Patent GB-655909-A (GB)
Title: Manufacture of copperable disazo and polyazo dyestuffs
IPC: C09B35/00
Filed: 1948-09-14
Abstract: Diamines of the general formula <FORM:0655909/IV (b)/1> wherein X means a direct linkage or a divalent member of the formula -S-, -SO-, -SO2-, -CH2-, -CO-, -NH-, -NH-CO-, or -NH-CO.NH- and wherein the benzene rings may contain further non-ionizing substituents (e.g. alkyl, alkoxy, or halogen) are prepared for use as intermediates in the preparation of azo dyestuffs (see Group IV (c)).  The method used may be that of Specification 341,970, i.e. the reaction of a 3-nitro-4-acyloxy or a 3-nitro-4-alkylcarbonato benzoyl chloride and a p-diamine of the diphenyl series, followed by hydrolysis and reduction, or a 3-nitro-4-hydroxybenzoyl chloride obtained by reacting the acid with thionyl chloride may be used.  Employed in the examples are 4 : 4-di-(311-amino - 411 - hydroxybenzoylamino) - 3 : 31 - dimethoxy diphenyl, 4 : 41-di-(311-amino-411-hydroxy-benzoylamino) -diphenyl, 4 : 41-di-(311-amino - 411 - hydroxybenzoylamino) - 3 : 31 - dimethyldiphenyl, 4 : 41 - di - (311 - amino - 411 - hydroxybenzoylamino) - 3 : 31-dichlorodiphenyl, 4 : 41 - di - (311 - amino - 411 - hydroxybenzoylamino) - diphenyl methane, 4 : 41 - di - (311 - amino - 411 - hydroxybenzoylamino) - diphenyl sulphone, N : N1 - di - (311 - amino - 4 - hydroxybenzoyl) - 1 - (41 - aminobenzoylamino) - 4 - amino benzene, 4 : 41 - di - (311 - amino - 411 - hydroxy - 611 - chlorobenzoylamino) - 3 : 31 - dimethoxy diphenyl, 4 : 41 - di - )311 - amino - 411 - hydroxy-511 - methylbenzoylamino) - 3 : 31 - dimethoxy diphenyl and 4 : 41-di-(311-amino-411-hydroxy-611 -methoxybenzoylamino)-diphenyl. Samples have been furnished of dyestuffs prepared from diamines of the above general formula in which X represents (I) a -CO-group, and (II) an -SO- group.  A table relates to further diamines, obtained by the hydrolysis and reduction of the products formed by the benzoylation of 4 : 41-diamino diphenyl, 4 : 41 - diamino - 3 : 31 - dimethoxydiphenyl, 4 : 41 - diamino - 3 : 31 - dichlorodiphenyl, 4 : 41 - diaminodiphenyl urea, 4 : 41 - diaminodiphenylmethane, 4 : 41 - diaminodiphenylsulphide or 4 : 41 - diaminodiphenylamine with a 3 - nitro - 4 - hydroxybenzoyl chloride which in some cases has a 6-chloro-, 5-methyl-, or a 5-bromo-substituent.ALSO:Copperable disazo and polyazo dyestuffs are made by coupling 1 mol. of a tetrazo compound of a diamine having the general formula <FORM:0655909/IV (c)/1> wherein X means a direct linkage or a divalent member of the formula -S-, -SO-, -SO2-, -CH2-, -CO-, -NH-, -NH-CO-, or -NH-CO-NH- and wherein the benzene rings may contain further non-ionizing substituents (e.g. alkyl, alkoxy or halogen) with 2 mols. of a naphthol sulphonic acid coupling in the ortho position to the hydroxyl groups and which may contain further substituents including azo groups. Particularly suitable are those naphthol sulphonic acids having also a substituted amino group.  