 77 77-100 100 105 107 109 113-115

4mm 3 we 2 2 2 2 7 2

6 4 4 4 13 19 19 11 12 8

1.4160 1.4245 1.4285 1.4460 1.4420 1.4410 1.4400 1.4370 1.4345

80 175 210 250 265 300 325 360 385

There is a fairly wide boiling range since the jasmyl monoacetate distills at a lower temperature than the diacetate. This is indicated by the gradual rise in ester values. The monoacetate has an ester value of 277, whereas the diacetate has an ester value of 460. The refractive index of the bulked material is about 1.4400, and the ester value about 320. 20. PHENYLACETALDEHYDE

DIMETHYLACETAL

E. Fisher ana F. Hoffa (1898)

CsHs.CH2CH(OCHS)2

Acetals are ethers derived from aldehydes. Unlike aldehydes, they are very stable to alkalies, but often weak in odor. In fact, many are odorless. The most useful acetal is phenylacetaldehyde dimethylacetal. The basic material is phenylacetaldehyde which is much used in perfumery, although it polymerizes rather quickly to the dimer. The dimer, however, retains odor but cannot be depolymerized by distillation for the preparation of the acetal. Therefore, only material freshly manufactured should be used.

Selected aromatic syntheses

399

Process

In a 12 / flask, prepare a solution of methanol (100%) containing exactly 2% HCl. Introduce HCl gas (dry) slightly in excess, titrate, and dilute with methanol to bring the concentration to 2%. Adjust the charge to 5 kg. Cool the flask with water, and add slowly 1 kg phenylacetaldehyde. Let stand 48 hours. Heat for 2 hours on the water bath to complete the reaction, keeping the temperature at 60°C, i.e. slightly under the boiling point of methanol. Let cool and neutralize with a solution of NaOH using litmus as an indicator. Add 5 kg of water, that is the same quantity as the methanol, and let separate. Two layers form, the upper layer of methanol 50%, and a lower layer of acetal. Wash several times with water containing 10% sodium chloride to facilitate the separation of the layers since the specific gravity of the acetal is close to 1. Dry the acetal and rectify under vacuum. A small fraction of phenylacetaldehyde distills first (BP 75°C at 5mm), the acetal distilling at 126°C and 5 mm. There is very little residue. The yield from 1 kg phenylacetaldehyde is 1.1 kg acetal, or 80% of theory. The recovered methanol is rectified. It contains almost no acetal. All acetals can be prepared by this method. 21. MENTHOL M. Dumas (1833)

Menthol is now isolated from Brazilian or Japanese peppermint oil. However, the synthesis of menthol from citronellal retains its theoretical as well as practical interest. Two steps are required:

1. Isomerization of citronellal to isopulegol 2. Hydrogenation of isopulegol to menthol: CH,

a

Le

GH

CH CH,

H.C

CH,

H.C

i

—

H.C

‘CHO

CH,

:

uN

a

H.C

CHOH

Ee

H.C

CHOH

i

‘

Vhong

CH; CH.

CH, CH,

Citronellal

Isopulegol

154

(Clsle

HG

+H

re

Hee

A

GH,

Menthol

156

400

Selected aromatic syntheses

Isomerization

In a 250 Gal stainless steel kettle with anchor agitation and a short column, charge: 1000 lbs Citronellal, distilled

50.Ibs Silica gel, E. Merck Co. When charging admit a very slow stream of CO2. Avoid long exposure of the gel to air since this reduces its activity. Heat to 105-110°C, when reaction sets in. Cut off steam, as temperature continues rising to 130-135°C. Maintain this temperature first by cooling, later by heating. After a few hours, start checking the refractive index to record reaction progress. The reaction is completed when the refraction index reaches 1.4720 and the aldehyde content is 2% or lower. This should take about 24 hours, but may vary to 36 hours depending on the activity of the catalyst. Filter through a press, using pressure from CO2. The catalyst can be reused after asddition of 5-10% fresh material.

Hydrogenation In a small autoclave, charge:

500 Ibs Isopulegol 2 lbs Raney catalyst Admit hydrogen at 125-150 Ibs/sq. in. Gradually raise the temperature to 100°C when absorption starts. Control the temperature at 125-135°C by adjusting the rate of hydrogen admission. Agitation must be very good, or the reaction is slow. As the reaction nears completion, raise the pressure to 150 Ibs and the temperature to 150°C until no more hydrogen is absorbed. Let settle the catalyst and filter. Wash with water and distill under vacuum. The fraction at 85-100°C at 8 mm consists mainly of racemic menthol which may be purified by crystallization.

Selected aromatic syntheses

401

22. MUSK AMBRETTE A. Bauer (1891)

The basic raw material for the preparation of musk ambrette is m-Cresol. This is converted into musk ambrette by successive methylation, butylation and nitration: CH;

CH; Me.2SO,

Cl.C(CHs)3

SS

>

OH

OCH;

m-Cresol 108

m-Cresyl methyl ether

t-Butyl chloride 92.5

122

CH;

CH; HNO;

O.N

NO,

—

OCH;

OCH;

C(CHs)s

C(CHs)s

p-t-Butyl-

Musk

3-methoxytoluene 178

ambrette 268

1. Methylation The methylation of m-cresol by means of dimethylsulfate is theoretically simple. Both methyl groups of the sulfate are utilized: CH;

CH; y

+ Me2SO, + 2NaOH

——>

OH

+ Na2SO, + H.0

2 OCH;

The first methyl group reacts at 25°C, the second at 100°C. In a 5 / flask, charge: A 750 g Water 140 g NaOH 95%

324 g m-Cresol FP 11°C, 3 moles B 315 g Dimethyl sulfate, 2.5 moles C 175 g Water 140 g NaOH 95% 216 g m-Cresol, 2 moles

402

Selected aromatic syntheses

Cool the neutralized m-cresol solution A to 25°C. Add the dimethyl sulfate B at the rate of 10g every 15 minutes at 20-30°C. Take all necessary precautions in handling dimethyl sulfate which is extremely toxic. Hold for 2 hours, then add solution C. After this addition, the temperature of the solution is 36°C. Now reflux for 10 hours, let stand another 10 hours and steam distill. The yield is 490 g m-cresyl methyl ether, BP 171-172°C. The residue of the steam distillation gave, after acidification, 40 g of recovered m-cresol. 2. p.t-Butyl-3-Methoxytoluene

This intermediate is obtained by butylation of the cresyl ether with t-butyl chloride by means of a Friedel-Crafts reaction. In a 1 / flask, charge: ; A 366 g m-Cresyl methyl ether, 3 moles 12 g Aluminum chloride, anhydrous powder B 185 g t-Butyl chloride, 2 moles

Stir and cool the mixture A to — 10°C, then add B over 15 minutes. Apply a vacuum of about 60 mm at the start of the addition and hold overnight to remove HCl formed in the reaction. Dilute with ice, separate, wash with salt water and neutralize. The yield of crude is 500 g which gave by distillation 220 g of t-butyl methoxytoluene, boiling range 95-105°C at 10mm. This is a yield of 62% of theory based on t-butyl chloride. 3. p.t-Butyl Chloride This chemical, which is needed in the previous operation, can be obtained as follows. In a 2 / flask, charge:

412 g Hydrochloric acid 20°Bé (31%) 222 g t-Butyl alcohol, 3 moles 180 g Calcium chloride CaCl, flakes Add the butyl alcohol slowly to the hydrochloric acid, keeping the temperature below 30°C. Add the calcium chloride flakes over 10 minutes at 20-25°C. Stir 8 hours and let settle overnight. Separate and distill. The yield is 255 g, or 90% of theory. 4. Nitration

The nitration was conducted as specified in U.S. Patent 2 023 565 (1935) by W.V. Wirth. Results reported in the patent were verified, except for minor differences in the yield and melting point of the musk.

Selected aromatic syntheses Example.

403

In a 2 / flask, charge:

A 195 g B 178 g 260 g C 315 g

Acetic anhydride, 1.5 moles t-Butyl-3-methoxytoluene, 1 mole Acetic anhydride, 2 moles Fuming nitric acid, 5 moles

Cool the acetic anhydride to — 10°C with dry ice. Then, over 2% hours, add simultaneously solution B and acid C, keeping temperature at — 10°C. Hold an additional 1 hour. This will require a total of 1500 g dry ice. Drown in 1100 water and 1700 g crushed ice, filter off the crystalline material, wash and neutralize with 10% sodium carbonate solution. The yield of crude is 250 g. Purification. Take up the crude in 1000 g petroleum naphtha. Reflux for 15 minutes at 70°C, then hold at 40°C for 15 minutes, filter and distill off the naphtha at 5O mm. Reflux the residue for 1 hour with 500 g SD Alcohol 2 B and 2.5 g Darco. Filter and crystallize. Repeat the crystallization without Darco. The yield is 125 g, or 46% of theory. 23. CYCLIC MUSKS ETHYLENE GLYCOL BRASSYLATE W.H. Carothers (1930)

The most commonly used cyclic musks are the following: 1. Ambrettolide, hexadecen-7-olide H.(CH2)sCO CH.(CH2)sO

This musk is found in oil of ambrette seed. 2. Dihydro ambrettolide. This musk is obtained by hydrogenation of the above musk. 3. Pentadecanolide (Exaltolide, Thibetolide) CH?2.(CH2):3.-CO.O

eee |

4. Ethylene glycol brassylate (Musk BR) OC .(CH2)11-€O sie 4

s&,

Of these four musks, the last is the easiest to synthesize. Two methods are available for the preparation of brassylic acid, the basic material. The first starts with azelaic acid, a commercial chemical obtained by oxidation of castor oil. The chain of this acid is lengthened in a series of well-known reactions, the

404

Selected aromatic syntheses

last one of which is a malonic ester condensation that yields brassylic acid on saponification. This can be indicated as follows: HOOC.(CH2)7.COOH

H oak

HOCH.(CH2)7CH2OH

Azelaic acid

itu

1,9-Nonanediol

OOEt Br(CH2)sBr

+

2 CH2

— >

HOOC.(CH2)::.COOH

COOEt 1,9-Dibromononane

Malonic ethyl ester

Brassylic acid

The second synthesis starts with rapeseed oil that is used to isolate erucic acid. This acid is oxidized to brassylic and pelargonic acids by means of potassium permanganate: CH;3(CH2)7CH:CH(CH2):1,\COOH

+

40

= CH;3(CH2);COOH

Erucic acid

Pelargonic acid

338

158

+ HOOC.(CH2)::.COOH Brassylic acid

After esterification of these acids with methanol, methyl brassylate is easily separated by distillation. This is polymerized with ethylene glycol to form long chain polyesters. The final reaction, depolymerization to the monomer, yields the cyclic musk. The detailed operations are as follows. A. Preparation of Rapeseed Oil Fatty Acids

In a 10 / flask, charge:

1500 ml 1200 g_ 500 g 250g

Alcohol SD No. 1 Rapeseed oil Water NaOH

Reflux gently overnight. Add 2 / water, then 320 g sulfuric acid 66°Bé. Separate, wash twice with water. B. Isolation of Erucic Acid

In a S / flask, charge:

600 g Rapeseed fatty acids 1920 g Methanol 240 g Water

Dissolve the rapeseed acids in methanol. Add the water under agitation. Cool to +3°C. After 5to 10 hours, filter at 3°C. Wash crystals with methanol containing water, same proportions as above. Dry at 80°C to constant weight. The yield is 36% by weight. FP 31°C.

Selected aromatic syntheses

405

C. Oxidation of Erucic Acid to Brassylic and Pelargonic Acids

Prepare the following two solutions: A 3600 g Water 36 g Ammonia 29% NH; 208 g Erucic acid 90%, 0.5 mole B 2800 g Water 280 g KMnO,

Note that 1 mole erucic acid requires 4 moles O for complete oxidation. Mix A into B, adding ice to keep the temperature between 30 and 40°C. This requires about 1 hour. Dissolve the MnO, that is formed with 250 g sodium bisulfite, then, over 1 to 2 hours, add a solution of 285 g sulfuric acid

66°Bé and 475 g water. There occurs some foaming until the mass becomes clear white and slightly acid to Congo (pH range 3.0 to 5.0). The crude mixture of acids is filtered off, washed and dried. The yield of crude acids is 210 to 220 g. D. Esterification of the Acids

In a 2 / flask, charge:

210 500 25 100

g g g g

Crude acids Methanol HCl conc. Calcium chloride

Reflux overnight. Dilute with 800 g water, separate the oil, wash free of calcium chloride, and wash with soda ash solution until alkaline (pH about 8.0). The yield of crude methyl esters is 230 g. E. Distilled Methyl Brassylate

The crude esters (230 g) are distilled under vacuum at 2 mm. The following fractions are obtained: i 2 3. 4, 3 Residue

40- 64°C 64- 70 70-150 150-152 152-190

20 g 40 g 8g 90 g 5g 62 g

Lower esters Methyl pelargonate Intermediates Methyl brassylate, FP 28-30°C Intermediates Esters of dihydroxyacids

225g

The yield of methyl brassylate is 44% by weight of erucic acid, or 54% of theory.

406

Selected aromatic syntheses

F. Polymerization

In a 2 / distilling flask with a 45 cm column, charge: 220 g Ethylene glycol, pure 1.5 g Sodium, metallic 300 g Methyl brassylate The sodium must be dissolved, before the methyl brassylate is added. Heat until methanol begins to distill over (iq. temp. 180°C) and continue heating for 2 hours from 180 to 230°C until no more methanol distills and the glycol starts coming over. About 70 g methanol and 5 g glycol are recovered. The residue (440 g) is a clear solution of polymer in excess glycol. Cool to 60°C and add 7 g HCl conc. Test is slightly acid to Congo. Replace the column with a short neck and descending air condenser. Distill off the glycol at 2-3 mm, oil bath temperature to 240°C. About 120 g of glycol is recovered. The yield of polymer is 320 to 330g. It contains some glycol. Acid value is 5 to 10. G. Depolymerization and Distillation Allow the polymer to cool below 100°C, add 3.3 g SnCl2.2 H20, or 1% of the weight of the polymer. Immerse the flask completely in the oil bath to prevent condensation and back flow. Distill using a Megavac pump with dry ice trap. Vacuum should be better than 0.5 mm. As the oil bath is heated from 180° to 265°C, about 40 ml of intermediates are collected. At 270°C (oil bath temperature), the cyclic ethylene glycol brassylate distills for 3 hours at a rate of 70 ml per hour. This rate slows down and the bath temperature has to be increased to 290°C. After 5 hours the rate drops to about 10 ml per hour. The residue, about 50 g, is discarded. The distillate is taken up in ether, filtered to remove a small amount of dimer and is washed with water to remove all glycol and traces of SnCl.. H. Fractionation

The distillate (250 g) is fractionated under vacuum at 2mm maximum. The first and last fractions must be redistilled. The main fraction (200 g) is good material. BP 137-144°C at 2 mm, nD/20°C 1.4752. The yield is 70% of theory.

