P. F. Gordon P. Gregory Organic Chemistry in Colour

Transcription

1 P. F. Gordon P. Gregory Organic Chemistry in Colour

2 P. F. Gordon. P. Gregory Organic Chemistry in Colour With 52 Figures and 59 Tables Springer-Verlag Berlin Heidelberg New York London Paris Tokyo

3 Dr. Paul Francis Gordon Mr. Peter Gregory Imperial Chemical Industries PLC Organics Division Hexagon House Blackley, Manchester M9 3DA, U.K. ~~N:~ER ~TVDZ ~lr/of--j Springer study edition is a reprint of the original hard cover edition (Springer-Verlag Berlin Heidelberg 1983) ISBN-13: : / e-isbn-13: Library of Congress Cataloging in Publication Data. Gordon, P. F. (Paul Francis), 1954 ~ Organic chemistry in colour. "Springer study edition." Includes bibliographies and indexes. 1. Dyes and dyelng Chemistry. 2. Chemistry, Organic. I. Gregory, P. (Peter), II. Title. TP9l0.G ' ISBN-13:978-3-S This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically those of translation, reprinting, re-use of illustrations, broadcasting, reproduction by photocopying machine or similar means, and storage in data banks. Under 54 of the German Copyright Law where copies are made for other than private use a fee is payable to "Verwertungsgesellschaft Wort". Munich. by Springer-Verlag Berlin Heidelberg 1987 The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. 2152/

4 Preface The foundations of the chemical dyestuffs industry were laid in 1856 when W. H. Perkin discovered the dye Mauveine. At approximately the same time modern chemistry was establishing itself as a major science. Thus, the chemistry of dyes became that branch of organic chemistry in which the early scientific theories were first used. This early eminence has now been largely lost. In fact, many of our academic and teaching institutions pay little attention to this vitally important branch of organic chemistry. We believe that this book will help to rectify this unfortunate situation. The majority of books that have been published on the subject of dyes have been technologically biased and, in our opinion, do not appeal to the mainstream organic chemist. We have, therefore, aimed at producing a book which emphasises the role of organic chemistry in dyestuffs and we have included appropriate modern theories, especially the modern molecular orbital approaches. We have assumed that the reader possesses a knowledge of the basic principles of organic chemistry;* the only other requirement is a general interest in organic chemistry.** The book should interest the newcomer to chemistry, the established academic, and the dyestuffs chemist himself. We owe a large debt of gratitude to the many people who have helped and encouraged us in the preparation of this book. In particular, we would like to thank Professor C. W. Rees of Imperial College, London, Dr.~J. Griffiths of Leeds University and Dr. R. Price and Mr. B. Parton ofici Organics Division for reading the entire script and passing on their valuable criticisms. We would also like to thank our colleagues within Research Department for their invaluable help. A special thanks must also go to those who aided us in the preparation of the finished manuscript; to Pat Marr and especially Vera Gregory for translating our handwriting into a readable typescript, and to Derek Thorp, Andrew Gordon and Ed Marr for proof-reading. We are grateful to Miss A. Boardman, Miss D. Hutchinson and Mrs. J. Prince for their help * Basic colour physics and colour perception are not included in the book. However, a bibliography for these subjects is provided in Appendix I. ** We had also intended to include a chapter on photographic dyes; however, this was. omitted in order to keep the book to a reasonable length.

5 VI Preface in photocopying the finished manuscript. Finally, we thank Dr. G. Booth who, on behalf of lei Organics Division, gave us access to vital library and secretarial facilities. Blackley, Manchester, U.K. November 1982 Paul Francis Gordon Peter Gregory

6 Table of Contents 1 The Development of Dyes. 1.1 Introduction Pre-Perkin Era - The Natural Dyes Introduction Yellow Dyes Red Dyes Purple Dyes Blue Dyes Black Dyes. 1.3 Perkin and Beyond - The Synthetic Dyes Introduction Perkin's Discovery of Mauveine The Post-Mauveine Era Kekule's Contribution Alizarin Indigo The Introduction of Novel Chromogens. 1.4 Future Trends 1.5 Summary Bibliography Classification and Synthesis of Dyes 2.1 Introduction Classification of Dyes Azo Dyes Anthraquinone Dyes Vat Dyes Indigoid Dyes Polymethine Dyes Aryl-Carbonium Dyes Phthalocyanine Dyes Nitro Dyes Miscellaneous Dyes