Examples describe (1) the coupling of 2 mols. of 1-acetyl-amino - 8 - hydroxynaphthalene - 4 - sulphonic acid to one mol. of the tetrazo compound from 4 : 41 - di - (311 - amino - 411 - hydroxybenzoylamino) - 3 : 31 - dimethoxy diphenyl, 4 : 41-di - (311 - amino - 41 - hydroxybenzoylamino)-diphenyl, 4 : 41 - di - (311 - amino - 411 - hydroxy benzoylamino) - 3 : 31 - dimethyldiphenyl, 4 : 41 - di - (311 - amino - 411 - hydroxybenzoylamino) - 3 : 31 - dichlorodiphenyl, 4 : 41 - di-(311 - amino - 411 - hydroxybenzoylamino)-diphenylmethane, 4 : 41 - di - (311 - amino-411 - hydroxybenzoylamino) - diphenyl sulphone, or N : N1 - di - (311 - amino - 411-hydroxybenzoyl) - 1 - (41 - aminobenzoylamino)-4-amino benzene; (2) 2 mols. of a monoazo dyestuff obtained by the acid coupling of diazotized p-aminosalicylic acid with 2-amino - 5 - hydroxynaphthalene - 7 - sulphonic acid are coupled to 1 mol. of the tetrazo compound from 4 : 41 - di - (311 - amino - 411-hydroxybenzoylamino) - 3 : 31 - dimethoxy diphenyl, 4 : 41 - di - (311 - amino - 411 - hydroxy-61 - chlorobenzoylamino) - 3 : 31 - dimethoxy-diphenyl, 4 : 41 - di - (311 - amino - 411 - hydroxy-511 - methylbenzoylamino) - 3 : 31 - dimethoxy-diphenyl, or 4 : 41 - di - (311 - amino - 411-hydroxy - 611 - methoxybenzoylamino) - diphenyl; (3) 2 - hydroxynaphthalene - 6 - sulphonic acid is coupled to the tetrazo compound from one of the first four diamines specified in (1).  The application of the product of (1) to cotton and coppering are described.  Samples have been furnished under Sect. 2(5) of dyestuffs prepared by coupling 2 - hydroxynaphthalene - 6 - sulphonic acid with tetrazo compounds of diamines of the above general formula where X represents (I) a -CO- group, and (II) an -SO- group.  A table relates to the use of further components, specified being naphthol sulphonic acids: 1- or 2-hydroxynaphthalene 4- or 5-sulphonic acids, 2-hydroxynaphthalene 4-, 5-, or 7-sulphonic acids, 2-(31- or 41-aminobenzoylamino) - 5 - hydroxynaphthalene - 7 - sulphonic acid, 2 - acetylamino - 5 - hydroxynaphthalene 4 - sulphonic acid, 1 - acetylamino hydroxynaphthalene - 4 - sulphonic acid, 2-acetylamino - 8 - hydroxynaphthalene - 6-sulphonic acid, 2-benzoylamino-5-hydroxynaphthalene - 7 - sulphonic acid, 2 - (31 - aminobenzoylamino) - 5 - hydroxynaphthalene - 1-sulphonic acid, 1-benzoylamino-8-hydroxynaphthalene-4-sulphonic acid; diamines: those obtained by the reduction of the products formed by the benzoylation of the diamines 4 : 41 - diaminodiphenyl, 4 : 41 - diamino-3 : 31 - dimethoxydiphenyl, 4 : 41 - diamino-3 : 31 - dichlorodiphenyl, 4 : 41 - diaminodiphenyl urea, 4 : 41 - diaminodiphenyl-methane, 4 : 41-diamino-diphenyl sulphide or 4 : 41-diamino-diphenyl-amine, with a 3-nitro-4-hydroxy-benzoyl chloride which may have a 6-chloro-, 5-methyl-, or a 5-bromo-substituent.  The diamines may also be prepared (see Group IV (b)), by the method of Specification 341,970, using a 3-nitro-4-acyloxy or alkylcarbonato-benzoyl chloride followed by hydrolysis and reduction of the intermediate.  The Specification as open to inspection under Sect. 91 states that when an acyloxy- or alkyl-carbonates group is present in the diamine formed by the benzoylation, it may remain until the dyestuff is formed and then hydrolysed a hydroxy group.  This subject-matter does not appear in the Specification as accepted.