Geoffrey Hallas

The Chemistry and Application of Dyes

1. Introduction: The Evolution of Present-Day Dye Technology.- I. Background.- II. The Historical Development of Synthetic Dyes.- A. The Early History up to 1865.- B. Developments in Dye Chemistry from 1865 to Modern Times.- III. The Development of Color and Constitution Theory.- References.- 2. Classification of Dyes by Chemical Structure.- I. Introduction.- II. Azo Dyes.- A. Basic structure.- B. Synthesis.- C. Tautomerism.- 1. Azo/Hydrazone Tautomerism.- 2. Azo/Imino Tautomerism.- 3. Azonium/Ammonium Tautomerism.- D. Metallized Azo Dyes.- E. Carbocyclic Azo Dyes.- F. Heterocyclic Azo Dyes.- III. Anthraquinone Dyes.- A. Basic structure.- B. Synthesis.- C. Tautomerism/Metal Complexes.- D. Properties.- IV. Benzodifuranone Dyes.- V. Polycyclic Aromatic Carbonyl Dyes.- VI. Indigoid Dyes.- VII. Polymethine and Related Dyes.- A. Azacarbocyanines.- B. Hemicyanines.- C. Diazahemicyanines.- VIII. Styryl Dyes.- IX. Di- and Tri-Aryl Carbonium and Related Dyes :.- X. Phthalocyanines.- XI. Quinophthalones.- XII. Sulfur Dyes.- XIII. Nitro and Nitroso Dyes.- XIV. Miscellaneous Dyes.- XV. Summary.- References.- 3. Dyes for Cellulosic Fibers.- I. Introduction.- II. Fiber Reactive Dyes.- A. Historical Development.- B. Reactive Systems.- C. Chromogens in Reactive Dyes.- 1. Azo Reactive Dyes.- 2. Anthraquinone Reactive Dyes.- 3. Phthalocyanine Reactive Dyes.- 4. Triphenodioxazine and Formazan Reactive Dyes.- III. Direct Dyes.- A. Azo Direct Dyes.- 1. Monoazo Dyes.- 2. Disazo Dyes.- 3. Trisazo Dyes.- 4. Metal Complex Dyes.- 5. Mixed Chromophore Dyes.- B. Aftertreatments.- C. Triphenodioxazine dyes.- IV. Azoic Dyes.- V. Vat Dyes.- A. Anthraquinone Vat Dyes.- B. Fused Ring Polycyclic Vat Dyes.- C. Indigoid Vat Dyes.- VI. Sulfur Dyes.- A. Sulfurized Vat Dyes.- VII. Syntheses of Reactive Dyes.- A. Analysis of Dyes and Intermediates.- B. Methods of Diazotization.- C. Coupling Methods.- D. Synthetic Examples of Reactive Dyes.- VIII. Synthesis of Direct Dyes.- A. Synthetic Examples of Direct Dyes.- IX. Synthesis of Vat Dyes.- A. Synthetic Examples of Vat Dyes.- X. Synthesis of Sulfur Dyes.- A. Synthetic Examples of Sulfur Dyes.- Acknowledgments.- References.- 4. Dyes for Polyester Fibers.- I. Introduction.- II. Anthraquinone Dyes.- A. Preparative Index.- B. Discussion.- III. Methine Dyes.- A. Preparative Index.- B. Discussion.- IV. Nitrodiphenylamine Dyes.- A. Preparative Index.- B. Discussion.- V. Azo Dyes.- A. Preparative Index.- B. Discussion.- 1. Diazonium Components.- 2. Coupling Components.- 3. Dyes.- VI. Miscellaneous Classes.- A. Preparative Index.- B. Discussion.- References.- 5. Dyes for Polyacrylonitrile.- I. Introduction.- II. Pendant Cationic Dyes.- A. Yellow dyes.- 1. Miscellaneous Chromogens.- 2. Azopyridone Dyes.- B. Red Dyes.- C. Blue Dyes.- 1. AzoDyes.- 2. Anthraquinone Dyes.- D. Miscellaneous Cationic Groups.- III. Delocalized Cationic Dyes.- A. Comparison with Pendant Dyes.- B. Protonated Azo Dyes.- C. Yellow Dyes.- 1. Azacarbocyanines.- 2. Diazacarbocyanines.- 3. Triazacarbocyanines.- D. Red Dyes.- 1. Hemicyanines.- 2. Diazahemicyanines.- E. Blue Dyes.- 1. Oxazines.- 2. Thiazines.- 3. Triphenylmethanes.- 4. Naphtholactams.- 5. Diazahemicyanines.- IV. Synthesis.- A. Pendant Cationic Dyes.- 1. Azopyridone Yellow.- 2. Azobenzene Red.- 3. Anthraquinone Blue.- B. Delocalized Cationic Dyes.- 1. Azacarbocyanine Yellow.- 2. Diazacarbocyanine Yellow.- 3. Triazacarbocyanine Yellow.- 4. Hemicyanine Red.- 5. Diazahemicyanine Red.- 6. Oxazine Blue.- 7. Triphenylmethane Green.- 8. Naphtholactam Blue.- 9. Diazahemicyanine Blue.- V. Summary.- References.- 6. Dyes for Polyamide Fibers.- I. Introduction.- II. Dyes for Wool and Other Animal Fibers.- A. Historical.- B. Acid Dyes.- 1. Azo Dyes.- 2. Chrome Mordant Dyes.- 3. Metallized Dyes.- a. 1:1 Complexes.- b. 2:1 Complexes.- 4. Anthraquinone Acid Dyes.- 5. Miscellaneous Dyes.- a. Vat Dyes.- b. Xanthene Dyes.- c. Triphenylmethane Dyes.- d. Nitro Dyes.- e. Reactive Dyes.- f. Phthalocyanine Dyes.- III. Dyes for Nylon.- IV. Synthesis of Dyes.- A. CI Acid Yellow 19.- B. CI Acid Red 57.