Anthraquinone dyes

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]

Anthraquinone

Members 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
Alizarin

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 laccainic 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

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).

Synthese von 1-Aminoanthrachinon
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.

Synthese von Bromaminsäure
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.

Synthese von C.I. Reactive Blue 19
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:

Synthese von Indanthron
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]

References
  1. Hunger, Klaus, ed. (2003), Industrial Dyes: Chemistry, Properties, Applications, Weinheim: WILEY-VCH Verlag, pp. 35 ff., ISBN 978-3-662-01950-4
  2. 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
  3. Entry on Anthrachinon-Farbstoffe. at: Römpp Online. Georg Thieme Verlag, retrieved 14. Dezember 2018.
  4. 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.
  5. 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.
  6. 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.
  7. Hunger, Klaus, ed. (2003), Industrial Dyes: Chemistry, Properties, Applications, Weinheim: WILEY-VCH Verlag, pp. 200 ff., ISBN 978-3-662-01950-4
  8. Heinz-Gerhard Franck, Jürgen W. Stadelhofer (1978), Industrielle Aromatenchemie: Rohstoffe · Verfahren · Produkte (in German), Berlin, Heidelberg: Springer Verlag, pp. 365 ff., ISBN 978-3-662-07876-1
  9. DE 4422160, Andreas Von Der Eltz, "Verfahren zur Herstellung von C.I. Reactive Blue 19", issued 1996-04-01, assigned to Hoechst AG
  10. DE 965902, Johannes Heyna, Willy Schumacher, "Verfahren zum Fixieren wasserloeslicher organischer Verbindungen auf Unterlagen faseriger Struktur", issued 1957-09-19, assigned to Hoechst AG
  11. 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
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