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.

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1 The Development of Dyes.- 1.1 Introduction.- 1.2 Pre-Perkin Era - The Natural Dyes.- 1.2.1 Introduction.- 1.2.2 Yellow Dyes.- 1.2.3 Red Dyes.- 1.2.4 Purple Dyes.- 1.2.5 Blue Dyes.- 1.2.6 Black Dyes.- 1.3 Perkin and Beyond - The Synthetic Dyes.- 1.3.1 Introduction.- 1.3.2 Perkin's Discovery of Mauveine.- 1.3.3 The Post-Mauveine Era.- 1.3.4 Kekulé's Contribution.- 1.3.5 Alizarin.- 1.3.6 Indigo.- 1.3.7 The Introduction of Novel Chromogens.- 1.4 Future Trends.- 1.5 Summary.- 1.6 Bibliography.- 2 Classification and Synthesis of Dyes.- 2.1 Introduction.- 2.2 Classification of Dyes.- 2.2.1 Azo Dyes.- 2.2.2 Anthraquinone Dyes.- 2.2.3 Vat Dyes.- 2.2.4 Indigoid Dyes.- 2.2.5 Polymethine Dyes.- 2.2.6 Aryl-Carbonium Dyes.- 2.2.7 Phthalocyanine Dyes.- 2.2.8 Nitro Dyes.- 2.2.9 Miscellaneous Dyes.- 2.3 Synthesis of Dye Intermediates.- 2.3.1 Synthesis of Aromatic Carbocycles.- 2.3.2 Synthesis of Aromatic Heterocycles.- 2.4 Synthesis of Dyes.- 2.4.1 Azo Dyes.- 2.4.2 Anthraquinone Dyes.- 2.4.3 Vat Dyes.- 2.4.4 Phthalocyanine Dyes.- 2.4.5 Indigoid Dyes.- 2.4.6 Polymethine Dyes.- 2.4.7 Di- and Tri-Arylcarbonium Dyes.- 2.5 Summary.- 2.6 Bibliography.- 3 Azo Dyes.- 3.1 Introduction.- 3.2 Basic Structure of Azo Dyes.- 3.3 Tautomerism.- 3.3.1 Tautomerism of Hydroxyazo Dyes - Azo-Hydrazone Tautomerism.- 3.3.2 Hydroxyazo Dyes of the Naphthalene Series.- 3.3.3 Hydroxyazo Dyes of the Benzene Series.- 3.3.4 Tautomerism of Aminoazo Dyes - Amino-imino Tautomerism..- 3.3.5 Protonated Azo Dyes - Azonium-Ammonium Tautomerism.- 3.4 Metal Complex Azo Dyes.- 3.4.1 Introduction.- 3.4.2 Medially Metallised Azo Dyes - Nature of the Bonding by the Azo Group.- 3.4.3 Types of Dyes and their Stability.- 3.4.4 Structure and Stereochemistry.- 3.4.5 Conìmercial Uses of Metal Complex Azo Dyes.- 3.4.6 Properties of the Metallised Dyes.- 3.4.7 Terminally Metallised Dyes.- 3.5 Colour and Constitution.- 3.5.1 Introduction.- 3.5.2 Early Theories.- 3.5.3 Modern Theories.- 3.5.4 Experimental Observations. Monoazo Dyes - Derivatives of 4-Aminoazobenzene.- 3.5.5 Application of VB and MO Theories.- 3.5.6 Protonated Azo Dyes.- 3.5.7 Azo-Hydrazone Tautomers.- 3.5.8 Polyazo Dyes.- 3.5.9 Steric Effects.- 3.6 Summary.- 3.7 Bibliography.- 4 Anthraquinone Dyes.- 4.1 Introduction.- 4.2 Structure of Anthraquinone Dyes.- 4.3 Tautomerism.- 4.3.1 Tautomerism of Hydroxyanthraquinone Dyes.- 4.3.2 Reduced Hydroxyanthraquinone Dyes - Leuco-Quinizarin.- 4.3.3 Aminoanthraquinone Dyes.- 4.3.4 Reduced Aminoanthraquinone Dyes.