- C. CI Acid Orange 67.- D. CI Acid Yellow 76.- E. CI Acid Orange 3.- F. CI Mordant Yellow 8.- G. CI Mordant Red 7.- H. CI Mordant Orange 6.- I. CI Acid Red 249.- J. CI Acid Black 60.- K. CI Acid Blue 129.- L. CI Acid Green 25.- M. Coumarin Acid Dye.- N. Phthalocyanine Acid Dye.- References.- 7. Application of Dyes.- I. Introduction.- A. Classification of Dyes and Pigments.- B. Textile Fibers.- 1. Mass Pigmentation.- 2. Gel Dyeing.- 3. Loose State Dyeing.- 4. Yarn Dyeing.- 5. Fabric Dyeing.- 6. Garment Dyeing.- C. Dyeing Methods.- 1. Immersion (Exhaustion) Methods.- 2. Impregnation-Fixation Methods.- D. Fastness of Dyed Textiles.- II. Dyeing of Wool.- A. Nonmetallized Acid Dyes.- 1. Azo.- 2. Anthraquinoid.- 3. Triphenylmethane.- 4. Dissolving the Dyes.- 5. Dyeing Behavior.- B. Mordant Dyes.- 1. Anthraquinone.- 2. Azo.- 3. Triphenylmethane.- 4. Xanthene.- 5. Dissolving the Dyes.- 6. Dyeing Behavior.- C. Metal-Complex or Premetallized Dyes.- 1. Dissolving the Dyes.- 2. 1:1 Metal-Complex (Acid Dyeing Premetallized) Dyes.- 3. 2:1 Metal-Complex (Neutral Dyeing Premetallized) Dyes.- D. Reactive Dyes.- 1. Dissolving the Dyes.- 2. Dyeing Behavior.- E. Dyeing Shrink-Resist Treated Wool.- 1. Reactive Dyes.- 2. Mordant Dyes.- 3. 2:1 Premetallized Dyes.- III. Dyeing of Cellulosic Fibers.- A. Direct Dyes.- 1. Azo.- 2. Stilbene.- 3. Phthalocyanine.- 4. Dioxazine.- 5. Miscellaneous Dyes.- 6. Dissolving the Dyes.- 7. Dyeing Behavior.- 8. Aftertreatments.- B. Vat Dyes.- 1. Indigoid and Thioindigoid.- 2. Anthraquinone.- 3. Dyeing Behavior.- 4. Dyeing Auxiliaries.- 5. Oxidation.- 6. Soaping.- 7. Acidification.- 8. Dispersing the Dyes.- 9. Leuco Dyeing.- 10. Pigmentation Processes.- 11. Solubilized Vat Dyes.- 12. Sulfurized Vat Dyes.- 13. Dyeing with Indigo.- C. Sulfur Dyes.- 1. CI Sulfur Dyes.- 2. CI Leuco Sulfur Dyes.- 3. CI Solubilized Sulfur Dyes.- 4. CI Condense Sulfur Dyes.- 5. Dyeing Behavior.- 6. Batchwise Dyeing Processes.- 7. Semicontinuous Processes.- 8. Continuous Processes.- D. Azoic Colorants.- 1. Coupling Components.- 2. Diazo Components.- 3. Azoic Compositions.- 4. Dyeing Behavior.- 5. Application of Coupling Components.- 6. Removal of Surplus Coupling Component.- 7. Development.- 8. Aftertreatment.- E. Reactive Dyes.- 1. Dissolving the Dyes.- 2. Dyeing Behavior.- 3. Aftertreatment.- IV. Dyeing of Secondary Acetate and Triacetate Fibers.- A. Disperse Dyes.- 1. Azo.- 2. Anthraquinone.- 3. Nitrodiphenylamine.- 4. Styryl.- 5. Dispersing the Dyes.- 6. Dyeing Behavior.- 7. High-Temperature Dyeing.- 8. Carrier Dyeing.- 9. Barre Effects.- 10. Dyeing Auxiliaries.- 11. Aftertreatment.- 12. Dyeing Processes.- B. Azoic Colorants.- C. Vat Dyes.- D. Other Dyes.- V. Dyeing of Polyester Fibers.- A. Disperse Dyes.- 1. Dispersing the Dyes.- 2. Dyeing Behavior.- 3. Barre Effects.- 4. Oligomers.- 5. Dyeing Auxiliaries.- 6. Aftertreatment.- 7. Batchwise Dyeing.- 8. Semicontinuous Dyeing.- 9. Continuous Dyeing.- B. Azoic Colorants.- C. Vat Dyes.- D. Dyeing of Modified Polyester Fibers.- 1. Dyeing of Deep-Dyeing Polyester Fibers.- 2. Dyeing of Noncarrier Dyeing Polyester Fibers.- 3. Dyeing of Anionic-Modified PET Fibers.- 4. Dyeing of Differential-Dyeing PET Fibers.- VI. Dyeing of Polyamide Fibers.- A. Nonmetallized Acid Dyes.- 1. Dissolving the Dyes.- 2. Dyeing Behavior.- 3. Aftertreatment.- B. Disperse Dyes.- C. Mordant Dyes.- D. Premetallized Acid Dyes.- 1. 1:1 Metal-Complex Dyes.- 2. 2:1 Metal-Complex Dyes.- E. Direct Dyes.- F. Reactive Dyes.- G. Dyeing of Modified Nylons.- VII. Dyeing of Acrylic Fibers.- A. Basic Dyes.- 1. Positive Charge Delocalized over the Dye Cation.- 2. Positive Charge Localized on an Ammonium Group.- 3. Dissolving the Dyes.- 4. Dyeing Behavior.- 5. Aftertreatment.- 6. Cooling of the Dyebath.- 7. Exhaustion Dyeing.- 8. Continuous Dyeing.- 9. Migrating Cationic Dyes.- B. Disperse Dyes.- C. Dyeing Modacrylic Fibers.- References.- 8. Nontextile Applications of Dyes.- I. Introduction.- II. Dyes for Displays.- III. Laser Dyes.- IV. Dyes for Optical Data Storage.- V. Organic Photoconductors.- VI. Nonlinear Optics.- VII. Conclusion.- References.- Index of Dyes.