Selected aromatic syntheses 24. PHENYLETHYL

407

ALCOHOL

B. Radziszewski (1876)

Phenylethyl alcohol is prepared by means of Friedel-Crafts’ condensation of benzene and ethylene oxide. AICI; CoHe

=

H;C—>-CH;

———

CsH;.CH»CH20H

O Benzene

Ethylene oxide

Phenylethyl alcohol

78

44

122

In a 5 / flask with stirrer and cooling bath, charge: A

B_

720 g Benzene, thiophene free

300 g Aluminum chloride, anhydrous 40 mesh 100g Ethylene oxide 1450 g Benzene, thiophene free

Cool mixture A to 15°C. Add solution B over 2% hours. Keep the temperature between 10to 15°C. After addition, stir for half an hour longer. Drown the reaction mixture in 1800 g crushed ice and 600 g water. Stir thoroughly keeping the temperature below 25°C. After all the aluminum chloride is dissolved, separate the benzene, layer, wash with 300 ml of a 2% solution of NaHCO;. Wash with water and distill to recover the benzene. The yield of crude is 150 g. The crude oil contains some phenylethyl chloride that must be eliminated by boiling for several hours with an equal amount of a 5% solution of caustic soda. This should be done with stirring under reflux. Wash neutral and fractionate. There is a 4g first fraction and a last fraction of about 10g. These are returned to the next distillation. A residue of about 8 g of dibenzyl is left in the still. The main fraction (125 g) of phenylethyl alcohol boils at a constant temperature of 104°C at 12 mm. Refractive index nD/20° 1.5300-1.5310. The yield is 85% of theory.

408

Selected aromatic syntheses 25. PINENE AND CAMPHENE

DERIVATIVES

The basic raw material of the pinene derivatives is oil of turpentine which consists mainly of a-Pinene and 6-Pinene:

C7

oa

eel

he

C

G

Say

He ee

| H;C-C-CH;3 H2C

‘ |

Pe H;3C-C-CH, GH

H2C

rie

CH

a-Pinene

st ae

B-Pinene

sa

These formulas are usually written for short as follows:

a-Pinene

G-Pinene

The main product of this series, terpineol, is manufactured in two steps. Pinene is first hydrated to terpin hydrate, and the hydrate is gently dehydrated to terpineol, a mixture of a and @ isomers:

OH

-OH >

OH Terpin hydrate

->

OH a-Terpineol

me B-Terpineol

The a isomer predominates in the mixture but the 8 isomer is the most valuable because of its fine lilac note. Unfortunately, it is difficult to isolate or prepare as a main ingredient. When pinene is treated with glacial acetic acid, terpinyl acetate can be obtained directly without starting with terpineol.

Selected aromatic syntheses

409

The preparation of isobornyl acetate from pinene is more involved since bornyl chloride and camphene must be obtained first:

SD

a-Pinene

HCl

D el NaOH

Bornyl chloride

as AcOH

Camphene

OAc

Hy

Isobornyl acetate

Camphene is manufactured industrially for the production of camphor. Pinene can also be converted to yield simultaneously linalyl and geranyl acetates. The basic material is actually myrcene which is obtained by pyrolysis of 6-Pinene. Although myrcene occurs in several essential oils it is more economical to use the synthetic material. This is treated with hydrogen chloride (gas) to form a mixture of linalyl and geranyl chlorides. The mixture, after acetylation with sodium acetate, forms linalyl and geranyl acetates. Finally, saponification yields the respective alcohols which can be used as such or oxidized to citral. The process is described in various patents, e.g. U.S. Patent 2 871 271 (1954). The reactions are simple, but the separation of the end products is quite difficult because of close boiling range and formation of byproducts. Terpineol.

O. Wallach (1909)

Although terpineol is the most widely used aromatic, little details about its manufacture can be found in the literature. This is particularly true for betaterpineol, the finer perfume grade of terpineol. The basic material is pinene. Turpentine oil is equally suitable, being a mixture of alpha and beta pinene. In a 3 / flask, charge:

400 g Pinene 1000 g H2SO, 30% solution Stir for 48 hours at 25°C. The hydration can be followed by checking the weight increase of the cake. After 24 hours this was 200 g, after 48 hours 300g. This is a 75% yield. The cake of terpine hydrate is separated from the oil by filtration. It can be purified by crystallization in alcohol, or by removing traces of oil by steam distillation. Usually, it is simply washed with dilute alcohol. The solubility of terpine hydrate in alcohol is 7% at 15°C, in water 0.3% at 20°C. The dehydration procedure is as follows. In a 5 / flask, charge: 300 g Terpine hydrate, purified 1800 g Phosphoric acid, 0.2% aq. solution 300 g Toluene

410

Selected aromatic syntheses

Reflux for 9hours. Separate, wash, distill off the toluene and fractionate. The yield is 200 g terpineol. Sulfuric acid 0.2% solution has also been used for this reaction. Terpinyl Acetate.

J. Lafont (1888)

Terpinyl acetate is obtained by reacting pinene with glacial acetic acid. In this reaction, pinene is hydrated and esterified in one step. In a 2 / flask, charge:

A 400 g Glacial acetic acid 80 g ZnCl, anhydrous, powdered B 300 g Pinene

Stir and cool mixture A to 10°C. Then add B over half an hour, maintaining temperature at 11-19°C. Hold at 19°C for one hour, then at 25°C for 2 hours. Add 1/ iced water, separate and neutralize. The yield of crude oil is 350 g (50% ester). Fractionation yields 150 g terpinyl acetate. Direct acetylation of terpineol is unsatisfactory since isobornyl acetate is formed in a side reaction. Isobornyl Acetate.

A. Haller (1889)

Isobornyl acetate is obtained by reacting camphene and glacial acetic acid. This reaction is a direct addition of acetic acid with removal of a carbon bridge. In 1 3 / flask, charge: 900 g Camphene 600 g Glacial acetic acid 40 g Sulfuric acid 66°Bé The sulfuric acid is asdded over 2 hours. Hold 15 hours at 35-36°C. Drown in iced water, separate and neutralize. The crude (1200 g) is fractionated under vacuum and yields 450 g isobornyl acetate 85% and 550 g isobornyl acetate 98% ester. Bornyl Acetate

Bornyl acetate is obtained by esterification of borneol. In a 3 / flask, charge: 1000 g Glacial acetic acid 200 g H2SO,

66°Bé

1000 g Borneol, crude

In mixing the acids, the temperature rises to 34°C. Cool to 20°C and add the borneol over half an hour. Hold at 25°C for 20 hours. Drown in iced water, separate, neutralize and fractionate. The yield is 330 g borneol acetate 85% ester and 400 g bornyl acetate 96% ester.

Chapter VII Outline of Aromatic Syntheses! 1. CARVONE /-Carvone is the main ingredient (70%) of spearmint oil which is widely used as a flavor material. Although carvone could be extracted from this oil by means of the bisulfite compound, it is more economical to prepare it from limonene. The synthesis is achieved in three steps:

1. Addition of nitrosyl chloride CINO to d-limonene. In this reaction the optical rotation changes from +95° to +226°. 2. Conversion of the nitrosochloride to carvoxime. Again this changes the rotation from +226° to —40.3°. 3. Decomposition of carvoxime by steam distillation to form /-carvone, aD/20° —58.8°. The compounds that are formed in this series are the following: Cl

coed

SS Limonene 136

| NOH

SS CINO derivative

NOH

+

SN Carvoxime

O

—

SS Carvone 150

The nitrosyl chloride is prepared in situ at a temperature of +10°C by simultaneous addition of sodium nitrite NaNO, and hydrochloric acid to the limonene. The yield is 80% of theory. The nitrosyl chloride compound that is formed (which is not stable) is immediately boiled in a solution of urea or dimethylformamide in isopropyl alcohol. This converts the limonene nitrosochloride to carvoxime. The progress of the reaction is easily followed by the change in rotation of the solution. The yield is 83% of theory. 'The syntheses of aromatic chemicals that are given under this heading were not fully investigated for publication alongside the main processes. Some were not tested for production, others need improvements in procedures and yields. These preliminary notes should be helpful in correcting these shortcomings.

412

Outline of aromatic syntheses

Finally the carvoxime is decomposed in a steam distillation, maintaining the pH at 0.7 to 0.9. In order to minimize the time of contact of the carvoxime and carvone in the acidic medium, carvoxime is added gradually as a slurry in water. Carvone is steam distilled out as rapidly as it is formed. The yield is 83% of theory. The following procedure is due to R.H. Reitsema as described in J. Org. Chem. 23, 2099 (1958). See also U.S. Patents 2 803 647 and 2 796 428. Limonene Nitrosochloride

A solution of 40.8 g (0.3 mole) of (+)-limonene (aD + 95°) in 40 ml of isopropyl alcohol was cooled below 10°. To this were added simultaneously through separate dropping funnels a solution of 120 ml of concentrated hydrochloric acid in 80 ml of isopropyl alcohol and a concentrated aqueous solution of 20.7 g (0.3 mole) sodium nitrite. The addition was adjusted so as to maintain the temperature below 10°. The mixture was stirred for an additional 15 min and was allowed to stand in the refrigerator for 1 hr. The solid, isolated by filtration, was washed with enough cold ethanol to make a thick slurry to provide a water white product. A small amount of additional solid could be isolated from the mother liquors from the washing by cooling and filtration. A total of 161.4 g (80.7% of theory) of product with a rotation in ethanol of 226° was obtained. Carvoxime

Eight grams of limonene nitrosochloride and 4 ml of dimethylformamide were boiled 30 min under reflux in 25 ml of isopropyl alcohol. The product at the end of this time had a constant negative rotation. It was poured into 150 ml of cracked ice and water, stirred vigorously, and was filtered after the ice was melted. The solid was washed three times with 10 ml of cold water and once with 3 ml of cold isopropyl alcohol. The dry product weighed 5.47 g (83.5%) MP 66-69°, aD —40.3°, and was pure enough for further work. Carvone

A one liter three-necked flask was fitted with a Beckman high temperature glass electrode 8890-15, a reference electrode 8970-92, and outlets which allowed addition of sulfuric acid, addition of oxime, and distillation of waterproduct azeotrope. In the flask was placed 700 ml of water which was brought to boiling, and the pH was adjusted to 0.8 with 3 Nsulfuric acid. About 50 ml of acid was required. Then carvoxime was added dropwise from a separatory funnel in which solid oxime was melted in portions by means of an infrared lamp. Evolution of carvone was nearly instantaneous and the addition was so regulated that the carvone in the still pot could be voided within 5 min. About 1.25 hr were required for the addition. Dilute sulfuric acid was added portionwise during the reaction to maintain the pH at 0.7-0.9. A total of 85 ml of 3N sulfuric acid was used. The product was isolated in a continuous separator and the condensate water returned to the still pot. A total of 18.6 g (83% yield) of white carvone with a rotation of —58.8° was obtained. A similar reaction was run in which solid carvoxime was added through a condenser directly to the still pot without prior melting. The yield was 18.8 g and the rotation again was — 58.8°.

Outline of aromatic syntheses

413

2. CINNAMYL ALCOHOL G. Chazel.

Isolation from Storax (1919)

CeH;.CH:CH.CH,2OH

Cinnamyl alcohol can be extracted on a commercial basis from storax since the chief constituent of this resin is cinnamyl cinnamate. The resin is first treated with caustic soda to extract cinnamic acid and acid resins. A subsequent extraction with toluene yields free and esterified cinnamyl and pheny]lpropyl alcohols. The final residue is saponified, extracted and distilled. In a 5 / flask with efficient agitation, charge: $00 1700 100 500

g g ml ml

Storax Water NaOH 40°Bé (35%) Toluene

Heat for 1 hour under reflux while stirring. Separate the toluene, and repeat two further extractions with 500 ml toluene. Distill off the toluene from the combined extractions. Saponify the residue with 30 g NaOH 40°Bé and 280 ml ethyl alcohol 50% vol, heating the mixture for six hours under reflux. Distill off the alcohol, and extract the residue with 3 x 120 ml toluene at boiling point. Wash the toluene extracts with water and distill off the toluene. The crude cinnamy] alcohol is distilled under vacuum in order to separate the resins which may form 25 to 40% of the mass. Finally, the cinnamyl alcohol is fractionated under vacuum and allowed to crystallize. The mother liquors that separate are sold as phenylpropyl alcohol. The alkaline solutions that were extracted are treated with sulfuric acid to precipitate the cinnamic acid and the acid resins. The residue is dissolved in a boiling solution of 20% sodium carbonate. Sulfuric acid 50% is added to barely neutralize the solution in order to separate the resins. Cinnamic acid precipitates on making the solution strongly acid. The yield from 1000 g storax is 110 g cinnamyl alcohol, 100 g cinnamic acid, and 5 g phenylpropyl alcohol. Cinnamy] alcohol is of course usually prepared by selective hydrogenation of cinnamic aldehyde.

414

Outline of aromatic syntheses

3. COUMARIN W.H. Perkin (1868) Coumarin is obtained by Perkin’s synthesis which is still used today. The process consists in condensing salicylic aldehyde and acetic anhydride in the presence of a small amount of fused sodium acetate. The acetic acid that is formed is distilled off as the reaction proceeds: CHO

CH=CH.CO.O.COCH; OH

OH +

2(CH3;CO)2.0

Salicylic

Acetic anhydride

aldehyde

102

=

+

Intermediate 5

2CH;COOH

Acetic acid

condensate

122 C=

—>

CH O.CO

+

CH3;COOH

Coumarin

146

The condensate splits off acetic acid to form coumarin. The crude coumarin is distilled under vacuum and purified in the following operations: Two crystallizations in ethyl alcohol Vacuum distillation over 0.3% ZnCl, to get a white product Air blowing for five days at 55°C to remove traces of volatile impurities The impurities are in part acetic acid, acetic anhydride, acetyl cresol, chlorocoumarin, salicylic dialdehyde (formed by elimination of water from two hydroxyl groups). Furthermore, traces of remaining salicylic aldehyde are difficult to eliminate because of the odor intensity which is one of the highest. The purification procedure is of such complexity as to make the process unattractive unless a simpler procedure becomes available. Note 1.

