Acylaminoanthraquinone Dyes Based on 2,2'-Diphenic Acid
Abstract Generated abstract
This paper reports the synthesis and characterization of acylaminoanthraquinone dyes derived from 2,2′-diphenic acid, motivated by the use of phenanthrene oxidation products in industrial organic synthesis. Monoanthraquinonylamides, dianthraquinonylamides, and mixed diamides were prepared by acylation methods using diphenic anhydride or diphenic acid in the presence of phosphorus trichloride, followed by recrystallization and analytical characterization. The resulting water-insoluble dyes produced mainly yellow to red shades from a hydrosulfite vat on cotton, showed comparatively weak affinity for cellulose fiber, and were suggested as suitable for coloring plastic masses and synthetic fibers in the mass. Spectrophotometric absorption curves and basic coloristic properties were recorded for the synthesized compounds.
Full Text
ACYLAMINOANTHRAQUINONE DYES BASED ON 2,2′-DIPHENIC ACID
L. P. Kulev, G. M. Stepnova, P. F. Gabinskaya
Polycyclic vat dyes, encompassing the entire range of shades, give the most valuable dyeings, unsurpassed in fastness to light and to wet treatments. Of interest in this series are acylaminoanthraquinone dyes obtained by acylation of aminoanthraquinones or oxyaminoanthraquinones with carboxylic acids. Benzoic (1, 2), methoxybenzoic, sulfonylmethylbenzoic (3), isophthalic (4), 4,4′-diphenic (5), and 1,9,5,10-anthradipyrimidine-2,6-dicarboxylic acids are used as acylating agents. Especially valuable are dyes of this class obtained by acylation of aminoanthraquinones with dicarboxylic acids.
With the aim of utilizing phenanthrene oxidation products in industrial organic synthesis, we have obtained monoanthraquinonylamides (I), dianthraquinonylamides (II), and mixed diamides (III) of 2,2′-diphenic acid.
The dyes obtained are insoluble in water; from a hydrosulfite vat on cotton they give yellow and red dyeings. The dyes have comparatively weak affinity for cellulose fiber. They can be used for dyeing plastic masses and synthetic fibers in the mass. Spectrophotometric absorption curves have been determined for all the dyes.
Fig. 1. Spectrophotometric absorption curves of the amides of 2,2′-diphenic acid:
I — mono-1-anthraquinonylamide, II — di-1-anthraquinonylamide,
III — mono-2-chloro-1-anthraquinonylamide, IV — di-2-chloro-1-anthraquinonylamide,
V — 4-nitrophenyl-1-anthraquinonylamide, VI — 2-nitrophenyl-1-anthraquinonylamide, VII — phenyl-1-anthraquinonylamide.
Experimental Part
Mono-1-anthraquinonylamides of 2,2′-diphenic acid were synthesized by heating diphenic anhydride with an equimolecular amount of 1-aminoanthraquinones (4 hours, 145°). Di-1-anthraquinonylamides of 2,2′-diphenic acid were obtained from diphenic acid and 1-aminoanthraquinones in the presence of phosphorus trichloride (3 hours, 120°). Mixed diamides were synthesized by acylation of the corresponding aromatic amines with monoanthraquinonylamides of diphenic acid in the presence of phosphorus trichloride (3 hours, 120°). The compounds obtained were purified by repeated recrystallization to constant melting point from chlorobenzene or xylene. The characteristics of the dyes are given in the table.
| Amides of 2,2′-diphenic acid | m.p., °C | % N found | % N calc. | Color |
|---|---|---|---|---|
| Mono-1-anthraquinonylamide | 261 | 3.24 | 3.13 | Yellow |
| Di-1-anthraquinonylamide | 215 | 4.49 | 4.29 | Red |
| Mono-2-chloro-1-anthraquinonylamide | 255—256 | 3.14 | 2.91 | Yellow |
| Di-2-chloro-1-anthraquinonylamide | 229—230 | 3.02 | 3.26 | Brown |
| Phenyl-1-anthraquinonylamide | 206—207 | 5.30 | 5.36 | Yellow |
| 2-Nitrophenyl-1-anthraquinonylamide | 252—253 | 7.35 | 7.41 | Yellow |
| 4-Nitrophenyl-1-anthraquinonylamide | 263—264 | 7.27 | 7.41 | Yellow |
Conclusions
Acylaminoanthraquinone dyes, derivatives of 2,2′-diphenic acid, were synthesized; their spectrophotometric absorption curves were recorded, and their coloristic properties were studied.
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