Patent GB-561420-A (GB)
Title: Process for the preparation of new acylamines of the anthraquinone series
IPC: C09B1/42
Filed: 1941-11-06
Abstract: Acylaminoanthraquinone derivatives which are vat dyes are obtained by condensing a vattable 1 - benzoylamino - 4 - (carboxy)phenylamino-anthraquinone, which may be substituted, e.g. in the anthraquinone nucleus by halogen, in the phenyl nucleus of the benzoyl group by halogen or by methoxy or nitro groups and in the phenyl nucleus of the phenylamino group by halogen or alkyl, with a vattable anthraquinone derivative carrying at least one primary amino group.  Specified first components are 1-benzoylamino-4-(o-, m- and p-carboxyphenyl)amino - anthraquinones, 1-benzoylamino-4-(31-carboxy-41-chlorophenyl) -amino-anthraquinone and the corresponding 1 - (21 - chloro) - benzoylamino derivative, 1-(41 - methoxy-, 41 - nitro-, 21 - chloro- or 21 : 41-dichloro) - benzoylamino - 4 - (p - carboxyphenyl)-amino-anthraquinones and 1 - benzoylamino-4-(41 - carboxy - 21 - methylphenyl)amino - anthraquinone.  Specified second components are 2-aminoanthraquinone, 1-aminoanthraquinone and its 3-and 4-bromo, 5-, 6-, 7- and 8-chloro, 6 : 7-dichloro 4- 5- and 8-hydroxy 4-methoxy and 4-(41-diphenyl)amine derivatives 1 : 4-1 : 5- 1 : 8- and 2 : 6-diaminoanthraquinones 1 : 5 - diamino - 5 : 8 - dihydroxyanthraquinone, 1-amino-4-, 5- and 8-benzoylamino-anthraquinones, 1 - amino - 5 - phenylaminoanthraquinone, 1 - amino - 4 - phenylaminoanthraquinone and its 21-, 31- and 41-chloro, 21 : 51-dichloro, 41-methyl and 21- and 41-methoxy derivatives, 1-amino-4-phenylamino-6- and 7-chloro-anthraquinones and their derivatives substituted in the phenyl nucleus by halogen, alkyl or alkoxy, 4-amino-N-methyl-1(N) : 9-anthrapyridone and its C-acetyl and C-carbethoxy derivatives, the C1-carbethoxy, C-carbomethoxy, C-benzoyl, C-acetyl and C-cyano derivatives of 4 - amino - 2 - methyl - 1(N) : 9-anthrapyridone, 5-amino-C-carbethoxy-1(N) : 9-anthrapyridone, 4- and 5-amino-1 : 9-anthrapyrimidines, 4 - aminoanthraquinone - 2 : 1(N)-benzacridone and its 41-chloro derivative, 5- and 8-amino-anthraquinone-2 : 1(N)-benzacridones, 4- and 5-amino-1 : 11- and 1 : 21-dianthrimides, 5-amino-61-chloro-1 : 11-dianthrimide, 4 : 41-, 5 : 51- and 4 : 51-diamino-1 : 11-dianthrimides and 4 : 41 - diamino - 6 : 61 - dichloro - 1 : 11-dianthrimides.  The condensation may be effected (a) by first converting the carboxylic acid, by treatment with phosphorus tri- or penta-chloride or thionyl chloride in a solvent, such as chlorobenzene, o-dichlorobenzene or nitrobenzene, into the acid chloride, which is then heated with the amino component and with or without an acid-binding agent such as pyridine, dimethylaniline or an alkali acetate, or (b) by heating the carboxylic acid with the amino component in the solvent, with or without the acid-binding agent, in the presence of a condensing agent such as phosphorus pentoxide, oxychloride, trichloride or pentachloride, zinc chloride, aluminium chloride, ferric chloride or thionyl chloride.  Examples relate to the condensation of (1) 1-benzoylamino-4-o- or p-carboxyphenyl)-amino-anthraquinone with 1-amino-5-benzoylamino - anthraquinone by heating the acid chloride with the amine in nitrobenzene at 130-140 DEG  C., (2) 1-benzoylamino-4-(p-carboxyphenyl)amino-anthraquinone with 1-amino-4-phenylamino-anthraquinone by heating the acid chloride with the amine in o-dichlorobenzene at 140 DEG  C. in presence of pyridine, (3) 1-benzoylamino - 4 - (p - carboxyphenyl)amino - anthraquinone with 1-amino-4-phenyl amino-anthraquinone or its 21-, 31- or 41-chloro, 21-, 31- or 41-methyl or 21- or 41-methoxy derivatives by heating the acid chloride with the amine in o-dichlorobenzene at 130-140 DEG  C. in presence of pyridine, (4) 1-benzoylamino-4-(m-carboxyphenyl)amino-anthraquinone with 1-amino-4-phenylamino-anthraquinone or its 6-chloro derivative by heating in o-dichlorobenzene at 140 DEG  C. in presence of thionyl chloride and pyridine, (5) 1 - benzoylamino - 4 - (p - carboxyphenyl)amino - anthraquinone with 4 : 41-diamino-1 : 11-dianthrimide or its 6 : 61-dichloro derivative by heating in o-dichlorobenzene at 170 DEG  C. in presence of thionyl chloride, (6) 1 - benzoylamino - 4 - (m - carboxyphenyl)aminoanthraquinone with 4 : 41 - diamino - 1 : 11-dianthrimide by heating in trichlorobenzene at 200 DEG  C. in presence of thionyl chloride.  