Outline of aromatic syntheses

415

Procedure

In a 500 ml flask with slow stirrer, short reflux, and distilling condenser, charge: A

0.3 3 2 20 B_ 0.3 3 122 174 C 30

g g g g g g g g g

Sodium acetate, fused or anhydrous Glacial acetic acid Salicylic aldehyde Coumarin, crude or distilled. Note 2 Sodium acetate Glacial acetic acid Salicylic aldehyde, 1 mole Acetic anhydride, 1.7 moles Acetic anhydride, 0.3 moles

Prepare parts A and B, dissolving first the sodium acetate in the acetic acid. Heat mixture A in the flask to 225°C, and add mixture B at a uniform rate over a period of 3 hours, keeping the temperature at 225-230°C. After a few minutes, acetic acid starts to distill from the top of the reflux condenser. The temperature at the top of the column is 115-116°C. The acetic acid distills through the condenser under atmospheric pressure. As soon as the addition of B is completed, add acetic anhydride C until the column temperature reaches 120°C. About 160 g acetic acid (98%) distills over. When this is collected, the heat is shut off and vacuum put on. The distillation is continued at 60 mm until the temperature at the column reaches 120°C. About 20 g of intermediates are obtained with the following approximate composition: 8 8 0.5 4 20.5

g g g g

Acetic acid Acetic anhydride Acetyl cresol Coumarin

The crude coumarin (170 g) that is left in the flask is distilled under high vacuum, except for the initial 50 g that will be used for the next operation. The following fractions are obtained from a 100 g load. Material

Flask

Column

Vacuum 10 mm

Weight

Acetyl cresol

160°C

140°C

Heads FP 67°C

150

140

4

8

Coumarin

170 210

140

3

85 1

Tails

Residue

2g

4 100

416

Outline of aromatic syntheses

Heads and tails are fractionated to recover coumarin which is purified by crystallization with the main load. The yield from 100 g salicylic aldehyde (100%) is 100 g coumarin perfume grade, or 85% of theory. Notes

1. Since coumarin has a very low vapor pressure, volatile impurities tend to predominate in the odor. Purification through crystallizations cannot be avoided. A similar case arises in the preparation of heliotropine from isosafrole. For the purification of coumarin via the bisulfite coumpound, see literature references in West, Strausz and Barton, Synthetic Perfumes, p 213. 2. In making the batch for the first time, regular coumarin must of course be used. In subsequent batches this is replaced by crude coumarin. After 5 or 6 batches, distilled (but not recrystallized) coumarin is used to avoid accumulation of impurities. 4. DIMETHYLBENZYLCARBINYL

ACETATE

V. Grignard (1900)

Dimethylbenzylcarbinyl acetate is an important aromatic chemical. The basic alcohol must be specially prepared by Grignard’s reaction, but it is otherwise little used because of its faint, although pleasant odor. The odor is greatly enhanced as an acetate. The reactions are as follows:

CsHs.CH.Cl

+ Mg =

Benzyl chloride 127

CoHs.CH.MgCl —> Benzyl magnesium chloride

151 CHs

+

CO

CHs

= CsHs.CH2COMgCl

CH;

O

—

CHs

CsHs.CH:.C.OH

CH;

Acetone 58

CH; Dimethylbenzylcarbinol

150

Dimethylbenzylcarbinol

In a 5 / flask with stirrer, charge: A

100g 1000 g B_ 505 g 400 g C 235g 240 g

Magnesium, 4 moles = 96 Ethyl ether, anhydrous 99% min. Benzyl chloride, anhydrous, 4 moles Ethyl ether, anhydrous Acetone, anhydrous, 4 moles Ethyl ether, anhydrous

cl

+ Mg

OH

Outline of aromatic syntheses

417

To the mixture A in the flask, add about 35 g of the benzyl chloride solution B, and stir until the reaction starts. At this point, cool the flask with water and ice and add slowly the balance of the solution. When all the magnesium is dissolved, cool the flask on ice and salt and add slowly the acetone solution C. Let stand, the temperature rising slowly. Pour on ice, add 440 g sulfuric acid 66°Bé, i.e., sufficiently to dissolve the magnesium. Wash until neutral, distill off the ether, and boil with a solution of 5% soda ash to remove the excess of benzyl chloride. Wash again, and distill under vacuum. BP 110-115°C at 15 mm. The yield is 380 g of pure material, or 64% of theory. See also H.O. House, Modern Synthetic Reactions, W.A. Benjamin, Editor, 2nd Ed., p 817 (1972). Esterification

In a 3 / flask fitted with reflux and distilling condenser, charge: 900 g Dimethylbenzylcarbinol, 6 moles 918 g Acetic anhydride, 9 moles

Heat under reflux for 1 hour, then distill off the acetic acid that formed in the reaction; about 400 g is collected over a period of 4 to 5 hours. The temperature in the liquid rises to 145-150°C,

bur vapors must remain under 120°C, or

the distillation must be slowed. After cooling, wash 4 times with 2 / water, or until the water is neutral. Then wash with very little 5% soda ash solution, and again with water. Distill under high vacuum. BP 120-124°C at 4 mm. The yield is 80% of theory. West, Strausz and Barton, Synthetic Perfumes, recommend addition of 0.6% fused sodium acetate as catalyst. 5. HELIOTROPIN Ciamician and Silber (1890)

Heliotropin is produced on a commercial scale from safrole. This raw material is isolated from camphor oil or preferably from Brazilian sassafras oil which contains 92% safrole. The reaction involves conversion to isosafrole and oxidation to heliotropin: CH,—CH=CH,

CH =CH—CH;

KOH

Bae Oxidation

2

Safrole

162

CHO

2

Isosafrole

162

+ CH,;,CHO

O—CH,

Heliotropin

150

418

Outline of aromatic syntheses

Isomerization

The isomerization of safrole can be achieved almost quantitatively by means of potassium hydroxide in powder form.! In a 3 / flask, fitted with agitation, charge: 1000 g Safrole 50 g KOH, fine pulverized powder

Heat for 10 hours under vacuum and strong agitation to maintain the KOH powder in suspension. The temperature should be kept at 140-150°C with little ebulition and practically no distillation, especially at the beginning. Let stand overnight and wash first with 150 g water, then with salted water (sp gr > 1.2). Dry under vacuum. The yield is 950 g of light amber colored safrole. BP 255°C at 760 mm. Sp. Gr. 1.117. About 10 g of safrole that distilled over is recuperated. The isomerization can also be done in alcoholic solution as described in the literature. However this is slow, and the yield is poor. In contrast, the operation with powdered KOH is simple and quantitative. Oxidation

The oxidation is the critical part of the process. The crude distilled heliotropin that is obtained in the example given below is only 80% pure. The further purification requires a crystallization and a second distillation. This yields a white product that is nearly 100% pure, however the odor is not satisfactory due to traces of isosafrole. Three further crystallizations in alcohol are required. This recalls the conditions described in the process for coumarin, although the odor contamination is milder. What is needed is a better oxidation procedure, or a purification over the bisulfite compound as was suggested for coumarin. Experimental Part In a 5 / reaction flask fitted with agitator, charge:

A 162 g 400 g 10 g 1g B 290 g 400 g 400 g

Isosafrol, 1 mole Water Sulfanilic acid Iron filings Sodium bichromate Na2Cr207.2 H,O Water Sulfuric acid 66°Bé

The addition of sulfanilic acid controls the oxidation, whereas the iron filings increase the yield by 5%. The mixture A in the reaction flask is heated to exactly 54°C, temperature taken in the liquid under agitation. The heating is then stopped and the oxidation mixture B is added over a period of 4 hours. This brings the temperature ‘If unavailable, pulverize KOH dry flakes in Mikropulverizer.

Outline of aromatic syntheses

419

to 56-58°C which must be maintained. If necessary cool. After the introduction is completed, let the temperature fall to 50°C while continuing the agitation. Extract with 160 g toluene, mixing for 5 minutes and decanting. Repeat the extraction with 160 g toluene, but before decanting siphon off the lower layer of chromium oxide Cr203. Distill off the toluene of the combined extractions at atmospheric pressure. Finish under poor vacuum to remove the last traces of toluene. Wash with 5% soda ash solution to separate any piperonic acid that may have formed. Distillation

The crude heliotropin must now be distilled under good vacuum. The flask should be fitted with a cork stopper acting as a safety valve. The thermometer well should be placed 1 cm from the bottom of the flask to control the temperature of the resins at the end of the distillation. These resins should not be overheated. Should this occur, spontaneous release of a considrable volume of gas may take place and blow out the safety valve. Although there is no danger of explosion, a lucite screen should be placed in front of the flask, as should be done for all vacuum distillations. The condenser should be kept at 40°C to prevent obstructions due to crystallization. The first fraction should be collected slowly since it contains nearly all of the unreacted isosafrole. The balance is distilled without fractionation. The yield is 130 g of light brown colored heliotropin, purity 95% as determined with hydroxylamine hydrochloride. Purification

The first distilled crude heliotropin is now cooled to —25°C and left to crystallize. The liquid that is centrifuged off is recycled to the first distillation of the next operation. The crystals are redistilled under vacuum without fractionation. The crystals are white and titrate nearly 100% heliotropin. However, the odor is off due to traces of isosafrole. As mentioned before, several recrystallizations in alcohol are required to eliminate this contamination. Crystallization

Equal parts of heliotropin and alcohol (95%) are dissolved at a temperature of 40°C. The solution is cooled to — 25°C, and after crystallization and centrifugation the yield in crystals is 90% or more. This is repeated at least twice. The mother liquors are redistilled to recover the alcohol, and the residue of heliotropin is recycled in the next operation. The overall yield of heliotropin is 60% based on the weight of safrole. The process can probably be simplified by purification of the crude heliotropin through the bisulfite compound, but recrystallization with alcohol cannot be avoided. Benzene could be used as a solvent, but this is less satisfactory since even at — 15°C the solution retains 50% heliotropin, whereas little remains in

solution with alcohol.

420

Outline of aromatic syntheses

TRIMETHYL

6. ISOCYCLOCITRAL TETRAHYDROBENZALDEHYDE Diels-Alder (1929)

Isocyclocitral is obtained by Diels-Alder’s condensation of crotonic aldehyde and 1,1-dimethyl butadiene-1,3: CH; CH; Seto

PE

i

|

CH

CH; “Sr

- i

= ieth

CH.CHO CH.CH;

Se

cen

CH;

Metacto

apt

CH

ere CH.CH;

Sc,

H,

Dimethyl butadiene

Crotonic aldehyde

Isocyclocitral

The reaction is made in an autoclave at 150°C. Cf. Diels-Alder, Liebig’s Annalen der Chemie, 470, 86 (1929). Isocyclocitral is used for its strong citrus note. It should not be confused with a or 8-cyclocitral which are made according to German Patent 123 747 (1901). Isocyclocitral can be condensed with acetone, resulting in a ionone-like product. However, its odor is weak and may actually be due to traces of unreacted isocyclocitral. 7. METHYL

NONYL

ACETALDEHYDE

G. Darzens (1903)

Methyl nonyl acetaldehyde is prepared by saponification of ethyl methyl nonyl glycidate and subsequent decomposition of the glycidic acid. The ethyl glycidate that is needed for the reaction is prepared from methyl nonyl ketone by means of the procedure that was given for ethyl methyl phenyl glycidate. The reactions can be shown as follows:

CH,

Yeo + Cl.CH;COOC,H,

N20GHe,

C,H»

C,Hi,

Methyl] nonyl ketone

nays

CH

CH;

C,H,

“SC——CH.COOC.H, \o%

Ethyl glycidate

Cl cH coon \o%

Glycidic acid

ts.

CH;

CH.CHO + CO,

CyHi»

Methyl nonyl acetaldehyde

Outline of aromatic syntheses

421

The raw material for methyl nonyl ketone is Algerian or Spanish oil of rue which contains 80 to 90% ketone. A single rectification under vacuum is all that is required to isolate this product. BP 95°C at 15 mm. In a 5 / flask fitted with reflux condenser, charge:

A 2000 g 100 g B_ 680g $10 g

Butyl alcohol, dry Sodium Methyl nonyl ketone, 4 moles Ethylchloroacetate, 4 moles = 490

Heat mixture A in the reaction flask to dissolve the sodium. Then place the flask in a mixture of ice and salt, start agitation and cool to 0°C. Slowly add mixture B taking care that the temperature does not rise above 5°C. After addition, let stand for 48 hours, the temperature rising slowly in the tightly closed flask. Wash 3 times with water and distill off the butyl alcohol under poor vacuum. It is now necessary to determine the saponification value of the crude glycidate, using alcoholic KOH and heating under reflux for two hours. From this value, calculate the quantity of sodium required for saponification. As an example, assume that this is 90 g. Prepare a 6% solution of sodium in butyl alcohol, in this example using 1500 g butyl alcohol and 90 g sodium. As soon as the sodium is dissolved, add the glycidate fairly rapidly, and continue heating the mixture under reflux for 2 hours. Distill off the butyl alcohol at atmospheric pressure. Pour the residue in about 2 liters of water, and extract 3 times with 100 g benzene.

Acidify the glycidate solution with sulfuric acid 40% conc., decant the oil, exhausting the water layer with a little benzene. Wash the oil with water until neutral, dry with anhydrous sodium sulfate. Distill the oil, first using poor vacuum since carbon dioxide is released as the glycidic acid decomposes. Finally, distill the methyl nonyl acetaldehyde between 100to 130°C at 10mm. The yield is 440 g, or about 75% of theory in the first reaction, and 85% in the second.

422

Outline of aromatic syntheses 8. UNDECALACTONE SO-CALLED “ALDEHYDE C 14” E. Blaise and L. Huillon (1905)

Undecalactone is obtained by treating undecylenic acid with sulfuric acid. This causes shifting and hydration of the double bond, and subsequent lactonization of 4-oxyundecylic acid: 10-Undecylenic acid:

CH2:CH.(CH2)s.

COOH

3-Undecylenic acid:

CH:;(CH2)6.CH:CH.CH2.COOH

4-Oxyundecylic acid:

CH3(CH2)s.CH.CH2CH2.COOH

J

Undecalactone:

OH CH;3(CH2)s6CH.CH2CH2.CO

[mache

10-Undecylenic acid is obtained in the pyrolysis of castor oil for the production of commercial heptaldehyde. In a 3 / flask fitted with good agitation, charge:

600 g Undecylenic acid, 80-85% 300 g Sulfuric acid 66°Bé (92%) Cool the flask with water while adding slowly the sulfuric acid. Keep the tem-

perature below 50°C. After all the acid is added, heat slowly to 95-100°C. The reaction mixture becomes black and evolution of SO, is noted. Continue heating for 20 hours and let cool to 50°C. Add 600 g cold water and agitate for half an hour. Allow to settle, siphon

off the water and repeat a second identical washing. Add 500 g toluene and a 10% solution of soda ash until distinctly alkaline. Agitate slowly and heat to 80°C in order to facilitate the separation. Allow to settle. Wash the toluene with water; reaction must remain alkaline, adding soda ash if necessary. Allow to settle. The alkaline waters are extracted with 200 g toluene at 80°C in order to recover some undecalactone. Distill off the toluene in a 500 ml flask at atmospheric pressure up to 130°C. Finally, distill rapidly under high vacuum until the temperature in the liquid reaches 200°C. This gives 240 g crude undecalactone of yellow color and sharp odor. Purification is as follows. Wash with a solution of 5% soda ash, keeping the temperature again at 80°C in order to facilitate the separation. Then wash with a cold solution of 1% NaOH. This last treatment lowers the yield, but extracts all the oxyundecylenic acids. Dry over anhydrous sodium sulfate and fractionate under vacuum over a few flakes of NaOH. The first and last fractions, about one tenth of the total, are blended as intermediates to be redistilled. The balance is pure undecalactone. The yield. from 100 Ibs undecylenic acid (80%) is 32 lbs of undecalactone perfume grade.