- 4.4 Protonated and Ionised Anthraquinone Dyes.- 4.4.1 Introduction.- 4.4.2 Anthraquinone.- 4.4.3 Aminoanthraquinone Dyes.- 4.4.4 Hydroxyanthraquinone Dyes.- 4.4.5 Aminohydroxyanthraquinone Dyes.- 4.5 Metal Complexed Anthraquinone Dyes.- 4.5.1 Introduction.- 4.5.2 Commercial Dyes.- 4.5.3 Structure and Properties.- 4.6 Colour and Constitution.- 4.6.1 Introduction.- 4.6.2 Experimental Results.- 4.6.3 VB/MO Explanation of Colour and Constitution.- 4.6.4 Steric Effects.- 4.7 Summary.- 4.8 Bibliography.- 5 Miscellaneous Dyes.- 5.1 Introduction.- 5.2 Vat Dyes.- 5.2.1 Introduction.- 5.2.2 The Anthraquinonoid Vat Dyes.- 5.2.3 Sulphur-containing Vat Dyes.- 5.2.4 Colour and Constitution of Anthraquinonoid Vat Dyes.- 5.3 Indigoid Dyes.- 5.3.1 Introduction.- 5.3.2 Structure and Unusual Features of Indigo.- 5.3.3 Colour and Constitution of Indigoid Dyes.- 5.3.4 Other Indigoid Dyes.- 5.3.5 Protonation and Ionisation.- 5.3.6 Commercial Indigoid Dyes.- 5.4 The Phthalocyanines.- 5.4.1 Introduction.- 5.4.2 The Discovery of the Phthalocyanines.- 5.4.3 Elucidation of the Structure of Phthalocyanine.- 5.4.4 Colour and Constitution of Porphyrins and Phthalocyanines.- 5.4.5 Copper Phthalocyanine Dyes.- 5.5 Polymethine Dyes.- 5.5.1 Introduction.- 5.5.2 Oxonols and Merocyanines.- 5.5.3 Cyanine Dyes and their Derivatives.- 5.5.4 Colour and Constitution.- 5.6 Di- and Tri-aryl Carbonium Dyes and their Derivatives.- 5.6.1 Introduction.- 5.6.2 Structural Interrelationships.- 5.6.3 General Colour-Structure Properties.- 5.6.4 Steric Effects.- 5.6.5 Phenolphthalein.- 5.6.6 Heterocyclic Derivatives of Di- and Tri-phenylmethanes.- 5.7 Nitro (and Nitroso) Dyes.- 5.7.1 Introduction.- 5.7.2 Nitrodiphenylamine Dyes.- 5.7.3 Nitroso Dyes.- 5.8 Summary.- 5.9 Bibliography.- 6 Application and Fastness Properties of Dyes.- 6.1 Introduction.- 6.2 Textile Fibres - Types and Structures.- 6.2.1 Introduction.- 6.2.2 Natural Fibres.- 6.2.3 Semi-Synthetic Fibres.- 6.2.4 Synthetic Fibres.- 6.3 Application and Wet Fastness of Dyes.- 6.3.1 Introduction.- 6.3.2 Physical Adsorption.- 6.3.3 Solid Solutions.- 6.3.4 Insoluble Aggregates within the Fibre.- 6.3.5 Ionic Bonds.- 6.3.6 Covalent Bonds.- 6.4 Light Fastness of Dyes.- 6.4.1 Introduction.- 6.4.2 Test Methods.- 6.4.3 Basic Photochemical Principles.- 6.4.4 Mechanism of Fading.- 6.4.5 Effect of Aggregation on Light Fastness.- 6.4.6 Catalytic Fading.- 6.4.7 Phototendering of Dyed Fibre.- 6.5 Photochromism.- 6.6 Heat Fastness of Dyes.- 6.7 Bleach Fastness of Dyes.- 6.8 Metamerism.- 6.9 Solvatochromism.- 6.10 Summary.- 6.11 Bibliography.- Appendix I.- Appendix II.- Author Index.