Patent GB-560988-A (GB)
Title: New anthraquinone dyes
IPC: C09B29/00
Filed: 1942-10-09
Abstract: Water-soluble dyestuffs of the anthraquinone series, believed to be phthaloylcarbazole derivatives, are obtained by treating a 4-p-benzeneazo-anilino-anthraquinone carrying an acylamino group in at least one of the positions 1, 5 and 8, the other such positions being unsubstituted or halogen-substituted, the 2-position being unsubstituted or substituted by halogen, alkyl or a sulphonic acid group, and in which the benzene nuclei of the p-benzene-azoanilino group may be substituted by hydroxyl, alkoxyl, amino, alkyl or nitro groups or by halogen atoms, providing that at least one position ortho to the NH group is unsubstituted, with sulphur trioxide or chlorosulphonic acid, preferably in sulphuric acid as a solvent, and, if necessary, further treating the product with a sulphonating agent. The products, in the form of their sodium salts, dye wool deep brown shades, very fast to light and to washing.  The starting materials are obtainable by acylating the corresponding amino - 4 - halogenoanthraquinone and condensing the products with p-amino-azo-benzene or its appropriate substitution product or by condensing the amino-4-halogenoanthraquinone with the p-amino-azo-benzene and thereafter effecting the acylation, in which case the acylation and the treatment with oleum or chlorosulphonic acid may be performed in one operation.  Specified acylamino - 4 - p - benzene - azo - anilino - anthraquinones are 1 - benzoylamino - 4 - p - benzene-azo-anilino-anthraquinone and its derivatives substituted in the 2-position by chlorine or bromine or by a sulphonic acid or a methyl group, 1 - benzoylamino - 4 - p - (p1 - butylbenzene - azo) - anilino - 2 - methyl - anthraquinone, 1 - benzoylamino - 4 - p - (p1 - hydroxybenzene - azo) - anilino - 2 - methyl - anthraquinone, 8 - benzoylamino - 4 - p - benzene - azo - anilino - anthraquinone, 1 - acetylamino - 4 - p - benzene - azo - anilino - 2 - methyl - anthraquinone, 1 - benzoylamino - 4 - p - (o1 - tolueneazo) - anilino - 2 - methyl - anthraquinone, 1 - p - nitrobenzoylamino - 4 - p - benzene - azo - anilino - 2 - methyl - anthraquinone, 1 - m - chlorobenzoylamino - 2 - bromo4 - p - benzene - azo - anilino - anthraquinone and 1 - benzoylamino - 2 - bromo - 5 - chloro - 4 - p - benzene - azo - anilino - anthraquinone.  Specified sulphonating agents are concentrated solutions of sulphuric acid monohydrate, oleum of various concentrations and chlorosulphonic acid.  Examples relate to (1), (2) and (3), treatment of the 2-methyl, 2-chloro and 2-bromo derivatives respectively of 1-benzoylamino-4-p-benzene-azo-anilino-anthraquinone with 20 per cent oleum at room temperature; (4) treatment of 1 - benzoylamino - 2 - methyl - 4 - p - benzene-azo - anilino - anthraquinone with chlorosulphonic acid for 1 hour at 20 DEG  C. followed by 4 hours at 50 DEG  C. and sulphonating the product with 20 per cent oleum; (5) treatment of 1 - benzoylamino - 2 - methyl - 4 - p - (p1 - butylbenzene - azo) - anilino - anthraquinone with 20 per cent oleum at 12-15 DEG  C.; (6) treatment of 1 - benzoylamino - 2 - methyl - 4 - p - (p1 - hydroxybenzene - azo) - anilino - anthraquinone with 20 per cent oleum at room temperature; (7) treatment of 1 - benzoylamino - 4 - p - benzene - azo - anilino - anthraquinone with 20 per cent oleum at 35-45 DEG  C.; (8) treatment of 8 - benzoylamino - 4 - p - benzene - azo - anilino-anthraquinone with 20 per cent oleum at 30-35 DEG  C.; (9) treatment of 1-acetylamino-4-benzene-azo-anilino-anthraquinone with 20 per cent oleum at 18-20 DEG  C.; (10) treatment of 1 - m - chlorobenzoylamino - 2 - bromo - 4 - p - benzene - azo - anilino - anthraquinone with 20 per cent oleum at 20 DEG  C.; (11) treatment of 1 - benzoylamino - 2 - bromo - 5 - chloro - 4 - p - benzene - azo - anilino - anthraquinone with 20 per cent oleum at 20 DEG  C.; (12) treatment of sodium 1 - amino - 4 - p - benzene - azo - anilinoanthraquinone - 2 - sulphonate with benzoyl chloride and chlorosulphonic acid at 18-20 DEG  C.; (13) treatment of sodium 1-amino-4-p-benzene-azo - anilino - anthraquinone - 2 - sulphonate with acetic anhydride and chlorosulphonic acid at 18-20 DEG  C.; (14) treatment of 1-benzoylamino - 2 - methyl - 4 - p - benzene - azo - o - methylanilino-anthraquinone with 20 per cent oleum at 35 DEG  C. Specification 478,665 is referred to.  1 - Benzoylamino - 2 - bromo - 5 - chloro - 4 - p - benzene - azo - anilino - anthraquinone is obtained by benzoylating the corresponding 1-amino-compound, which is obtainable by condensing with p-amino-azo-benzene the product of di-bromination of 1 - amino - 5 - chloro - anthraquinone. p