Outline of aromatic syntheses

423

Specifications Refractive index nD/20°: Specific gravity 20°C: Saponification value: Acid value:

1.4510 0.9430 307.0 0.4 9. VANILLIN

E. Erlenmeyer, Synthesis from Eugenol (1876)

Although vanillin is now produced from lignin obtained from wood sulfite liquors, its preparation from eugenol after conversion to isoeugenol is still of considerable theoretical interest. A method that was widely used is based on oxidation of isoeugenol with nitrobenzene: CH=CH.CH;

CHO CsHsNO, ——>

OCH;

OCH;

OH

OH

Isoeugenol 164

Nitrobenzene 123

Vanillin 152

Aniline, azobenzene and vanillidene-aniline are formed in the reaction. The isomerization procedure for converting eugenol into isoeugenol has already been given. Assuming that 100 g of oil of clove (or cinnamon leaf) is being processed, the solution of potassium isoeugenolate that is obtained is brought to a total of exactly 320 g by addition of water. Oxidation

In a 1 / flask equipped with a reflux condenser and a separator such as a Bidwell tube, charge:

A 320 60 B 125 145

g g g g

Potassium isoeugenolate solution as specified above Sodium hydroxide, 95% flakes Nitrobenzene Toluene

Heat mixture A to 103°C, then add solution B over 7 hours. During the process, the toluene refluxes and the water is separated rather than returned to the reaction flask. Usually after 1% hours there is a vigorous reaction, the temperature rising to 107°C. If the temperature does not rise, water is withdrawn. This withdrawal is necessary not only to keep the temperature up, but also to cause the proper crystallization of the potassium salt of vanillin when the mixture is cooled. Over 7 hours, about 35 g of water must be withdrawn.

424

Outline of aromatic syntheses

The temperature is kept at 107°C for 5 hours longer with the stirrer running. Cool the reaction mixture while stirring. Filter and wash the cake with toluene until the washings are of a light straw color. About 140 g are needed. The washed cake should weigh 260 g. Extraction In a 2 / flask, charge:

400 g Water

110 g H2SO, 66°Bé 180 g Toluene 260 g Washed cake Heat to 60°C. When the cake is dissolved, continue stirring for 10 minutes. Let stand and separate. Note 1. Repeat the extraction with toluene several times, each with 100 g toluene. Note 2. The toluene extracts are combined and washed with sodium bicarbonate solution. The toluene is distilled off and the residue of crude vanillin (100 g) is vacuum distilled. The boiling point is 150°C at 5 mm. Crystallization The distillate is melted and dissolved in 60 g hot toluene and allowed to crystallize. The crystals are filtered off and washed with 10 g cold toluene. The recovery in this crystallization is about 95%. The crystals are now dissolved in 16times their weight of boiling water. The solution is filtered hot and cooled to 10°C for crystallization. The crystals are washed with a small amount of water and dried. The aqueous filtrate is evaporated to one quarter its volume and yields a second crop of crystals. The average yield is 60 to 65 g. The odor meets the quality standards for vanillin from eugenol. In determining the theoretical yield it should be noted that oil of clove rarely contains more than 72% eugenol, although it may titrate higher because of the presence of other phenols. The yield of vanillin from cinnamon leaf oil (68% eugenol) is slightly lower, but the odor quality remains the same. Notes

1. The water layer contains anilin sulfate and also some nitrobenzene and azobenzene. The aniline and vanillidene-aniline can be recovered. The latter is reoxidized in a subsequent batch. 2. Chloroform is a better solvent since much less is required and separates as a lower layer.

Outline of aromatic syntheses

425

10. TOTAL SYNTHESES OF LINALOOL, LINALYL ACETATE AND CITRAL The basic raw materials for the Hoffmann-LaRoche total syntheses are acetylene and acetone. A series of preliminary reactions yield methylbutenol (3-methyl-1-butene-3-ol, CH2:CH.C(CHs)2) and diketene (CH2:CO)2. When OH these chemicals are reacted (ketonization) they form methylheptenone, a wellknown aromatic ketone that occurs in minor quantities in some essential oils. This ketone is also the key ingredient for the synthesis of linalool as had already been shown in 1919 by Ruzicka and Fornasir. In this reaction, methylheptenone was condensed with sodium acetylide CH = CNa to give dehydrolinalool which was converted into linalool on reduction with sodium in moist ethereal solution. This is shown in the following series of reactions: HC.

C=CH.CH,.CH,.CO.CH;

Hc”

+ CH=CNa

Methylheptenone

CH, HC

|

C=CH.CH,.CH,.C.C=CH

Red

OH Dehydrolinalool Na/moist ether

CH; H3C\

H.C”

|

~=CH._CH.- CH.

©. CH—CGH: OH

Linalool

See Helv. Chim. Acta 2, 182 (1919); also Favorskii et al Chem. Abs. 33, 1298

(1939). The total synthesis of linalool hinges on the preparation of methylheptenone which appears to be of considerable complexity. Perhaps, a simpler synthesis could be achieved by condensing commercially available 3-methyl1,2-butadiene and acetone according to Diels-Adler: CH;

CH;

Om

a

|

CH:

+

co

cf, ‘cH; 3-Methyl1,2-butadiene

Acetone

=%

3

a chi CH,

peer

Sch

cH

Methylheptenone

426

Outline of aromatic syntheses

As can be seen, this reaction is quite similar to Diels-Adler’s synthesis of isocyclocitral from dimethylbutadiene and crotonaldehyde. As for the synthesis of linalyl acetate, it is easily realized by acetylation of dehydrolinalool and subsequent hydrogenation. The synthesis of citral by the Roche process is more complex since it involves a rearrangement of dehydrolinalool. This is shown in the following reactions: CHO

Z

a

Co

Rearrangement ——_____5

ve

me

OH Dehydrolinalool

Citral

| Hydrogenation

OH Linaloo!

See A. Ofner et al J. Org. Chem. 23, 153 (1958).

Appendix Analytical Procedures 1. ANALYSIS OF HYDROGEN

PEROXIDE. IODOMETRIC METHOD

The volumetric determination of hydrogen peroxide consists in titrating the iodine liberated from an acidified solution of peroxide and potassium iodide: H.0,

+

2HI

=

2H2O

+

I,

The iodine liberated is titrated with sodium thiosulfate: 2 Na2S,0;3

+

I. =

Na2S40¢

+

2 Nal

I = Na2S.0; = as = 17.01 Reagents Chloroform Dilute hydrochloric acid (10%) Potassium iodide (powder)

Ammonium molybdate solution Sodium thiosulfate 0.1 N. Fisher reagent Starch solution or thyodene powder indicator, Fisher Cat. No. T-138 Ammonium Molybdate Solution. FMC Method!

To 6.5 g finely ground pure ammonium molybdate (NH4)s6MO7024.4 H20, add 22.5 g ammonium nitrate NH4NOs, 1.5 ml concentrated ammonium hydroxide NH,OH, and 60 ml water. Filter after crystals have dissolved and dilute to 100 ml. Starch Indicator

Stir up 1 g of soluble starch in cold distilled water. Add to 100 ml of boiling distilled water, stir and cool. This solution should be prepared fresh every week, or kept in the refrigerator at 4°C. Fresh indicator must be prepared when the end point of the titration fails to be sharp from blue to colorless. Procedure

Weigh approximately 1 g sample in a 250 ml flask. Add about 10 ml chloroform and swirl to dissolve fats. Add 50 ml water, 15 ml dilute acid and one scoop (about 1 g) potassium iodide. Then add 3 drops ammonium molybdate solution. The solution turns dark due to liberated iodine. 'See also Preparation of Reagents, in Handbook of Chemistry and Physics, The Chemical Rubber Publishing Co.

428

Appendix

Titrate with 0.1 N sodium thiosulfate to a bright amber color. Add several drops of starch solution, or approximately 0.2 g thyodene. Complete titration with 0.1 N sodium thiosulfate to a colorless end point.

% H,O> = LEO®) A = ml sodium thiosulfate used for titration N = Normality of sodium thiosulfate W = Weight of sample in gram

2. ANALYSIS OF HYDROGEN PEROXIDE. POTASSIUM PERMANGANATE METHOD The determination of hydrogen peroxide by the permanganate method is somewhat simpler than by the iodometric method. However, this method should be used only in the absence of oxidizable organic matter. The method is based on the following reaction: 2 KMn0O,

+

5H202

+

3 H2SO,

=

K,SO,

+

2MnSO,

+

8H,O

+

O,

2KMnO. ae Se_H202 at _= to Procedure

Place 2 ml peroxide solution in a 250 ml Erlenmeyer using a 2 ml pipette. Weigh this sample on the analytical scale. Add 20 ml water and 20 ml sulfuric acid 1 N H2SOx,. Heat to 40°C.! Titrate with 0.1 NKMnO, to a faint pink end point that should last 15 seconds.

rec omeauil! LAMN) A N W

= ml potassium permanganate used for titration \ Normality of potassium permanganate = = Weight of sample in gram

3. PEROXIDE STABILITY TEST. FMC METHOD, MODIFIED FOR TESTING PEROXIDE CREAMS Apparatus

Automerse heater for constant temperature bath (95°C); Fisher No. 11-463-14 Small agitator for constant temperature bath Glass jar for heating fluid 15 x 19cm; Fisher Cat. No. 2-525 C 'The titration does not go to completion at room temperature.

Cat.

Appendix

429

Heating fluid: Silicon 200, Dow Corning 12 Test tubes with glass stopper 100 x 13 mm Pyrex No. 9810 T 9; Fisher Cat. No. C 9810-13 Small oven for drying glassware (100°C) Clamps for supporting test tubes and thermometer Pacification of the Test Tubes

Cleanliness of the test tubes is very important. Prior to use, fill the test tubes with nitric acid 10% and let stand for 1 hour. Rinse thoroughly with deionized water and dry in oven at 100°C. Procedure

Place approximately 1 g cream peroxide into the test tube. Transfer is best achieved by means of a small diameter PVC tube, blowing out the cream at the bottom of the test tube. Clamp the test tube in the constant temperature bath so that the cream surface is level with the surface of the bath fluid, to allow maximum reflux. Keep at 95°C for 24 hours while agitating the bath fluid. At the end of this period, transfer and rinse the content of the test tube, while still hot, into a 250 ml flask. Analyze as usual for peroxide content. Final H2O> concentration Initial H2O.2 concentration

% Stability =

Stability test should be run in duplicate. Stability of peroxide cream should be better than 95%.

4. ANALYSIS OF THIOGLYCOLIC ACID IN DEPILATORIES. IODOMETRIC METHOD The volumetric determination of thiglycolic acid is based on oxidation of the acid to dithioglycolic acid: HS.CH2COOH

S.CH2COOH

=a

Oe |

HS.CH2COOH

+ 2HI

S.CH,COOH

I = HS.CH2COOH = 92.11 The determination can be done by titrating directly with 0.1 N Iodine, or the titration can be made with 0.1 N KIO; after addition of KI to the acidified solution: KIO;

J

+ 5KI

_ KIO; ee:

+ 6HCl

=

6KCl

+ 3H20

+ 3I2

= 35.67

The iodine that is liberated reacts as mentioned above.

430

Appendix

Reagents Hydrochloric acid, conc. Potassium iodide (powder) Potassium iodate 0.1 N KIO3;. Fisher reagent Congo Red paper Starch solution or thyodene powder indicator Procedure

Weigh approximately 10 g of depilatory on a watch glass. Transfer to a 500 ml beaker containing 100 ml water. Add 20 ml hydrochloric acid to liberate the thioglycolic acid. Solution should be strongly acid to Congo Red paper. Warm the contents to 60-70°C for 3 minutes and cool to 50°C. Add approximately 1 g of potassium iodide KI. Titrate with 0.1 N KIO3. Before the solution turns slightly amber (due to free iodine), add indicator and complete the titration to a faint lilac color endpoint. The solution is not blue, due to the organic matter that is present. % Thioglycolic acid =

9.211 WwW (A)(N)

A = ml potassium iodate used in the titration N = Normality of potassium iodate W = Weight of sample in gram

5. ANALYSIS OF AMMONIUM THIOGLYCOLATE IN HAIR WAVING PREPARATIONS The ples as mined, Iodine,

volumetric determination of thioglycolic acid follows the same princioutlined for depilatory. After the ammonia content has been deterthe titration of thioglycolic acid can be made directly with 0.1 N or 0.1 N KIO; after acidification and addition of KI.

Reagents Hydrochloric acid 0.1 N. Fisher reagent Methyl Red indicator Iodine 0.1 N. Fisher reagent Starch solution or thyodene powder indicator. Procedure

1. Weigh approximately 2 g sample in a 250 ml flask. Add about 75 ml water and 3 drops Methyl Red indicator. Titrate with 0.1 N hydrochloric acid to end point when color changes from yellow to faint orange.

Appendix

431

A = ml Hydrochloric acid used in the titration N = Normality of hydrochloric acid W = Weight of sample in gram 2. To the above titrated sample, add enough dilute acid to turn the solution to bright pink. Add starch or thyodene powder indicator (about 0.2 g). Titrate with 0.1 N Iodine to dark purple endpoint % Thioglycolic acid = 7) A = ml Iodine used in the titration N = Normality of the iodine W = Weight of sample in gram

6. ANALYSIS OF AMMONIUM

BISULFITE IN HAIR RELAXERS

The volumetric determination of ammonium

bisulfite is based on the fol-

lowing iodometric oxidation: NH.,HSO;

I

+

I, +

_= NH.HSO; Mies

HO

=

NH,4HSO,

+

2 HI

= 49.55

The acidified solution can be titrated directly with 0.1 N Iodine or the titration can be made with 0.1 N KIO; after addition of KI to the acid solution. This releases iodine as was shown for the analysis of thioglycolic acid. Procedure

Weigh approximately 2 g sample in a 250 ml flask. Add 50 ml water and 5 ml glacial acetic acid. Titrate with 0.1 N Iodine. As the endpoint is reached (slow disappearance of the iodine coloration), add starch or thyodene indicator and complete the titration to a blue endpoint. This analysis gives the bisulfite content expressed as NH4HSOs: %

NH4HSO;

=

2m)

A = ml Iodine used in the titration N = Normality of the iodine W = Weight of sample in gram Note that hair relaxers contain added ammonia in addition to the commercial ammonium bisulfite solution that is used in these preparations. The analysis of sodium bisulfite is similar:

% NaHSO;

= ao”)

432

Appendix

7. ANALYSIS OF HYDROQUINONE FORMULARY METHOD

IN CREAMS. NATIONAL

In a 250 ml flask, weigh accurately 4 g of cream. Disperse with about 100 ml water. Add 10 ml 0.1 N sulfuric acid and 10 drops of diphenylamine (1% in EtOH). Titrate with 0.1 N Ceric sulfate! to a violet end point. 1 ml of 0.1 N Ceric sulfate is equivalent to 5.506 mg hydroquinone. Note: This test should be run against a blank that does not contain hydroquinone.