Synthesis and spectral properties of azo dyes derived from 2-aminothiophenes and 2-aminothiazoles

A series of thienylazo and thiazolylazo disperse dyes has been prepared from their corresponding coupling components, 2-aminothiophenes and 2-aminothiazole. Depending on the various substituents present in the diazo component, absorption maxima varied from 437 to 534 nm in toluene. The spectroscopic properties of the azo dyes were examined with respect to the effects of 3- and 4-substituents present in the coupling component. Thus, the appropriate Hammett substituent constants could be related to the observed bathochromic shifts in the order CONH2<<CN<CO2Et<<H at the 3-position of the thiophene ring. However, the resonance effect of the 4-phenyl group contributed to the red shifts observed, unlike the corresponding 4-methyl group. PPP–MO gave reliable predictions of absorption maxima by using new modified parameters for the terminal nitrogen atom in the coupling component.

Synthesis and properties of novel aziridinyl azo dyes from 2-aminothiophenes—Part 2: Application of some disperse dyes to polyester fibres

A series of yellow to greenish-blue aziridinyl azo dyes and their azo precursors containing a thienyl coupling moiety has been applied to conventional polyester fibre as well as microdenier polyester by high temperature exhaust dyeing. Heat transferability of these dyes onto polyester fibre has also been examined, using conventional heat-transfer printing techniques. The relevant dyeing characteristics, heat transferability, build-up, dyeability on microfibre polyester, washfastness and lightfastness are given. These aziridinyl dyes are reactive to polyester fibres under HT dyeing conditions. Fabrics dyed with aziridinyl dyes are more resistant to solvent extraction than those dyed with conventional dyes. Residual liquors showed only a pale colour when fabric dyed with aziridinyl dyes was dissolved and then precipitated, whereas a coloured polyester precipitate was obtained.

