Patent GB-566872-A (GB)
Title: New anthraquinone dyestuffs
IPC: C09B5/38
Filed: 1943-05-18
Abstract: Anthraquinone vat dyes in which an anthraquinone-acridone grouping is connected with an anthraquinone - 1(N) - carbazole grouping through an aminoaroylamino grouping are obtained by interaction of (a) a 3-, 4-, 5-, 6-, 7- or 8-halogenoaroylaminoanthraquinone-2 : 1 (N)-acridone or a 3-, 4-, 5-, 6-, 7- or 8-carboxyarylaminoanthraquinone - 2 : 1(N) - acridone or an amide-forming derivative thereof with a carbazole from a 4-, 5- or 8-amino-1-arylaminoanthraquinone, or (b) a 3-, 4-, 5-, 6-, 7- or 8-aminoanthraquinone - 2 : 1(N) - acridone with a carbazole from a 4-, 5- or 8-halogenoaroylamino-1-arylamino-anthraquinone or from a 4-, 5- or 8 - carboxyarylamino - 1 - arylamino - anthra - quinone or an amide-forming derivative thereof.  Specified halogenoaroylaminoanthraquinone - 2 : 1(N)-acridones (made by acylation of the corresponding aminoanthraquinone - 2 : 1(N) - acridones with the appropriate halogenoaroyl halides, obtained by the action of thionyl chloride on the corresponding acids are the 3-, 4- and 5-p-bromobenzoylamino, 4-p-(p1-bromophenyl) - benzoylamino, 4- and 5 - m - bromo - benzoylamino, 4- and 5-o-chlorobenzoylamino, 4-(31 : 51-dichloro-41-bromobenzoylamino) and 4-(p-bromo-a -naphthoylamino) derivatives of anthraquinone-2 : 1(N)-benzacridone. Specified carboxyaroylaminoanthraquinone - 2 : 1(N) - acridones are the 4-p-carboxyanilino and 5-m-carboxyanilino derivatives of anthraquinone-2 : 1(N)-benzacridone.  Specified aminoanthraquinone-2 : 1(N)-acridones are the 3-, 4-, 5- and 8-amino and the 4-amino-51-methyl derivatives of anthraquinone - 2 : 1(N) - benzacridone.  Specified aminoanthraquinone-carbazoles are those from 4 - amino - 1 - p - tolylaminoanthra - quinone and 4- or 5-amino-1-b -naphthylaminoanthraquinone.  Specified halogenaroylaminoanthraquinone-carbazoles are those from the 4 - m - or p - bromobenzoylamino, 4 - o - chloro - benzoylamino, 4-p-(p1-bromophenyl)-benzoylamino and 5-m-bromobenzoylamino derivatives of 1-b -naphthylaminoanthraquinone.  Specified carboxyarylaminoanthraquinone-carbazoles are those from 4- or 5-p-carboxyanilino-1-b -naphthylaminoanthraquinone and from 4-m-carboxyanilino - 1 - p - tolylamino - anthraquinone. Examples relate to the condensation of (1) 4-aminoanthraquinone - 2 : 1(N) - benzacridone with the carbazole from 4-p-bromobenzoylamino-1-b -naphthylaminoanthraquinone, or the corresponding 4-m-bromo or 5-p-bromo compound, by boiling for 12 hours in nitrobenzene under reflux in presence of sodium carbonate and cuprous chloride; (2) 4-p-bromobenzoylaminoanthraquinone - 2 : 1(N) - benzacridone with the carbazole from 4-amino-1-p-tolylaminoanthraquinone similarly; (3) 5-o-chlorobenzoylaminoanthraquinone - 2 : 1(N) - benzacridone with the carbazole from 5 - amino - 1 - b  - naphthylamino - anthraquinone similarly; (4) 5 - m - bromo - benzoylaminoanthraquinone - 2 : 1(N) - benz - acridone, or the corresponding 5-p-bromo or 5-o-chloro compounds, with the carbazole from 4 - amino - 1 - b  - naphthylaminoanthraquinone similarly; (5) 4-p-bromobenzoylaminoanthraquinone - 2 : 1(N) - benzacridone, or the corresponding 4-m-bromo or 4-o-chloro compound, with the carbazole from 4-amino-1-b -naphthylaminoanthraquinone similarly; (6) 4-p-(p1-bromophenyl) - benzoylaminoanthraquinone - 2 : 1(N)-benzacridone, or 4-(p-bromo-a -naphthoylamino)-anthraquinone-2 : 1(N)-benzacridone, with the carbazole from 4-amino-1-b -naphthylaminoanthraquinone similarly; (7) 4 - aminoanthraquinone - 2 : 1(N) - benzacridone with the carbazole from 4-p-(p1-bromophenyl)-benzoylamino - 1 - b  - naphthylaminoanthra - quinone similarly; (8) 4-aminoanthraquinone-2 : 1(N) - 51 - methyl - benzacridone with the carbazole from 4-p-bromobenzoylamino-1-b -naphthylaminoanthraquinone by heating for 18 hours in naphthalene at 210-215 DEG  C. containing sodium carbonate and cuprous chloride; (9) 3-aminoanthraquinone - 2 : 1(N) - benzacridone with the carbazole from 4-p-bromobenzoylamino - 1 - b  - naphthylaminoanthraquinone in boiling nitrobenzene as in (1); (10) the chloride of 4-p-carboxyanilinoanthraquinone - 2 : 1(N) - benzacridone with the carbazole from 4-amino-1 - b  - naphthylaminoanthraquinone in boiling nitrobenzene; (11) 4-aminoanthraquinone-2 : 1 (N)-benzacridone with the chloride of the carbazole from 4-p-carboxyanilino-1-b -naphthylaminoanthraquinone in boiling nitrobenzene; (12) 3 - p - bromobenzoylaminoanthraquinone - 2 : 1(N)-benzacridone with the carbazole from 4-amino-1-b -naphthylaminoanthraquinone in boiling nitrobenzene as in (1); (13) 4-p- or m-bromobenzoylaminoanthraquinone - 2 : 1(N) - benzacridone with the carbazole from 5-amino-1 - b  - naphthylaminoanthraquinone similarly; (14) 4-(31 : 51-dichloro-41-bromobenzoylamino)-anthraquinone-2 : 1(N) - benzacridone with the carbazole from 4-amino-1-b -naphthylamino - anthraquinone similarly.  Halogenoaroylaminoanthraquinone - 2 : 1(N) - acridones are obtained by acylation of the corresponding aminoanthraquinone - 2 : 1(N) - acridones with the appropriate halogenoaroyl halides, such as those obtained by the action of thionyl chloride on the corresponding acids. Carboxyarylaminoanthraquinone - 2 : 1(N) - acridones are obtained by condensing the corresponding aminoanthraquinone - 2 : 1(N) - acridones with the appropriate halogenoarylcarboxylic acid or an ester thereof, followed by hydrolysis if necessary.  Carbazoles from halogenoaroylamino - 1 - aryl - aminoanthraquinone are obtained by (a) acylation with the appropriate halogenoaroyl halides of the carbazoles from the corresponding amino - 1 - arylaminoanthraquinones, made by hydrolysing the carbazoles from the corresponding benzoylamino-1-arylaminoanthraquinones, or (b) treating with sulphuric acid, with or without oxidation, the condensation product of a corresponding halogeno-1-halogenobenzoylaminoanthraquinone with the appropriate arylamine.  Carbazoles from 4-benzoylamino-1-p-tolylaminoanthraquinone and 4- and 5-benzoylamino-1-b -naphthylaminoanthraquinones are obtained by treating the parent materials with 85-90 per cent sulphuric acid below 35 DEG  C., followed, in the case of the first-mentioned compound, by oxidation with sodium bichromate.  Carbazoles from carboxyarylamino - 1 - aryl - aminoanthraquinone are obtained by condensation of the carbazole from the corresponding amino - 1 - arylaminoanthraquinone with the appropriate halogenoarylcarboxylic acid or an ester thereof, followed by hydrolysis if necessary.  The acid chlorides of 4-p-carboxyanilinoanthraquinone-2 : 1(N)-benzacridone and of the carbazole from 4 - p - carboxyanilino - 1 - b  - naph - thylaminoanthraquinone are obtained by the action of thionyl chloride in nitrobenzene on the parent acids.  3 - Aminoanthraquinone - 2 : 1(N) - benzacri - done is obtained by hydrolysing with sulphuric acid the product of reaction of p-toluenesulphonamide with 3-bromoanthraquinone-2 : 1(N)-benzacridone.  4 - Aminoanthraquinone - 2 : 1(N) - 51 - methylbenzacridone is similarly obtained from 4-bromoanthraquinone-2 : 1(N)-51-methyl-benzacridone, obtained by treating with benzoyl chloride in o-dichlorobenzene the product of condensation of 1-chloro-4-bromoanthraquinone-2-carboxylic acid with p-toluidine.  3 : 5 - Dichloro - 4 - bromobenzoic acid chloride, for use in preparing the benzacridone component of example (14), is obtained by treating diazotised 3 : 5-dichloro-4-aminobenzoic acid with cuprous bromide.