8. ANALYSIS OF ETHYLENE OXIDE IN SURFACTANTS Apparatus

50 ml flask fitted with reflux condenser and gas tube inlet. Procedure

In the 50 ml flask, place 100 to 500 mg of the sample with 5 ml hydroiodic acid (HI, 50-60% active). Reflux for 1 hour at about 140°C, while passing nitrogen through the mixture. After cooling, titrate the iodine that is formed with 0.1 N sodium thiosulfate using starch as an indicator. One mole ethylene oxide liberates 2 I. 1 ml 0.1 N sodium thiosulfate is equivalent to 2.2025 mg ethylene oxide. There are several other analytical methods. None are entirely satisfactory because of poor accuracy or lengthy analytical procedure. A method based on thin layer chromatography (TLC) and high pressure liquid chromatography (HPLC) appears to overcome these limitations. Thin layer chromatography is used to estimate the molecular weight range of the polyglycols that are present. High pressure liquid chromatograms are then determined for the unknown and a similar sample of known composition. After visualization of the developed chromatograms with iodine vapor, the molecular weight of the polyglycols in the sample is estimated by comparison of the spot positions with those of the standard. See Journ. of the Amer. Oil Chemists’ Society 53, 691 (1976), L.P. Turner et al.

The ethylene oxide content is usually given as moles per basic alcohol or it can be obtained from the HLB value which by definition is one-fifth of the percentage of ethylene oxide. For instance, a surfactant with HLB 18 contains 90% of ethylene oxide and 10% lypophilic base. Finally, the degree of ethoxylation can be obtained from the ester value when the qualitative composition is known. For instance, for Arlacel 165 (glyceryl monostearate and POE 100 stearate, according to CTFA) the saponification values are respectively 100, 170 and 10. It is therefore easy to calculate that Arlacel 165 is a mixture of 57% glyceryl monostearate and 43% polyoxyethylene 100 stearate, and that the ethylene oxide content is 40%. 'Certified Fisher reagent

Appendix

433

It would be of interest to synthesize Glyceryl monostearate 5 POE, a product that would have the same saponification value and the same ethylene oxide content as Arlacel 165. This would complete the series of ethoxylated products that is now

available

for beeswax,

lanolin,

sorbitan,

and

other

similar

materials that can be ethoxylated.

9. VISCOSITY MEASUREMENT The viscosity of cosmetic creams is commonly determined by means of Brookfield’s viscometer model RV with helipath.' This instrument consists essentially of a T-bar spindle that penetrates the cream on a helicoidal path, while a viscosity reading is shown on a circular dial divided into 100 units. Knowing the speed of rotation and the type of spindle, a corresponding conversion factor gives the viscosity in centipoise. For cosmetic creams, spindle C is often used at 4 RPM. The dial reading multiplied by a conversion factor gives the viscosity at the temperature of the test. For liquid cosmetics such as shampoos, a cylinder or disk spindle must be used, for instance spindle No. 5 for a speed of 4 RPM. In the oil industry, viscosities are given in Saybolt seconds (SS). These are determined with Saybolt’s viscosimeter at 100°F for mineral oil and 210°F for petrolatum, test method ASTM D 88.

10. SPECIFIC GRAVITY OF CREAMS Specific gravity is an important factor in quality control of creams. Accidental aeration due to mixing or packaging is never desirable but is easily detected since it lowers the specific gravity. This is particularly objectionable when the proper weight cannot be filled because of limited capacity range. Specific gravity is usually determined by means of glass pycnometers. Since these cannot be easily filled with creams, it is best to use Fisher’s aluminum pycnometer? which has a wide opening and allows squeezing out the excess cream. ‘Brookfield Engineering Laboratories, Stoughton, Mass. 2Fisher Catalogue No. 3-247.

434

Appendix

Cooling tunnel (32 ft). A. Cold air duct (2 x 2 ft). B. Blower (3 HP). C. Cooling coils (8). F. Freon line (—25°C). V. Vanes. T. Tunnel entrance.

Four cavity elastomer soap mold. Rectangular plate insert is of copper for better heat transfer. Any print can be engraved on this plate.

Appendix

CONDENSER Pasi ew 1 | | | |

2

= Ri

rile ag arta aeRar Nea

|

|

| | |

|

|

7 eet

VENT atLINES cae a

aoe

|

435

a

|

|

|

TANK

FOR

FOR

SOLVENT

WASHINGS

CONDENSER

EXTRACTOR

RECEIVER

Flavor extraction unit (Schematic). Extractions of spices, herbs and other flavoring materials are often made at ambient temperature and are concentrated at atmospheric pressure. However, final extractions or washings are not concentrated since they are used for initial extractions. True fruit flavors are concentrated under vacuum to prevent spoilage at higher temperature. This requires efficient steam jet vacuum pumps and wide diameter heating coils for fast operation.

436

Appendix

262 050"

40°

50°

60°C

. . . . . . .

Benzyl alcohol Phenylethyl alcohol Phenylpropyl alcohol Methyl anthranilate Isoamyl salicylate Coumarin Vanillin

Chart I. Vapor pressures of some aromatic chemicals. Vapor pressure lines are obtained by plotting log P against 10?/T on semi-logarithmic paper. Data is determined from precise boiling points at 5 and 10 mm Hg. Vapor pressures at 25°C are shown at intersections for this

temperature.

Appendix

437

1000p

100p

. Aldehyde C . . . . . . .

10

P34

33

32

3.1

30

7

Aldehyde C 8 Aldehyde C 9 Aldehyde C 10 Aldehyde C 11, undecylenic Aldehyde C 11, undecylic Methyl nonyl acetaldehyde Aldehyde C 12, lauric

29

2.8

103/T

Chart II. Vapor pressures of some aromatic homologues. Vapor pressure lines can be obtained from single boiling points at 3 mm Hg, when pressure ranges are known for at least one of the homologues. In the chart, these are the lines for aldehyde C 10 and C7. The other lines are parallels drawn through the respective boiling points at 3 mm Hg.

438

Appendix

1600

==

HA+

Citronellal Methyl acetophenone Cinnamic aldehyde Undecalactone

Ethyl methyl phenyl glycidate

TYI

Chart III. Odor intensity at low concentrations in water. Straight lines are obtained by plotting the concentrations against the intensity I on semi-logarithmic paper. The minimum perceptible is shown at I = —10 which by definition is the intensity of a solution of citral at one part per million (1 ppm) in water. The intercepts below 0.1 ppm can be measured on any of the cycles.

Concluding Notes Although cosmetic chemists are constantly searching for new raw materials, few basic changes in formulations can be expected in the near future, except for revisions to comply with ingredient declaration, preference being given to well-defined chemicals rather than compounded specialties. It cannot be stressed too much that these declarations are the sole responsibility of the cosmetic chemist who cannot take for granted adopted names that may be misleading. Manufacturers are fully aware of this and have already revised many component declarations as can be seen in the 3rd Edition of the CTFA Cosmetic Ingredient Dictionary. Accurate information is of course needed for correct declarations as required by law. In the course of time, many ingredients now in use will no longer be available. Foremost among these will be mineral oil, petrolatum and other products of fossil origin that are rapidly being depleted. Far from condemning their use as was recently publicized in a trade magazine, we should be looking for replacements of these highly valuable cosmetic ingredients. The availability of perfume oils is even more critical as the shortage of essential oils becomes more acute due to reduced production and increased cost. We shall have to rely more and more on substitutes. In fact, the essential oil industry is already actively engaged in this work. Not to be forgotten, however, is that many chemicals now in everyday use are derived from coal which is still plentiful but finite in quantity. A return to natural products is inevitable. Hopefully, the source of these invaluable materials will be preserved.

Basic quantitative relations in perfumery (Summary)

1. Intensity relation I = 2.5 log ci This relation defines the intensity level I for a c% solution of aromatic material of absolute intensity i as defined in (2).

The intensity level 5 is defined as the intensity of synthetic citral for c = 100, andi = 1. For two different concentrations

of an aromatic

material,

the relation

gives

I, — I, = 2.5 log2 2

When ‘ = 2.512, I, — 1, = 1, i.e. the difference is one unit of intensity. 2

This allows the definition of all integral intensity levels. 2. Minimum perceptible relation of aqueous solutions @xi=1

The minimum perceptible @ of an aromatic material is defined as its concentration in parts per million (ppm) in water solution that has the same intensity level as an aqueous solution of one ppm citral. This corresponds to 1 = —10 for c = 10°*%. The equation defines the absolute intensity of the aromatics. For citral, i = 1. The mininum perceptible is best determined by extrapolation from several intensity levels at higher concentrations as shown in Chart III. 3. Partial vapor pressure relation for aromatic materials

oe

P ~ 100 This relation gives the partial vapor pressure p of a solution of c% aromatic material of vapor pressure P at 25°C. This relation is valid for mixtures of aromatic products and their solutions in water. 4. Olfactory equilibrium condition

¢ Rii=sc- Pei This equation determines the equivalent (or proportional) weights E of aromatic products in relation to citral for c’ = 100 g, P’ = 50 microns, and

i’ = 1. The equation then takes the form E

=

5000 pi?

—_e

E

—_

5000 P 0

eee

All perfume and flavor formulations in this book are based on these new quantitative relations. 440

Index Page numbers marked with an asterisk (*) indicate formulations; page numbers marked with an "i" indicate an illustration. Italic type page numbers indicate material in tables; boldface page numbers indicate syntheses.

"8 hour" natural lipstick 134, 142* "4711" type cologne 294* "A Suma" type perfume 279* acacia fragrance 301* acetophenone 252, 358 acetyl isoeugenol 254 Activating Cream (Helena Rubinstein) 79 activator,

curling 87 peroxide cream 82 peroxide powder 80, 82 aerosols 10-12 antiperspirant 55, 56, 60* bath spray 10, 13, 15* rapid shave 11 self-heating shave cream 11 shampoos 10, 172, 189* shaving cream 11, 12, 201* shower smoother 15 spray hair net 114* tanning oil 217* after shave 169* gel 204*, 205* lotion 199 after tan lotion 169* Aim toothpaste with fluoride (Lever) 49 "Aimant" type perfume 279* Air Spun Face Powder, ivory tone (beige) (Coty) 152 Alberto Culver VOS hair dressing 110 alcoholic beverages, flavors for 346* aldehydes 25] — violet leaf 25] C14 422 C16 378 C7, C8, C9, C10, C11 undecylenic, C12 lauric 25] aldehydic fragrance 312* aldehydine base 326* Algerian geranium oil 254 p-allyl anisole 253

allyl caproate 373 allyl hexanoate 256, 373

allyl ionone 256 all-purpose cream 33* Allyn s Cream Hair Relaxer (Allyn’s Intemational) 127 Almay Cream Mascara 152 almond fragrance 314* aloe skin freshener 229* Aloe Skin Freshener (Aloe Charm) 226 alpha ionone (white) 395 aluminum chlorhydrate preparations, processing equipment for 56 amber notes 256 ambra base 326* ambrene base 326* ammonium thioglycolate, analysis of 430-431 ammonium bisulfite,

analysis of 431 curling lotion 130* "Amour-Amour" type perfume 279* amyl benzoate 254 amyl caproate 374 amyl cinnamic aldehyde 359-360 amyl hexanoate 374 amyl phenylacetate 253 amy] salicylate 254 amyl undecylenate 255 amylcinnamic aldehyde 254 analysis, of hydrogen peroxide 427-428 of thioglycolic acid 429-430 of ammonium thioglycolate 430-431 of ammonium bisulfite 431 of hydroquinone 432 of ethylene oxide 432 of peroxide 427-428 anethole 253 Angel Face Pressed Powder (Chesebrough-Pond’s) 153 Angel Face powder (ChesebroughPond’s) 152

442

Index

angelica seed oil 255 animal notes 256 anise note 253 oil 253 anisic aldehyde 254, 360-361

anisyl acetate 255 anthranilic note 255 antidandmff shampoos 175 antiperspirants 55-63 aerosol 55, 56, 60*

Bain de Soleil suntan gelée (Charles of the Ritz) 215 Bain de Soleil suntan lotion (Charles of the Ritz) 215 Bain de Soleil suntan oil (Charles of the Ritz) 216 Balm Barr, Cocoa butter formula (Mennen) 25 balm, lip, medicated 139 protective, sun 214, 221*

cream 55-59, 60*, 61* cream deodorant 56

lotion 58 perfumes for 311*-312*

pump spray 60* roll-on 55-58, 61*

solid 59 stick 55, 56, 59, 63* antiseptic gel for tube packaging 83* antiseptic lotion (peroxide lotion) 83* apple blossom perfume 312*, 322* apple flavor 339* apricot flavor, true fruit 332 fragrance 349*

Aqua-fresh fluoride toothpaste (Beecham) 50 armoise 252 aromatics,

stability of 352-356 vapor pressure chart of 436-437 volatility of 231-234 "Arpege" type perfume 279* Arrid antiperspirant cream deodorant (Carter Products) 56 astringents 222 lotion 223, 226*

Avon Delicate Beauty liquid make-up, brown 144 Avon Nail Enamel 223 Avon Pink Beauty lipstick 137 Avon Rich Moisture Hand Cream 21 Avon Smooth as Silk Bath Oil 14 Avon Vita Moist Body Lotion 26

baby shampoos 172, 189* Badedas bath gel (Beecham) 13 Bain de Soleil suntan cream (Charles of the Ritz) 216

perfume 319* Ban antiperspirant cream (BristolMyers) 57 Ban roll-on antiperspirant deodorant (Bristol-Myers) 58 Ban solid antiperspirant (BristolMyers) 59 banana flavor 339* base bois 326* base poivre 327* basic fruit notes 256 basil oil 253 bath gel 13, 73* gelée 73*, 74* oil, floating 13, 15*

oil, foaming 13, 15*, 16* oils 13, 14, 15*, 16* salts, spa 16* bath preparations 13-16 perfumes for 312*-313* Baudecroux lipstick 133 bay oil 254 bay rum fragrance 319* beauty cream 22 beauty masks 226*, 228* bentonite 226* peel-off 228* beeswax cream, conditioning 40* beeswax, conditioning hand lotion with 44* "Bellodgia" type perfume 279* Benedictine, imitation flavor 346* bentonite beauty mask 226* benzaldehyde 25] benzophenone 252, 362-363

benzoylic aromatic note 252

Index

benzyl acetate 253 benzyl alcohol 253 benzyl formate 252 benzyl isoeugenol 254 benzyl propionate 253 benzyl salicylate 253 benzylic note 253 benzylidene acetone 252 bergamot oil 253 imitation 329* beverages, alcoholic, flavors for 346*