Synthesis and properties of novel aziridinyl azo dyes from 2-aminothiophenes—Part 1: Synthesis and spectral properties

Abstract A series of yellow to greenish-blue aziridinyl azo dyes and their azo precursors containing a thienyl coupling moiety has been prepared from 2-aminothiophenes. The 2-aminothiophenes were readily obtained by using the Gewald reaction. It was found that cyclisation of the precursor dyes to the corresponding aziridinoazo dyes brought about bathochromic shifts in absorption maxima. Further spectral comparisons with N-phenylazo dyes derived from other terminal cyclic groups, such as four-, five-, six-, seven- and eight-membered rings, showed that the N-thienylaziridinoazo dyes are relatively bathochromic. From the viewpoint of solvatochromism, a clear contrast existed between λmax values in different solvents; thus, a positive solvatochromism was observed in aprotic solvents, whereas a hypsochromic shift was brought about in polar protic solvents. PPP–MO calculations provided reliable predictions of absorption maxima for the various aziridinyl azo dyes and their precursor dyes.

Dyes derived from aminothiophenes. Part 4: Synthesis of some nitro-substituted thiophene-based azo disperse dyes

Abstract A series of thienylazo dyes has been prepared from nitro-substituted 2- and 3-aminothiophenes; colorants from the former were reddish-blue to green, whereas those from the latter were yellow to orange. The 2-aminothiophenes were obtained either by the amination of an activated chlorothiophene or by the functionalisation of thiophenes synthesised using the Gewald reaction. The thienyl-3-azo dyes were prepared from derivatised 3-amino-2-methoxycarbonylthiophenes. The 13 C NMR chemical shifts of a nitrothienyl-2-azo dye are reported together with those of a 5-nitrothiazolyl-2-azo analogue.

Dyes derived from aminothiophenes. Part 7: Synthesis and properties of some benzo[b]thiophene-based azo disperse dyes

Abstract A series of monoazo dyes has been synthesised from 2- and 3-amino-benzo[b]thiophene diazo components. The spectroscopic properties of the dyes were compared with literature data and theoretical expectations. Dispersions of the dyes were applied to hydrophobic fibres; the colorimetric and fastness properties of the resultant dyeings were evaluated.

A comparison of the properties of some 2-aminothiophene-derived disperse dyes

Abstract In the course of an investigation into the properties of monoazo disperse dyes synthesised from aminothiophene diazo components, significant discrepancies were observed between the spectroscopic and fastness data of some thienyl-2-azo dyes compared to that previously reported for closely related analogues. Considerable differences in λ max and e max values were noted; in some cases, light fastness ratings were at variance with previously disclosed figures.

Dyes derived from aminothiophenes. Part 1: Synthesis of some heterocyclic disperse dyes using the gewald reaction

Abstract A series of red to violet thienyl-2-azo disperse dyes has been derived from aminothiophenes synthesised directly by using the Gewald reaction. A variety of diazotisation conditions had to be employed owing to the differing basicities, hydrophobicities and stabilities of each thiophenamine. 13 C NMR data for certain derivatives are reported.

Dyes derived from aminothiophenes—Part 3. Application of some disperse dyes derived from 2-aminothiophenes to hydrophobic fibres

A series of thienyl-2-azo dyes has been milled and the dispersions applied to polyester, nylon and cellulose diacetate by conventional exhaustion dyeing techniques. The colour properties of the dyeings were examined and related to the molecular structure of the colorants. Generally, of the three substrates, polyester was found to be coloured most effectively; the nylon and acetate dyeings had lower colour yields. Although the dyeings were not of standard depth, correlations between dye structure and wash, perspiration and sublimation fastness were identified. Photostability was observed to improve as electron-withdrawing groups were attached to the thiophene ring.

Dyes derived from aminothiophenes. Part 6: Application of some nitro-substituted thiophene-based azo disperse dyes to hydrophobic fibres

Abstract Monoazo disperse dyes prepared from 2- and 3-aminonitrothiophenes were applied to three dydrophobic fibre types, furnishing reddish-blue to green and yellow to orange dyeings, respectively. Colour yields varied greatly: the dyes exhibited marked differences in build-up on polyester as a result of only small alterations in molecular structure, while the strengths of the nylon and diacetate dyeings were generally unsatisfactory. On the whole, levels of fastness on polyester were good; trends in wet and sublimation fastness were identified. The light-fastness ratings of the thienyl-2-azo dyes on polyester and diacetate were high and superior to those of the thienyl-3-azo analogues; however, on nylon, both dye types had poor photostability.