Anthraquinone dyes are an abundant group of dyes comprising a anthraquinone unit as the shared structural element. Anthraquinone itself is colourless, but red to blue dyes are obtained by introducing electron donor groups such as hydroxy or amino groups in the 1-, 4-, 5- or 8-position.[1] Anthraquinone dyestuffs are structurally related to indigo dyestuffs and are classified together with these in the group of carbonyl dyes.[2]
One of the most important anthraquinone dyes of herbal origin is alizarin, which is extracted from the dyer's madder (Rubia tinctorum). Alizarin is the eponym for a number of structurally related dyes that use alizarin dyes (sometimes synonymous with anthraquinone dyes). It was the first natural dye for which an industrial synthesis was developed as early as 1869.
Anthraquinone dyes include red insect dyes derived from scale insects such as carminic acid, kermesic acid, and laccaic acids. The colorant carmine with the main component carminic acid is used, for example, as an approved food colorant E 120.[4] The traditional methods for carmine production are labour, land, and insect-intensive. Because demand for red dyes is predicted to increase, researchers are exploring metabolic engineering approaches for the production of synthetic carminic acid.[5][6]
Synthetic anthraquinone dyesedit
The synthesis of most anthraquinone dyes is based on anthraquinone sulfonic acid (2) or nitroanthraquinone (3), which is obtained by sulfonation or nitration of anthraquinone (1).
Synthesis of 1-aminoanthraquinone
Sulfonation in α position is reversible and both the sulfonic acid groups and the nitro groups can be relatively easily replaced by amino, alkylamino, hydroxy and alkoxy groups. Aminoanthraquinone (4) is thus accessible by reaction of anthraquinone sulfonic acid with ammonia or by reduction of nitroanthraquinone.[7]
An important intermediate product for many acid anthraquinone dyes is bromamic acid (1-amino-4-bromoanthraquinone-2-sulfonic acid) (6), which can be obtained from 1-aminoanthraquinone (4) by sulfonation with chlorosulfonic acid and subsequent bromination.
Synthesis of bromamic acid
By replacing the bromine substituent with an aliphatic or aromatic amine, vibrant blue dyes are obtained.[8] For example, bromamic acid can be condensed with 3-(2-hydroxyethylsulfonyl)-aniline (7) to form the vibrant blue dye (8) (oxysulfone blue), from which the reactive dye C.I. Reactive Blue 19 is obtained after esterification with sulfuric acid.
Synthesis of C.I. Reactive Blue 19
Reactive Blue 19 is one of the oldest and still the most important reactive dyes,[9] patented in 1949.[10]
The first anthraquinone-based synthetic vat dye was indanthrone (C.I. Vat Blue 4) - the synthesis of which was developed by René Bohn in 1901:
Synthesis of indanthrone
By dimerization of 2-aminoanthraquinone (1) under strongly alkaline conditions at 220-235 °C, intermediate stage 3 is obtained in two steps, which is cyclized intramolecularly and oxidized to indanthrone 5.[11]
^Zollinger, Heinrich (2003), Color Chemistry: Syntheses, Properties, and Applications of Organic Dyes and Pigments (3rd ed.), Weinheim: WILEY-VCH Verlag, pp. 255 ff., ISBN3-906390-23-3
^Entry on Anthrachinon-Farbstoffe. at: Römpp Online. Georg Thieme Verlag, retrieved 14. Dezember 2018.
^Cooksey, C. J. (17 February 2019). "The red insect dyes: carminic, kermesic and laccaic acids and their derivatives". Biotechnic & Histochemistry. 94 (2): 100–107. doi:10.1080/10520295.2018.1511065. ISSN 1052-0295. Retrieved 28 March 2022.
^Miller, Brittney J. (25 March 2022). "Cochineal, a red dye from bugs, moves to the lab". Knowable Magazine. doi:10.1146/knowable-032522-1. Retrieved 28 March 2022.
^Seo, Seung-Oh; Jin, Yong-Su (25 March 2022). "Next-Generation Genetic and Fermentation Technologies for Safe and Sustainable Production of Food Ingredients: Colors and Flavorings". Annual Review of Food Science and Technology. 13 (1): 463–488. doi:10.1146/annurev-food-052720-012228. ISSN 1941-1413. Retrieved 28 March 2022.