Bio-Clear medicated gel (Helena

Rubinstein) 225

bisulfite curling lotions 119, 130* black pepper oil 255 blackberry flavor, true fruit 332 bleach, cream for skin 229* facial cream 81* bleaches, for hair 77-83 for skin 222 bleaching lotion, peroxide 80 blemish cover stick 159* Blistik medicated lip balm (Blistex) 139 "Blue Grass" type perfume 311*, 316*, 322% blush, cream 146, 154, 155 blush make-up gel for tube packaging 167" body lotion 26, 30 bois base 326* "Bois des Iles" type perfume 280* bomeol 253 bomy] acetate 410 bouvardia fragrance 301* brassylic acid 405 Brazilian safrol 252 Breck shampoo 179 Breck shampoo-in hair color 104 Breck wave lotion 122 brilliantine, liquid 109 solid 115* washable 115* bromostyrol 252 bronzing gel 220* broom absolute 255 brush-on hair remover 68 brushless shaving cream 199, 200, 201*, 202*

443

Brylcream (Beecham) 112 bubble bath,

herbal 14 perfumes for 312*-313* powder 16* Bulgarian rose otto 254 butter flavor 345* butter scotch 345* butter-type flavors 345* butyl benzoate 254 p-tert.-butyl chloride 402-403 p-tert. butyl cyclohexyl acetate 252 p-tert.-butyl-3-methoxytoluene 402 butyl salicylate 254 C7 aldehyde 25] C8 aldehyde 25] C9 aldehyde 25] C10 aldehyde 251 C11 aldehyde, undecylenic 25] C12 aldehyde, lauric 25] C14 aldehyde 422 C16 aldehyde 378 "Cabochard" type perfume 280* cade oil 252 cake make-up, sponge application 156* cake mascara 151 calamus oil 255 camphene derivatives 408-410 camphor 253 note 253 caramel artificial flavor 345*

caraway oil 252 cardamon oil 255 Caress soap (Lever Bros.) 210 carnation base, spicy 327* carnation fragrance 302* carrot oil 255 carvacrol 251, 252 carvone 252, 411-412

cascarilla oil 255 "Cashmere" type perfume 322* cassia oil 254 imitation 329* cassia-clove flavor 317* cassia-menthol flavor 317* cassia-peppermint flavor 318* cassie absolute 255 cassie fragrance 301* Castile shampoos 173, 190* castoreum resinoid 256

444

Index

castoreum synthetic base 327* cationic cream hair conditioner 89* lotion hair conditioner 89*, 90* shampoos 173, 190*, 191* cedarleaf oil 252 cedarwood oil 255 cedrol 255 cedryl acetate 255 celery seed oil 255 Cepacol Mouthwash (RichardsonMerrell) 51 Ceylon cinnamon oil 254 imitation 329* Ceylon citronella oil 253 chamomile oil 25] ; "Chanel No. 5" type perfume 280%, 298% 321" Chap Stick Lip Balm (Miller-Morton) 139 cherry flavor 339*-340* true fruit 333 cherry fragrance 349* Chesebrough-Pond 'sAngel Face Pressed Powder 153 Chesebrough-Pond’s Angel Face powder 152 CHR Moisture Creme Concentrate (Revlon) 21 chypre cologne 293* "Chypre" type perfume 280*, 300*, 322° chévrefeuille (honeysuckle) fragrance 303* cineol 251

note 25] cinnamic alcohol 254 cinnamic aldehyde 254, 364 cinnamic note 254 cinnamon leaf oil 255 cinnamon oil 254 Ceylon, imitation 329* cinnamy] acetate 254 cinnamy] alcohol 413 cinnamy] isobutyrate 375 "Cinq Fleurs" type fragrance 298* citral 253, 365-366, 425-426 citral-citronellal notes 253 citronella oil 253, 384 citronellal 253, 384-385 citronellol 254

citronellyl acetate 254 citronellyl oxyacetaldehyde 254, 366— 368 citronellyl propionate 254 citrus note cologne, conventional 294* floral 295* citrus perfume 319* flavors 343* citrus-vanilla (ambrene base) 326* civet imitations base 327* natural 256 synthetic base 327* Clairol Color Foam aerosol hair color 105 Clairol Color Hold 100 Clairol Great Day hair dye for men 100 Clairol Herbal Bubble Bath 14 Clairol Herbal Cream Rinse and Conditioner 85 Clairol Highlights Lotion peroxide bleaching lotion 80 Clairol Quiet Touch peroxide powder activator 80 clary sage oil 253 classification of odors 250, 251-256 Clausius-Clapeyron relation 237 cleanser,

astringent 223 liquid 32 rinse-off 29 skin 30 cleansing cream 17, 34* gel 75*

liquifying 34* without beeswax 17, 34*

clear gel hair conditioner for tube packaging 95* clear liquid gel 73* clear rinse 93* clear shampoos 187*, 188*

two layers 196* clear suntan lotion 217* Clinique, Dramatically Different Moisturizing Lotion (Estee Lauder) 30 Clinique, Extremely Soothing Body Lotion (Estee Lauder) 30 Clinique Amber Cream Blusher (Estee Lauder) 155

Index

Clinique Basic Shampoo (Estee Lauder) 185 clove oil 255 clover (trefle) fragrance 302* clove-cassia flavor 317* cocoa butter conditioner 93* formula for the skin 34* lotion 44* coconut

note 256 flavor 340*

code index aromatic chemicals 266, 268-271 capital letters 267 essential oils 271-273 natural aromatic products 27]—273 volatility of aromatic chemicals 274— 277 volatility of essential oils 274-277 codes used in formulary 265-277 cognac, imitation flavor 346* cola flavor 344* cold cream 20, 33*, 34* cold wave, clear lotion 128*

opaque lotion 128* neutralizer 128* Colgate toothpaste 45, 48 cologne 169* men’s type 297*-298* veil 76* fragrance (for creams) 314* fragrances 293*-300* gel 75* Tusse 295* soap perfume 323* color developer, cream 101 Color Foam aerosol hair color (Clairol) 105 Color Hold (Clairol) 100 color hold shampoo 103 color index 8 Colorsilk ammonia-free hair color (Revlon) 102 Colorsilk cream color developer (Revlon) 102 Colortone hair tinting shampoo, brunette (Helena Rubinstein) 186 compact powder 163* composition of Neo-Fats (Armak) 204

conditioners, conditioning conditioning conditioning 94* conditioning

445

hair 84-96, 89*-96* beeswax cream 40* cream 37*, 38* hair dressings 84, 93*,

hand lotion with beeswax

44*

conditioning shampoos 173, 191*,

192* confectionery rose flavor 347* conventional citrus note cologne 294* cooling tunnel 434i Coppertone suntan cream lotion (Plough) 214 Coppertone tanning oil (Plough) 215 coriander oil 253 cosmetics, fruit flavors for 349* perfumes for 311*-325* costus oil 256 Coty Air Spun Face Powder, ivory tone (beige) 152 coumarin 256, 414-416 Cover Girl cream make-up, ivory brown (Noxell) 145 cover mark 159* cover stick 146 Covermark (Lydia O’Leary) 147 cream, activating 79 all-purpose 33* antiperspirant 57, 59, 60*, 61* beauty 22 beeswax conditioning 40* cleansing 34* cold 33*, 34* conditioning 37*, 38*, 40*

dental 52* emollient 36*, 37* liquid dental 52* moisturizing 35* perfumes for 320* suntan 216, 218*, 219* throat 23 vanishing 38* vitamin E 39* cream activator, peroxide 82* Cream Bleach for the Face (Helena Rubinstein) 79 cream conditioner 91* bleach, facial 81*

446

Index

blush 146, 154, 155 cuticle remover 227* deodorant, antiperspirant 56 eye shadow 159* hair conditioners 84, 89*-92* hair dressing 113 relaxer 127

custard (artificial) flavor 345* cuticle products 222 cuticle remover (cream) 227* cyclamal 372 cyclamen aldehyde 254, 372-373 cyclamen fragrance 302* cyclic musks 403-406

remover 67, 68

straightener 127, 130*, 131* thickeners 86, 87, 94* lotion conditioner 89*, 90*

liquid soap 213* neutralizer 128* shampoo, pearlescent 195* shampoo, opalescent 195* shampoos 174, 182, 192* make-up 145, 147, 158* mascara 151, 152, 161* mascara (brown) 161* perfume 314*, 316* rinse. self-heating 84, 96* translucid, pearlescent 93* rinse and conditioner, herbal 85

rinses, fluid 84, 92*, 93* rouge 154, 155, 164* sachet 170* shampoos 174-175, 193*

skin bleach 229* creams, dental 45 perfumes for 314*-316* specific gravity of 433 vanishing 17, 38* and hand lotions 17-44, 41*, 42* creme color developer 101 creme shampoo, liquid 192* "Crépe de Chine" type perfume 281*, 299* Crest toothpaste (Procter & Gamble) 45,47 p-cresy] acetate 25] p-cresyl methyl ether 25], 361-362 p-cresyl phenylacetate 25] cresylic note 25] CTFA abbreviations 4 cubeb oil 255 cuir base 327* cuminic aldehyde 251, 368-369 curling lotions 119 bisulfite 119, 130*

Dalmatian sage oil 252 "Dans la Nuit" type perfume 281* Delicate Beauty liquid make-up, brown (Avon) 144 dental creams 45, 52* liquid 52*

dentifrices 45-54 ' liquid 46 flavors for 316*—318* deodorants 55-63 cream, antiperspirant 55, 56 perfumes for 311*-312* stick 55-56, 59, 62*, 63* depilatories 64-71, 69*, 70*, 71* fragrances for 318* detergents, perfume for 325* Diane Von Furstenberg Eye Shadow (D.V. F.) 150 dianthus base 327* dimethyl anthranilate 255 dimethyl] benzylcarbinyl acetate 252, 416-417 dimethyl hydroquinone 25] diphenyl oxide 252 Dorothy Gray Depilatory 67 Dorothy Gray Satura Throat Cream 23 dry rouge 165*, 166* dry skin cream 20 dyes, hair 97-108

"Eau de Coty" type cologne 295* eau de quinine fragrance 320* Edge aerosol shaving gel (S.C. Johnson) 10 EFA Shampoo for dry hair, with essential fatty acids (Intemational Playtex) 184 "8 hour", natural lipstick 134, 142*

elastomer soap mold 434i elemi oil 255 Elizabeth Arden loose powder 152 "Emeraude" type perfume 281* emollient cream 36*, 37*

Index

emollient eye balsam 24 emollient lotion 43* emollient gel for tube packaging 73* emulsified hair dressing 115*, 116* emulsions, perfumes for 314*-316* "En Avion" type perfume 282* enamel, nail 223

Enrich henna hair shampoo-in treatment (Ardell) 186 Erase cover mark stick (Max Factor) 146 erucic acid 404 Esoterica Medicated Cream (Norcliff Thayer) 224 essential oils imitations 329*-330* volatility of 234 used in flavors 336 ester interchange 376 ester syntheses 373-377 estragole 253 Eterna "27" beauty cream (Revlon) 22 ethyl chloroacetate 380 ethyl methyl phenyl glycidate 256, 378-380 ethyl phenylacetate 253 ethylene brassylate (cyclic) 256 ethylene glycol brassylate 403-406 ethylene oxide, analysis of 432 eucalyptol 25/ eucalyptus oil 25] eugenol 254, 381-382 note 254 evaporation law 236 evaporometer 233i "Evening in Paris" type perfume 282* extra body perm 121 eye balsam, emollient 24 Eye Cream (Helena Rubinstein) 25 eye shadow, cream 148, 159* pressed powder 149 stick 160* eyebrow pencil, or eyeliner 150 eyeliner 150, 161*

"Fab" detergent type perfume 325* face powder 152-153, 162* facial cream bleach 81* facial creams, 17, 20-25, 35*-38* "Farina" type cologne 294*

447

Fashion Liquid Make-Up, The, brown

(Helena Rubinstein) 145 fashion plate 158* fatty acids, rapeseed oil 404 "Femme" type perfume 282* fennel seed oil 253 "Fétes" type perfume 282* fig flavor 340* filling cosmetic creams 18 fir needle oil, imitation 329*

flavor aromatics, volatility of 337-338 flavor chemicals, vapor pressure of

335-336 flavor extraction unit 435i flavors for alcoholic beverages 346* for dentifrices 316*-318* for mouthwashes 316* for tobacco 347* (fruit) for cosmetics 349* "Fleurs d’Amours" type perfume 283* Flex Balsam shampoo for dry or color treated hair (Revlon) 183 Flex Balsam and Protein shampoo for oily hair (Revlon) 183 Flex Hair Rinse and Conditioner (Revlon) 86 floating bath oil 15* floral bouquet fragrance 314*-315*, 323* floral citrus note cologne 295* floral fragrances 301*-310* floral type perfume 311*, 312* flower notes 255 foaming bath oil 15*, 16* formic note 252 formulary, symbols and codes used in 265-277 "Fougeraie" type perfume 283* "Fougére Royale" type perfume 283* "Fougére" type cologne 296* "Fougeére" type perfume 312*, 321*, S230, fragrance products 168-171 fragrances for depilatories 318* for hair preparations 319*-320* French style perfumes 279*-292* fresh fragrance 315* fresheners, skin 169*, 226, 229*

448

Index

friction pour le bain 169* frosted gel for tube packaging 73* frosty liquid gel 76* fruit flavors 332, 339*-342* for cosmetics 349* fruit notes, basic 256 "Fruit Vert" type perfume 283*

galbanum oil 256 galbanum resinoid 256 gardenia fragrance 303* Gattermann-Koch reaction 369-370 Gay-Lussac’s law 234

gel,

aftershave 204*, 205* antiseptic, for tube packaging 83*

bath 13, 73*, 74* blush make-up for tube packaging 167* bronzing 214, 220*

cleansing 75* clear liquid 73* clear, for tube packaging 110 cologne 75* emollient, for tube packaging 73* frosted, for tube packaging 73*

frosty liquid 76* hair setting 76* medicated 225 peroxide 83* mnging 73*, 95* shaving 205* suntan 214, 219*, 220* tube-packaged 73*, 83*, 95* viscous translucid 75* gels 72-76 hair conditioner (clear) for tube packaging 95* hair relaxer 131* hand lotion 76* shampoos 175, 193*, 194*

shaving 198, 205* gelée, bath 73*, 74* suntan 215 geraniol-citronellol notes 254 geraniol 254, 384-385 geranium oil, Algeria 254 imitation 329* geranium perfume 323*

geranyl geranyl gerany] geranyl Gillette Gillette Gillette

acetate 254, 375 formate 252 phenylacetate 376 propionate 254 aerosol shave cream 11 Lather Shaving Cream 199 super dry roll-on antiperspirant

58 Gillette, Trac II aerosol shaving cream 12 ginger oil 255 ginger ale flavor 344* giroflée fragrance 310* Gleem, fluoride toothpaste (Procter & Gamble) 49 Glo-Fine, Moisturizing Cocoa Butter