7 VIII Table of Contents 2.3 Synthesis of Dye Intermediates Synthesis of Aromatic Carbocycles Synthesis of Aromatic Heterocycles Synthesis of Dyes Azo Dyes Anthraquinone Dyes Vat Dyes Phthalocyanine Dyes Indigoid Dyes Polymethine Dyes Di- and Tri-Arylcarbonium Dyes Summary Bibliography Azo Dyes Introduction Basic Structure of Azo Dyes Tautomerism Tautomerism of Hydroxyazo Dyes - Azo-Hydrazone Tautomerism Hydroxyazo Dyes of the Naphthalene Series Hydroxyazo Dyes of the Benzene Series Tautomerism of Aminoazo Dyes - Amino-imino Tautomerism Protonated Azo Dyes - Azonium-Ammonium Tautomerism Metal Complex Azo Dyes Introduction Medially Metallised Azo Dyes - Nature of the Bonding by the Azo Group Types of Dyes and their Stability Structure and Stereochemistry Conimercial Uses of Metal Complex Azo Dyes Properties of the Metallised Dyes Terminally Metallised Dyes Colour and Constitution 121 '3.5.1 Introduction Early Theories Modem Theories Experimental Observations. Monoazo Dyes 4-Aminoazobenzene Application of VB and MO Theories Protonated Azo Dyes Azo-Hydrazone Tautomers Polyazo Dyes Steric Effects 3.6 Summary Bibliography... Derivatives of

8 Table of Contents IX 4 Anthraquinone Dyes Introduction Structure of Anthraquinone Dyes Tautomerism Tautomerism of Hydroxyanthraquinone Dyes Reduced Hydroxyanthraquinone Dyes - Leuco-Quinizarin Aminoanthraquinone Dyes Reduced Aminoanthraquinone Dyes Protonated and Ionised Anthraquinone Dyes Introduction Anthraquinone Aminoanthraquinone Dyes Hydroxyanthraquinone Dyes Aminohydroxyanthraquinone Dyes Metal Complexed Anthraquinone Dyes Introduction Commercial Dyes Structure and Properties Colour and Constitution Introduction Experimental Results VB/MO Explanation of Colour and Constitution Steric Effects Summary Bibliography Miscellaneous Dyes Introduction Vat Dyes Introduction The Anthraquinonoid Vat Dyes Sulphur-containing Vat Dyes Colour and Constitution of Anthraquinonoid Vat Dyes Indigoid Dyes 'Introduction Structure and Unusual Features of Indigo Colour and Constitution of Indigoid Dyes Other Indigoid Dyes Protonation and Ionisation Commerci,al Indigoid Dyes The Phthalocyanines Introduction The Discovery of the Phthalocyanines Elucidation of the Structure of Phthalocyanine Colour and Constitution of Porphyrins and Phthalocyanines Copper Phthalocyanine Dyes

9 X Table of Contents 5.5 Po1ymethine Dyes Introduction Oxono1s and Merocyanines Cyanine Dyes and their Derivatives Colour and Constitution Di- and Tri-ary1 Carbonium Dyes and their Derivatives Introduction Structural Interrelationships General Colour-Structure Properties Steric Effects Phenolphthalein Heterocyclic Derivatives of Di- and Tri-pheny1methanes Nitro (and Nitroso) Dyes Introduction Nitrodipheny1amine Dyes Nitroso Dyes Summary Bibliography Application and Fastness Properties of Dyes Introduction Textile Fibres - Types and Structures Introduction Natural Fibres Semi-Synthetic Fibres Synthetic Fibres Application and Wet Fastness of Dyes Introduction Physical Adsorption Solid Solutions Insoluble Aggregates within the Fibre Ionic Bonds Covalent Bonds Light Fastness of Dyes Intmduction Test Methods Basic Photochemical Principles Mechanism of Fading Effect of Aggregation on Light Fastness Catalytic Fading Phofotendering of Dyed Fibre Photochromism Heat Fastness of Dyes Bleach Fastness of Dyes Metamerism Solvatochromism

10 Table of Contents XI 6.10 Summary Bibliography 304 Appendix I Appendix II. 306 Author Index. 307 SUbject Index. 310