^Heinz-Gerhard Franck, Jürgen W. Stadelhofer (1978), Industrielle Aromatenchemie: Rohstoffe · Verfahren · Produkte (in German), Berlin, Heidelberg: Springer Verlag, pp. 365 ff., ISBN978-3-662-07876-1
^DE 4422160, Andreas Von Der Eltz, "Verfahren zur Herstellung von C.I. Reactive Blue 19", issued 1996-04-01, assigned to Hoechst AG
^DE 965902, Johannes Heyna, Willy Schumacher, "Verfahren zum Fixieren wasserloeslicher organischer Verbindungen auf Unterlagen faseriger Struktur", issued 1957-09-19, assigned to Hoechst AG
^Zollinger, Heinrich (2003), Color Chemistry: Syntheses, Properties, and Applications of Organic Dyes and Pigments (3rd ed.), Weinheim: WILEY-VCH Verlag, p. 289, ISBN3-906390-23-3
April 12, 2024
anthraquinone, dyes, abundant, group, dyes, comprising, anthraquinone, unit, shared, structural, element, anthraquinone, itself, colourless, blue, dyes, obtained, introducing, electron, donor, groups, such, hydroxy, amino, groups, position, tuffs, structurally. Anthraquinone dyes are an abundant group of dyes comprising a anthraquinone unit as the shared structural element Anthraquinone itself is colourless but red to blue dyes are obtained by introducing electron donor groups such as hydroxy or amino groups in the 1 4 5 or 8 position 1 Anthraquinone dyestuffs are structurally related to indigo dyestuffs and are classified together with these in the group of carbonyl dyes 2 AnthraquinoneMembers of this dye group can be found in natural dyes as well as in synthetic dyes Anthraquinone dyestuffs are represented in mordant and vat but also in reactive and disperse dyes They are characterized by very good light fastness 3 Natural anthraquinone dyes edit nbsp AlizarinOne of the most important anthraquinone dyes of herbal origin is alizarin which is extracted from the dyer s madder Rubia tinctorum Alizarin is the eponym for a number of structurally related dyes that use alizarin dyes sometimes synonymous with anthraquinone dyes It was the first natural dye for which an industrial synthesis was developed as early as 1869 Anthraquinone dyes include red insect dyes derived from scale insects such as carminic acid kermesic acid and laccaic acids The colorant carmine with the main component carminic acid is used for example as an approved food colorant E 120 4 The traditional methods for carmine production are labour land and insect intensive Because demand for red dyes is predicted to increase researchers are exploring metabolic engineering approaches for the production of synthetic carminic acid 5 6 Synthetic anthraquinone dyes editThe synthesis of most anthraquinone dyes is based on anthraquinone sulfonic acid 2 or nitroanthraquinone 3 which is obtained by sulfonation or nitration of anthraquinone 1 nbsp Synthesis of 1 aminoanthraquinoneSulfonation in a position is reversible and both the sulfonic acid groups and the nitro groups can be relatively easily replaced by amino alkylamino hydroxy and alkoxy groups Aminoanthraquinone 4 is thus accessible by reaction of anthraquinone sulfonic acid with ammonia or by reduction of nitroanthraquinone 7 An important intermediate product for many acid anthraquinone dyes is bromamic acid 1 amino 4 bromoanthraquinone 2 sulfonic acid 6 which can be obtained from 1 aminoanthraquinone 4 by sulfonation with chlorosulfonic acid and subsequent bromination nbsp Synthesis of bromamic acidBy replacing the bromine substituent with an aliphatic or aromatic amine vibrant blue dyes are obtained 8 For example bromamic acid can be condensed with 3 2 hydroxyethylsulfonyl aniline 7 to form the vibrant blue dye 8 oxysulfone blue from which the reactive dye C I Reactive Blue 19 is obtained after esterification with sulfuric acid nbsp Synthesis of C I Reactive Blue 19Reactive Blue 19 is one of the oldest and still the most important reactive dyes 9 patented in 1949 10 The first anthraquinone based synthetic vat dye was indanthrone C I Vat Blue 4 the synthesis of which was developed by Rene Bohn in 1901 nbsp Synthesis of indanthroneBy dimerization of 2 aminoanthraquinone 1 under strongly alkaline conditions at 220 235 C intermediate stage 3 is obtained in two steps which is cyclized intramolecularly and oxidized to indanthrone 5 11 References edit Hunger Klaus ed 2003 Industrial Dyes Chemistry Properties Applications Weinheim WILEY VCH Verlag pp 35 ff ISBN 978 3 662 01950 4 Zollinger Heinrich 2003 Color Chemistry Syntheses Properties and Applications of Organic Dyes and Pigments 3rd ed Weinheim WILEY VCH Verlag pp 255 ff ISBN 3 906390 23 3 Entry on Anthrachinon Farbstoffe at Rompp Online Georg Thieme Verlag retrieved 14 Dezember 2018 Cooksey C J 17 February 2019 The red insect dyes carminic kermesic and laccaic acids and their derivatives Biotechnic amp Histochemistry 94 2 100 107 doi 10 1080 10520295 2018 1511065 ISSN 1052 0295 Retrieved 28 March 2022 Miller Brittney J 25 March 2022 Cochineal a red dye from bugs moves to the lab Knowable Magazine doi 10 1146 knowable 032522 1 Retrieved 28 March 2022 Seo Seung Oh Jin Yong Su 25 March 2022 Next Generation Genetic and Fermentation Technologies for Safe and Sustainable Production of Food Ingredients Colors and Flavorings Annual Review of Food Science and Technology 13 1 463 488 doi 10 1146 annurev food 052720 012228 ISSN 1941 1413 Retrieved 28 March 2022 Hunger Klaus ed 2003 Industrial Dyes Chemistry Properties Applications Weinheim WILEY VCH Verlag pp 200 ff ISBN 978 3 662 01950 4 Heinz Gerhard Franck Jurgen W Stadelhofer 1978 Industrielle Aromatenchemie Rohstoffe Verfahren Produkte in German Berlin Heidelberg Springer Verlag pp 365 ff ISBN 978 3 662 07876 1 DE 4422160 Andreas Von Der Eltz Verfahren zur Herstellung von C I Reactive Blue 19 issued 1996 04 01 assigned to Hoechst AG DE 965902 Johannes Heyna Willy Schumacher Verfahren zum Fixieren wasserloeslicher organischer Verbindungen auf Unterlagen faseriger Struktur issued 1957 09 19 assigned to Hoechst AG Zollinger Heinrich 2003 Color Chemistry Syntheses Properties and Applications of Organic Dyes and Pigments 3rd ed Weinheim WILEY VCH Verlag p 289 ISBN 3 906390 23 3 Retrieved from https en wikipedia org w index php title Anthraquinone dyes amp oldid 1210304797, wikipedia, wiki, book, books, library,