Lotion (B&W Formulators) 31 glycerin and rosewater lotion 43* glycerin curling activator 87 glycerin hair conditioner 95* glycerin soaps 206-213 molded 212* grape flavor 340* Great Day hair dye for men (Clairol)

100 green notes 252 green rose type notes 252

green woody type notes 252 grooming preparations, hair 109-116 guaiacwood oil 255 "Habanita" type perfume 284* hair bleaches 77-83 hair color 103 aerosol 105 cream 99 permanent 101 shampoo-in 104 hair conditioners 84-96, 89*-96* clear gel, for tube packaging 95* self-heating 88, 96*

hair curling lotion, heat activated 129* hair dressing 109-110, 114* cream 113 emulsified 115*, 116* gel 72, 76*

hair dyes 97-108 for men 100 lotion 106*, 107*

hair grooming preparations 109-116 hair lotion

Index

conditioner 111

for men 111 hair net, spray 114* hair pomade 116* hair preparations, fragrances for 319*320* hair relaxer, cream 127

gel 131* hair relaxing preparations 117-131 hair remover,

aerosol 12 brush-on 68 cream 67, 68 lotion 67 hair rinse and conditioner 86, 92* hair setting gel 76* hair softener and conditioner 94* hair spray 109, 117* non-aerosol 112 hair straightener, cream 127, 130*, 131* hair thickener 86787, 94*

hair waving preparations 117-131 hand cleaner, waterless 38* hand lotions 17-44, 41*, 42* conditioning, with beeswax 44* gel 76* perfumes for 314*-316* Hazel Bishop lipstick 137 Head & Shoulders Shampoo (Procter & Gamble) 180 heat activated hair curling lotion 129*

heat activated perm 120 Helena Rubinstein, Natural Moisture Cream 23 Helena Rubinstein Skin Life lipstick 139 Helena Rubinstein, The Fashion Liquid Make-Up, brown 145 heliotrope fragrance 303* heliotropin 256, 417-419 Hennalucent shampoo (Ardell) 177 Herbal Cream Rinse and Conditioner (Clairol) 85

herbal base 328* herbal fragrance 313* Herz effusion relation 237 "Heure Bleue" type perfume 284* 2-hexenal 25] cis-3-hexen-1-ol 25]

449

high volatility essential oils 336 Highlights Lotion peroxide bleaching lotion (Clairol) 80 honey base 328* honey note 253 honeysuckle (chévrefeuille) fragrance 303* hyacinth fragrance 303* hyacinth type notes 252 hydratropic aldehyde 252, 386 hydratropic aldehyde dimethy] acetal 252 hydrogen peroxide, analysis of 427-428 stability test 428-429 hydroquinone, analysis of 432 hydroxycitronellal 254, 387-393 hyssop oil 252

ideal gas law 234 "Ideal" type perfume 284* imitation flavors Benedictine 346* cognac 346* rum 346* sherry 346* whisky 346* imitation geranium oil 329* immortelle absolute 255 indol 256 ingredient label declaration 2 intensity of odor 243-248, 251-256 intensity of mixtures of odors 247 Intensive Care lotion (ChesebroughPond’s) 26 ionone 394 (alpha)-ionone (white) 395 ionone note 255 Irish Spring soap (Colgate-Palmolive) 209 isoamy] acetate 25] isoborny] acetate 253, 410 isobutyl phenylacetate 253 isobutylquinoline 255 isocyclocitral 253, 420 isoeugenol 254, 382-383 isojasmone 25] ivory soap perfume 323*-324*

jacinthe fragrance 303* jasmin (or jasmine)

450

Index

absolute 255 fragrance 303*, 321*, 324* type note 253, 254

jasminyl acetate 25] jasmy] acetate 396 Java citronella oil 253 "Je Reviens" type perfume 284* "Jean Naté" type cologne 295* Jellasheen shampoo (Redken) 181 Jergen’s Hand Lotion 27 Jergen’s Lotion for Dry Skin 27 Jheri Redding Milk and Honey Shampoo (Conair) 184 Jhirmack, EFA Shampoo for dry hair, with essential fatty acids (International Playtex) 184 "Jicky" type perfume 285* Jolen Cream Bleach 80 jonquil absolute 255 fragrance 304* "Joy" type perfume 285* juniper berry oil 255 juniper tar oil 252 Kolestral True Hair Conditioner (Wella) 86

fragrance 313*, 349* oil 25] lemongrass oil 253 Lightwaves One-step Softperm by Toni (Gillette) 125 lilac and muguet notes 254 lilac fragrance 305*, 316* Lilt Home Permanent (Procter & Gamble) 122 lime flavor 343* fragrance 349* oil 25] imitation 330* limonene note 25] linalool 253, 425-426 note 253 linalyl acetate 253, 375, 425-426 Line Tamer (Line Tamer) 223 lip balm, chapstick 139 medicated 139 lip gloss, roll-on 143* lip glosser, pan 143* lipsticks 132-143 base 140* Baudecroux 133 natural "8 hour" 134, 142*

label declaration 2 Lashbrite Cream Mascara, black (Del Laboratories) 151 lather shaving cream 199, 200, 202*, ; 203*

lathering skin cleanser 28 lavandin oil 253 lavender absolute 253 cologne 305* fragrance 305*, 313*, 316*, 319*, S21" 7324" note 253 oil 253 imitation 330* lavender spike oil 253 Lavoris Mouthwash (Vick Chemical, Division of Richardson-Merrell) 50 leaf odors 25] leather base 327* lemon flavor 343*

non-staining 132-133 perfumes for 320* staining 140*-141* processing 136 professional 136 transparent 133 liquid creme shampoo 192* liquid dental cream 52* liquid dentifrices 46 liquid make-up 144, 145, 157* liquid sachet 170* liquid soap 208 cream lotion 213* pearlescent 213* Listerine Mouthwash (WamerLambert) 50 Listerine Toothpaste (Wamer-Lambert) 47 "Liu" type perfume 285* L’Oréal cream lotion shampoo 182 L’Oréal Creme Color Developer 101 L’Oréal Extra Body perm 121

Index

L’Oréal Preference permanent hair color 101 lotions,

after tan 169* antiperspirant 58 antiseptic (peroxide) 83* astringent 226* balsam 85 body 26, 30 cocoa butter 44* cold wave 122* conditioning hand with beeswax 44* cream shampoos 174 emollient 43* glycerin and rosewater 43* hair dressing 110 hand 17-44, 41*, 42* hand (gel) 76* moisturizing 28, 30 perfumes for 314*-316* peroxide (antiseptic) 83* suntan 215, 217*, 218* wave 122 lovage oil 255 Love 5 Natural (Mellon) Essence Shampoo (Menley & James) 179 Lustrasilk pearlescent shampoo 181 "Lux Soap" type perfume 324*

"Ma Griffe" type perfume 286*, 299* "Madame Rochas" type perfume 286* magnolia fragrance 306* "Maja" type soap perfume 324* make-up, blush 167* cake, sponge application 156* cream 158* liquid 144, 145, 157* molded 158* perfumes for 320* preparations 144-167 remover 227* maltol 256 mandarin oil 251 imitation 330* maple flavor 345*

mascara, cake 151 cream 151, 152, 161* tablet 161* mask,

451

peel-off 228* beauty 226* Max Factor Cream Puff powder compact 153 Max Factor Erase cover mark stick 146 Max Factor Maxi-Glow Cream Blush 154 Max Factor Pan Cake pressed powder 148 Max Factor Pan Stick, brown 148 Maxi-Glow Cream Blush (Max Factor)

154 Maybelline Maybelline brown Maybelline Maybelline

Cake Mascara, brown 151 Comb-on Cream Mascara, 151 Cover Stick, light 146 Cream Blush, cinnamon brown 146 Maybelline Cream Make-Up, ivory brown 147 Maybelline Eye Shadow Cream, silver blue frost 148 Maybelline Eyebrow Pencil, brown 150 Maybelline Eyeliner, velvet black 150 Maybelline Eyeliner, brown 150 Maybelline lipstick 138

Maybelline Pressed Powder, beige 153 Maybelline Ultra Frost Eye Shadow, blue frost 149 measurement of vapor pressure 238, 251-256 meat flavors 348* medicated lip balm 139 medicated skin cream 224 medicated shampoos 175 medicinal flavor, water-soluble 317*

melon fragrance 349* Mennen AFTA after shave lotion 199 Mennen Brushless Shaving Cream 200 Mennen deodorant stick dry lime 59 Mennen Lather Shaving Cream 200 Mennen Protein "21" shampoo 180 "Men’s Leather" type perfume 299* men’s cologne (French type) 297* men’s type cologne 297*-298* menthol 252, 399-400

menthol-cassia flavor 317* menthone 252 menthyl acetate 252, 376 p-methy] acetophenone 252, 358

452

Index

methyl anthranilate 255 methyl benzoate 252 methyl brassylate 405 methyl cinnamate 254 methyl eugenol 254 methyl heptine carbonate 25] p-methy] hydratropic aldehyde 252 methyl indole 256 methyl ionone 255, 395-396

methyl isoeugenol 254 methyl napthy] ketone 256 methyl nony] acetaldehyde 25], 420— 421 methyl phenylacetate 253 methy] salicylate 252 methyl salicylate flavor 317* methyl salicylate-peppermint flavor 316* methyl salicylate-thymol flavor 317* p-methylquinoline 255 miel base 328* milk bath powder 16* mimosa absolute 255 fragrance 306* minimum perceptible vapor 241, 251256 mint notes 252 miscellaneous cosmetics 222-230 Miss Clairol hair color 103 Miss Clairol color hold shampoo 103 "Miss Dior" type perfume 263*, 286*, 299* "Mitsouko" type perfume 286* mixtures of odors, intensity of 247

Moist Rouge nonpermanent cream rouge (Stein Cosmetic) 154 moisture balsam 29 moisture creme concentrate 21 moisturizing cream 25, 32, 35*

moisturizing lotion 28, 30 moisturizing shampoo 181 mold, soap 207-208, 434i molded glycerin soap 206-213, 212* molded make-up 158* molded soaps 206-213 molding, soap 206-208 "Molyneux No. 5" type perfume 287* "Moment Supreme" type perfume 287* Moon Drops, Emollient Eye Balsam

(Revlon) 24

Moon Drop Moisture Balsam (Revlon) 29 moss and tobacco notes 255 "Moustache" type men’s cologne 297*, 298* mouthwash 50, 51, 53*, 54*

flavors for 316*-318* muguet and lilac notes 254 muguet fragrance 306*, 307* Mum cream antiperspirant (BristolMyers) 59 muscatel note 253 mushroom odors 25] musk ambrette 256, 401-402 musks, cyclic 403-406 "My Sin" type perfume 287*, 300* "Mylord" type perfume 287* myrth oil 256 myrtle oil 253 nail buffing polish 227* nail enamel remover 228* nail products 222 Nair, cream hair remover (Carter Products) 67 naphthylic note 256 "Narcisse Noir" type perfume 288* narcissus fragrance 307* natural "8 hour" lipstick 134, 142* Neet aerosol hair remover (Whitehall Laboratories) 12 Neet, cream hair remover, lemon

scented (Carter Products) 67 Neet, lotion hair remover with cocoa

butter (Whitehall Laboratories) 67 Neo-Fats (Armak), composition of 204 neroli fragrance 307* note 253

oil 253 nerolin 256 neutralizer, clear lotion 128* cream lotion 128* Neutrogena Transparent Soap 209

new mown hay type perfume 312* Nivea, Moisturizing Cream (Beiers-

dorf) 25 2,6-nonadienal 25] nonanediol acetate 25], 396-398

nonolactone 256

Index

non-aerosol hair spray 112 non-permanent cream rouge 154 non-staining lipstick 132-133 nonyl acetate 25] Noxell aerosol shaving cream 12

Noxell Cover Girl cream make-up, ivory brown 145 Noxema Brushless Shaving Cream (Noxell) 200 Noxema Skin Cream (Noxell) 20 Nudit brush-on hair remover (Helena Rubinstein) 68 Nudit cream hair remover for the legs (Helena Rubinstein) 68 Nudit cream hair remover for the face (Helena Rubinstein) 68 Nudit Gentle Skin Lightener with sunscreen (Helena Rubinstein) 225 "Nuit de Noel" type perfume 288* nutmeg oil 255

oak moss absolute 255 octyl acetate 25] Odol Mouthwash 51 odor intensity 243-248, 251-256 of mixtures 247 chart 438 odorimetry 231-256 Odorono antiperspirant cream deodorant (Chesebrough-Pond’s) 56 odors, classification of 250, 251-256 Ogilvie Hair Color cream for tube packaging 99 oil of citronella Java 384 Oil of Olay 28 oils, bath 13-16 hot formula 88 tanning aerosol 217* suntan 214, 216, 221* oleoresins 333-334 olfactory equilibrium 248 olibanol 262* base 328* olibanum oil 256 resinoid 256 opalescent cream lotion shampoo 195* "Ophira" type base 328* opoponax oil 256 orange flavor 343*

453

orange flower absolute 253 fragrance 308*, 318* orange note 255, 256 oil, sweet 25]

orchid note 254 fragrance 308*, 324* L’Oréal cream lotion shampoo 182 L’Oréal Creme Color Developer 101 L’Oréal Extra Body perm 121 L’Oréal Preference permanent hair color 101

"Origan" type perfume 288*, 322* origanum oil 252 Orlane, Paris, Creme Superhydratante B21 24 orris

absolute 255 note 255 palatone 256 palmarosa oil 254 Palmolive aerosol shave (ColgatePalmolive) 11 Palmolive Brushless Shave Cream (Colgate-Palmolive) 199 Palmolive Lather Shave Cream (Colgate-Palmolive) 199 pan lip glosser 143* pan stick, brown 148

Pantene Corrective hair lotion conditioner (Panthenol Division of Hoffmann-LaRoche) 111

Pantene Hair Lotion for Men (Panthenol Division of HoffmannLaRoche) 111 Pantene Shampoo for normal hair (Pantene Division of HoffmannLaRoche) 185 Pantene Supreme (Pantene Division of Hoffmann-LaRoche) 126 papaya fragrance 350* Paraguay petitgrain oil 253 patchouli oil 255 imitation 330* peach flavor 340*-341* fragrance 350* note 256