A table is also given showing the colours of the dyeings on cotton with the dyestuffs from various combinations of components.  1 - Amino - 6 : 7 - dichloroanthraquinone is obtained by reduction of the product of nitration of 2 : 3-dichloroanthraquinone. 1 - Benzoylamino - 4 - (carboxyphenyl)amino-anthraquinones are obtained by (a) condensation of 1 - benzoylamino - 4 - halogen - anthraquinones with aminobenzoic acids, (b) condensation of 1 - benzoylamino - 4 - aminoanthraquinones with halogenbenzoic acids, or (c) benzoylating the free amino groups in products obtained by splitting off the sulphonic acid group from 1 - amino - 4 - (carboxyphenyl)amino - anthraquinone-2-sulphonic acids, which are obtained by condensation of 1-amino-4-halogen-anthraquinone-2-sulphonic acids with aminobenzoic acids.  The Specification as open to inspection under Sect. 91 (4) (a) comprises also (a) the subject-matter of Provisional Specification 560,131, viz. the production of similar condensation products with the use as first component of a 4- or 5-(carboxy)phenylamino-1(N) : 9-anthrapyridone, (b) the use as first components of di - (carboxyphenylamino) - anthraquinone, e.g. the 1 : 4-di-, 1 : 51-di- and 1 : 8-di-compounds, (c) the use as first components of any carboxyphenylaminoanthraquinones, wherein the anthraquinone nucleus may be replaced by cyano, hydroxy, alkyl, alkoxy, amino or acylamino groups or the phenyl nucleus of the carboxyphenyl group by cyano or alkoxy groups, additional such components being 1-hydroxy-4-carboxyphenylaminoanthraquinones and their 2-bromo derivatives, 1-methoxy-4-carboxyphenylaminoanthraquinones, 1 - acyl - amino-4-, 5- or 8-carboxyphenylaminoanthraquinones.  Additional examples not included in the above Provisional Specification relate to the condensation of (1) 1-(p-carboxyphenyl) amino - anthraquinone with 1 - amino - 4 - (41-chlorophenyl)amino-anthraquinone by heating them together in o-dichlorobenzene at 130-140 DEG  C. in presence of thionyl chloride and pyridine; (2) 1-benzoylamino-5- or 8-(p-carboxyphenyl)amino-anthraquinone with 4-amino-N-methyl-1(N) : 9-anthrapyridone or 4-amino-2 - methyl - C - carbethoxy - 1(N) : 9 - anthrapyridone by heating in o-dichlorobenzene at 130-160 DEG  C. in presence of thionyl chloride and pyridine; (3) 1 : 4-di-(p-carboxyphenylamino)-anthraquinone with 1-amino 4- or 5-benzoylamino-anthraquinone by heating in o-dichlorobenzene at 130 DEG  C. in presence of thionyl chloride and pyridine; (4) 1 : 5-di-(p-carboxyphenylamino) - anthraquinone with 5-aminoanthraquinone-2 : 1(N)-benzacridone by heating the acid chloride with the amine in o-dichlorobenzene at 180 DEG  C.; (5) 1-(41-carboxyphenyl)aminoanthraquinone with 4 - amino-1 : 21-dianthrimide by heating in o-dichlorobenzene at 180 DEG  C. in presence of thionyl chloride.  Additional specified first components are 1-(0- and m-carboxyphenyl)amino-anthraquinones, 1 : 5- and 1 : 8-di-(o-carboxyphenyl)-amino - anthraquinones, 1 : 8 - di - (p - carboxyphenyl)amino - anthraquinone, 1 - hydroxy - 2-bromo - 4 - (p - carboxyphenyl)amino - anthra - quinone, 1-acetylamino- or chloracetylamino-4-(p - carboxyphenyl)amino - anthraquinone, 1-(21 : 51 - dichloroterephthaloyl)amino - 4 - (p-carboxyphenyl)amino - anthraquinone, 1 - (diphenyl - 2 : 21-dicarboxyl)amino-4-(p-carboxyphenyl)amino - anthraquinone, 1 - (anthraquinone-2-carbonyl)amino-4-(p-carboxyphenyl) amino-anthraquinone, 1 - (p-toluenesulphonyl)amino - 4 - (p - carboxyphenyl)amino - anthraquinone, 1-benzoylamino-5- or 8-(p-carboxyphenyl)amino-anthraquinone and 1 - amino-4-(p - carboxyphenyl)amino - anthraquinone.  An additional specified second component is 1-amino - 4 - (p - carboxyphenyl)amino - anthraquinone.  This subject-matter does not appear in the Specification as accepted.