454

Index

Pearl Drops, Tooth Polish (Carter Products) 51 pearlescent cream rinse 93* pearlescent liquid soap 213* pearlescent shampoos 175, 181 cream lotion 195* translucent 194* peel-off mask 228* pelargone 252 pelargonic acid 405 pennyroyal oil 252 pentadecanolid 256 pepper base 327* (black) oil 255 notes 255 peppermint oil 252 peppermint-methy] salicylate flavor 316* peppermint-cassia flavor 318* Pepsodent toothpaste (Lever) 45, 48 Perfume HC (Haute Couture type) 292" Perfume LA (Light Aldehydic) 292* Perfume WA (Woody Amber) 292* perfumes 168-171 concentration 2 for cosmetics 311*-325* for antiperspirants 311*-312* for bath preparations 312*-313* for bubble baths 312*-313* for creams 314*-316* for deodorants 311*-312* for detergents 325* for emulsions 314*-316* for hand lotions 314*-316* for lipstick 320* for lotions 314*-316* for make-up 320* for powders 321*-322* for shampoos 312*-313* for soaps 322*-325* formulations 278*-330* (French style) 279*-292* stability (in cosmetics) 351 stick, transparent 171* perfumed wax tablets 171* perfumed hair preparations 319*-320* perm, extra body 121 heat activated 120

instant styling for home use 124 soft 125 Perma Strate cream hair straightener (Perma Strate) 127 permanent, home 123

permanent hair color 101 peroxide, analysis of 427-428 bleaching lotion 80 cream activator 82* gel 83* lotion 83* antiseptic 83* powder activator 82* stability test 428-429 Peru resinoid 256 petitgrain oil 253 phellandrene 255 phenylacetaldehyde 252 phenylacetaldehyde dimethy] acetal 252 phenylacetic note 253 phenylacetic acid 253 phenylethy] acetate 254, 374 phenylethy] alcohol 254, 407 phenylethyl formate 252, 374 phenylethy] propionate 254 phenylethylic note 254 phenylpropyl acetate 254 phenylpropyl alcohol 254 phenylpropyl aldehyde 252 PhisoDerm l\athering skin cleanser (Winthrop Laboratories) 28 pimenta berry oil 254 pine fragrance 313*, 325* pine tar conditioner 94* fragrance 313* pineapple flavor 341* note 256 pinene derivatives 408-410 note 25] Pink Beauty lipstick (Avon) 137 pinocamphone 252 poivre base 327*

polish, nail buffing 227* tooth 51 pomade 116*

Index

sun balm (protective) 221* Pond’s Dry Skin Cream (ChesebroughPond’s) 20 Pond 's Cold Cream (ChesebroughPond’s) 20 Porcelana Medicated Skin Cream (Jeffry Martin) 224 powder activator, peroxide 80, 82* powder compact 153, 163* powder, perfumes for 320* pre-electric shave lotion 205* Preference permanent hair color (L’Oréal) 101 Prell concentrated shampoo (Procter & Gamble) 179 Prell shampoo (Procter & Gamble) 178 "Presence" type perfume 289* preservatives 2 Pre-Tan Starter (Germaine Monteil) 31 processing equipment for aluminum chlorhydrate preparations 56 processing lipsticks 136 professional shampoos 176, 196* p-propenyl anisole 253 protective sun balm 214, 221* Protein "21" shampoo (Mennen) 180 prune flavor 341* pump spray, antiperspirant 60* "Quelques Fleurs" type perfume 289*, S15* Quiet Touch peroxide powder activator (Clairol) 80

Rain Tree, Moisturizing Lotion (Noxell) 28 Raoult’s law 235 rapeseed oil fatty acids 404

raspberry

crystals 256 flavor 341* fragrance 350* Rave home permanent (ChesebroughPond’s) 124 raw materials index 5 Redken Moisturizing Shampoo 181 Redken Jellasheen shampoo 181 "Réplique" type perfume 289* reseda absolute 255 fragrance 308*

455

resin notes 256 Revlon Eterna "27" beauty cream 22 Revlon Eye Shadow, shy brown 149 Revlon Flex Balsam shampoo for dry or color treated hair 183 Revlon Flex Balsam and Protein shampoo for oily hair 183 Revlon Flex Hair Rinse and Conditioner 86 Revion Instant Styling Perm for home use 124 Revlon Moon Drop Moisture Balsam 29

Revion’s Super Clean-up astringent cleanser 223 Revlon Super Skin Cleanser 30 thodinol 254 Right Guard roll-on antiperspirant

(Gillette) 57

ringing gel 73*, 95* roll-on antiperspirant 57, 61* lip gloss 143* rose absolute 254 crystals 252 flavor 347* geranium 309* notes 254 otto, Bulgarian 254 perfume 308*, 309*, 316*, 321*, 32>” type note 254 rosemary oil 25] rosewater, glycerin and, lotion 43* rosewood oil 253 Rosy Amber Cream Blusher (Clinique Division of Estee Lauder) 155 rouge, cream 154, 164*

dry 165*, 166* stick (translucent) 167* Rubinstein Rinse-off Cleanser 29 rum, imitation flavor 346* "Rumeur" type perfume 290* russe cologne 295*

Safeguard soap (Procter & Gamble) 209 safrole 25] Brazilian 252

456

Index

sage oil 252 salad flavor 347* Salon Shampoo Concentrate de Pantene (Pantene Division of Hoffmann-LaRoche) 184 "Sandalwood" type men’s cologne

298* sandalwood oil 255 sassafras oil 252 Satura Throat Cream (Dorothy Gray) 23 "Scandal" type perfume 290* Scope Mouthwash (Procter and Gamble) 51 self-heating hair conditioner 96* "Shalimar" type perfume 290*, 300*, . B22 shampoos 172-196 aerosol, 172, 189*

antidandruff 175

baby 172, 189*

basic 172, 187*-188* Castile 173, 190* cationic 173, 190*, 191* clear 182, 187*, 188*

color hold 103 concentrated 179, 184

conditioning 173, 191* cream 174, 175, 178, 193* cream lotion 174 for dry hair, with essential fatty acids 184 for dry or color treated hair 183 gel 175, 193*, 194* liquid creme 192* medicated 175 milk and honey 184 for normal hair 185 for oily hair 183 opalescent cream lotion 195* pearlescent 175, 181 cream lotion 195* perfumes for 312*-313* professional 176, 196* translucent pearlescent 194* two layers 176, 196* shave lotion, pre-electric 205* shaving cream,

aerosol 12, 201* brushless 199, 200, 201*, 202* lather 199, 200, 202*, 203*

lotions 198 shaving gels 198, 205* shaving preparations 197-205 sherry, imitation flavor 346* shower smoother, aerosol 15

Siberian fir needle oil, imitation 329* skin bleaches 222

cream 222, 229* skin cream 200 medicated 224 skin fresheners 169*, 226, 229*

Skin Life lipstick (Helena Rubinstein) 139 skin cleanser 30 lathering 28 skin lightener 225 Smooth as Silk Bath Oil (Avon) 14 smoothers, wrinkle 222, 223, 230 soaps 206-213 cream lotion 213* molded glycerin 206-213, 212* liquid 208 molding 206-208 pearlescent liquid 213* molds 207-208, 434i perfumes for 322*-325* transparent 206-213 sodium bisulfite curling lotions 119, 130* sodium ethylate 380-381 soft drink flavors 344* Softsoap (Minnetonka) 210 solid brilliantine 115* solid sachet 170* Sommelet reaction 371 spa bath salts 16* spearmint oil 252 specific gravity of creams 433

spice type note 254 perfume 311*

spicy carnation base 327* sponge application cake make-up 156* spot stick 159* spray hair net 114* stability of aromatics 352-356 stability test, hydrogen peroxide 428—

429 staining lipstick 140*~141* Stein Cosmetic Moist Rouge nonpermanent cream rouge 154

Index stick, antiperspirant 63*

blemish cover 159* perfume, transparent 171* spot 159* stick deodorant 62*, 63* eye shadow 160* rouge, translucent 167* strawberry

aldehyde 378 flavor 341 *-342* fragrance 350* note 256 styralyl acetate 252 styrax oil 256 Suave clear hair shampoo (Helene Curtis) 182 sun balm, pomade (protective) 221* sun preparations 214-221 suntan lotion, clear 217* suntan cream 218*, 219* lotion 217*, 218* suntan gel 220*

for tube packaging 219* suntan oil 221* suntanning preparations 214-221 Supplegen, All-Day Moisturizing Cream (Germaine Monteil) 32 Supplegen, Liquid Cleanser (Germaine Monteil) 32 sweet notes 256 sweet pea fragrance 310* symbols used in formulary 265-277

"Tabac" type base 328* "Tabac Blond" type perfume 290* tablet mascara 161* tablets, wax perfumed 171* "Tabu" type perfume 291* tanning oil, aerosol 217*

tarragon oil 253 TCB Glycerin Curling Activator pH = 5 balanced (Alberto Culver) 87 terpeny] acetate 253 terpineol 254, 409 terpinyl acetate 410 tetrahydro p-methylquinoline 256 Thermique self-heating hair conditioner (Régime) 88 Thicket cream hair thickener (Madric) 86

457

thioglycolic acid, analysis of 429-430 throat cream 23 thujone 252 note 252 thyme oil 252 thymol 25]-252 thymol-methy] salicylate flavor 317* "Tide" detergent type perfume 325* tobacco flavors 347* tobacco and moss notes 255 Tolu resinoid 256 Toni Lightwaves One-step Softperm

(Gillette) 125 Toni Silkwave home permanent

(Gillette) 123

tooth polish 51 toothpastes 45-50 Top Brass hair thickener (Revlon) 87 Top Brass hair groom (Revlon) 113 "Toujours moi" type perfume 291* Trac II aerosol shaving cream (Gillette) 12 translucid cream rinse 93* translucid gel, viscous 75* translucent stick rouge 167* translucent pearlescent shampoo 194* transparent lipstick 133 transparent perfume stick 171* transparent soaps 206-213 trefle (clover) fragrance 302* Tressemmé, Hot Oil Formula (Alberto Culver) 88 trichloromethyl carbinyl acetate 252 trimethy] tetrahydrobenzaldehyde 253, 420 true fruit flavors 332 blackberry 332 apricot 332 cherry 333 True Hair Conditioner, Kolestral (Wella) 86 tube packaged gel’ 73*, 33°,.95% blush make-up 167* suntan gel 219* wrinkle smoother 230* tuberose absolute 255 fragrance 310* tutti frutti fragrance 350*

458

Index

two-layer shampoos 176 clear shampoo 196*

Ultima II CHR Moisture Creme Concentrate (Revlon) 21 Ultra Ban antiperspirant lotion (BristolMyers) 58 Ultra Max shampoo (Gillette) 178 Ultra Sheen cream shampoo (Johnson Products) 178 Ultra-Brite, Toothpaste (ColgatePalmolive) 48 undecalactone 256, 422-423 vanilla flavor 346* fragrance 350* type flavors 345*-346* vanillin 256, 423-424 vanishing cream 17, 38* vapor, minimum perceptible 241, 25]256 vapor pressure, of aromatics 231, 232, 233 chart 436-437 of flavor chemicals 335-336 measurement of 238, 251-256 Vaseline Intensive Care Lotion (Chesebrough-Pond’s) 26 veil cologne 76* verdyl acetate 252 vertenex 252 vetiver oil 255

vetiver acetate 255 vetiverol 377 vetiveryl acetate 377 "Veto" type perfume 311* Vidal-Sassoon clear shampoo 182 violet leaf aldehyde 251 violet leaves absolute 25] violet fragrance 310* viscosity measurement 433 viscous translucid gel 75* Vita Moist Body Lotion (Avon) 26 Vitabath bath gel (Beecham) 13 Vitalis Clear Gel (Bristol-Myers) 110

Vitalis hair dressing lotion (BristolMyers) 110 vitamin E cream 17, 39* Vitamin E Beauty Cream (Health Savings Center) 22 Vitapointe cream hair dressing

(Clairol) 113 VOS Hair Spray, non-aerosol (Alberto Culver) 112 "Vol de Nuit" type perfume 291*, 300* volatile flavors 25] volatility of aromatics 231-234 of essential oils 234 of flavor aromatics 337-338 wall flower fragrance 310* walnut flavor 342* washable brilliantine 115* water clouding flavor 318* waterless hand cleaner 38* water-soluble medicinal flavor 317* wax tablets, perfumed 171* Wella Conditioner 85 Wella Instant Conditioner balsam lotion 85 Wellaflex hair net (Wella) 111

whisky, imitation flavor 346* "White Shoulders" type perfume 292*, 300* wild cherry flavor 340* Wildroot (Colgate) 112 wisteria fragrance 310* witch hazel fragrance 320* woody base 326* notes 255 wrinkle smoothers 222, 223, 230*

yara-yara 256 ylang ylang oil 255 imitation 330*

"Zibeline" type perfume 292*, 325* Zotos Texture Foam heat activated perm 120

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Micelle Press specializes in books on cosmetics and fragrances and their ingredients. Write for our list of books on these pee

A selection from our range appears below.

A Formulary of Cosmetic Bereta € Cosmetics

Preparations,

Vol.

1:

\.L.L. Hunting Micelle Press, 1991

“

Contains over 250 formulations for decorative products. This first volume in an important new series is the only formulary available devoted exclusivel}

rf decorative

to

cosmetics.

Cosmetic

Preparations,

Vol.

C

A.L. L. M icelle

Hunting oe

E 1993

9

.

7

This volume contains over 570 recipes for cosmetic emulsions. The subjects covered include cold and cleansing creams and lotions, foundation and vanishing creams, night and other emollient creams, moisturizing products, creams and lotions for the hands, face or skin, baby products and

|

}

|

formulations for emulsifying specific ingredients.

Haarmann

|

‘The Perfume Set’

&

besa]

|

published by R. Gléss in two volumes The H&R Book of Perfume (1992) and Fragrance Guide: Feminine Notes, Masculine Notes (1994) 4 : Two beautifullyJ illustrated volumes guide to sacs ‘fragrances, : prosidiesg f a complete gu

am |

| |

from the sources and selection of the raw materials to the final marketing under famous trade names.

|

Natural Ingredients in Cosmetics M. Grievson, J. Barber and A.L.L. Hunting, editors

|

Micelle

Press,

1993

Based on papers read to the May 1989 meeting ofthe Society, of Cosmetic Scientists in London. Topics covered include natural fragrances, herbal extracts, natural colours and a natural deodorant. % Cosmetic Raw Material Analysis and Quality, Vol 1: Hydrocarbons, Glycerides, Waxes and Other Esters

|

H. Butler, editor Micelle

Press,

1994

a]

Published on behalf of the International Federation of Societies of Cosmetic Chemists, this first volume summarizes the many technologies employed for the analysis and quality assessment of certain cosmetic raw materials, specifically

those having a fat-like nature.

N Jature’s Way John

Handbook

of Skin Care

Woodr u ff

\Micelle -'Press,

1992

Commissioned by a UK supplier of cosmetics to the beauty therapy trade, this book deals aa skin conditions and recommended treatments,

aromatherapy

:

and the properties of essential oils, as well as other salon

products.

i”

Encyclopedia 5 I

A.L.L..

Hunting

Micelle

Press,

of Conditioningg Rinse

oe Shampoo

Oo

Press,

|

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T

aS 7 Ingredients ri

1983

/ , , These books contain monographs on individual conditioning rinse and }. ) ] shampoo ingredients and list*the ingredients of‘odactual products. oye:They are 3 ssential reference works for researchers and workers in cosmetics and chemical

laboratories

age

Ingredients

1987 re

Micelle

|

-

and al] interested in hair products.

|

,

|