Patent GB-708681-A (GB)
Title: Process for the production of azo dyestuffs
IPC: C09B39/00
Filed: 1952-02-14
Abstract: Compounds of the general formula <FORM:0708681/IV (b)/1> (wherein X represents a radical which contains one or more benzene or naphthalene rings or both and may also contain one or more pyrazolone rings, one Y represents NH2 and the other a carboxylic acid group which may be esterified, Z represents hydrogen or an alkyl, aralkyl or aryl group, and n is 1 or 2) are manufactured by the action of acid chlorides of the general formula <FORM:0708681/IV (b)/2> (wherein one A represents NO2 and the other COO. alkyl) on primary or secondary mono- or di-amines of the benzene or naphthalene series, which may contain further substituents (e.g. alkyl, aryl, aralkyl, hydroxy, acylamino or carboxylic or sulphonic acid groups, or halogen atoms), followed by reduction of the nitro group and, if desired, saponification of the ester group before or after the reduction. Specified amines, some of which are reacted in examples with 3 - carbomethoxy - 4 - nitrobenzoyl chloride or 3 - nitro - 4 - carbomethoxybenzoyl chloride, are: aniline and its 3- and 4-sulphonic acids and 2-, 3- and 4-carboxylic acids, o-, m-and p-toluidine, 2 : 4- and 2 : 5-dimethylaniline, o-, m- and p-chloraniline, 2 : 5-dichloroaniline and its 4-sulphonic acid, m- and p-phenylenediamine, 1 : 3-diaminobenzene-4-sulphonic acid, 1 : 4 - diaminobenzene - 31 - sulphonic and -3-carboxylic acid, p-acetyl- and -benzoyl-aminoaniline, p-carbethoxyaminoaniline, 4- and 5-aminosalicylic acids, 1-amino-4-hydroxy-3-carboxybenzene-5-sulphonic acid, benzidine, o-tolidine, dianisidine, 3 : 31-dichlorobenzidine, benzidine - 3 - sulphonic, - 3 : 31 - disulphonic and - 3 : 31 - dicarboxylic acids, 1 - amino - 4-(41 - aminobenzoylamino1 - benzene, 4 : 41 - diaminodiphenylurea, 4 : 41 - diaminostilbene-2 : 21 - disulphonic acid, 4 : 41 - diaminodiphenylamine, 4 : 41 - diaminobenzophenone, 4 : 41 - diaminodiphenylmethane, 4 : 41 - diaminodiphenyl sulphone, 1 -(41 - or 31 - aminophenyl) - 3 - methyl - 5 - pyrazolone, 4 - amino-41 - (311 - methyl - 511 - pyrazolonyl - 111) - stilbene - 2 : 21 - disulphonic acid, a  - and b -naphthylamine, 1 - naphthylamine - 5 -, - 6-and - 7 - sulphonic acids and - 3 : 6 -, - 3 : 8-and - 4 : 8 - disulphonic acids, 2 - naphthylamine - 6 - sulphonic acid and - 3 : 6 -, - 4 : 8-, -5 : 7- and -6 : 8-disulphonic acids, 1 : 8 : 4-, 2 : 5 : 7-, 2 : 8 : 6- and 1 : 8 : 6-aminonaphtholsulphonic acids, 1 : 8 : 2 : 4-, 1 : 8 : 3 : 6- and 2 : 8 : 3 : 6 - aminonaphtholdisulphonic acids, N-methyl-, N-ethyl- and N-benzyl-aniline, N-ethylaniline-3- and -4-sulphonic acids, N-ethyl-o- and p-toluidine, N-methyl-m-anisidine, and N-methyl-2 : 5 : 7- and 2 : 6 : 6-aminonaphtholsulphonic acids. Specifications 612,174, [Group IV (c)], and 630,452 are referred to.ALSO:Azo dyestuffs are manufactured by coupling a diazo or tetrazo compound of an amine of the general formula <FORM:0708681/IV(c)/1> (wherein X represents a radical which contains one or more benzene or naphthalene rings or both and may also contain one or more azo groups or one or more pyrazolone rings or both, one Y represents NH2 and the other a carboxylic acid group which may be esterified, Z represents hydrogen or an alkyl, aralkyl or aryl group, and n is 1 or 2) with a compound containing a methylene group capable of coupling or with a hydroxybenzene or hydroxynaphthalene derivative coupling in ortho position to the hydroxy group, and, if desired, treating the product, in substance or on the fibre, with an agent yielding metal (e.g. chromium, cobalt, nickel, lead, manganese or copper).  The products dye cellulose fibres in yellow, red, violet, blue, grey or green tints.  The diazo or tetrazo components are obtainable by the action of acid chlorides of the general formula <FORM:0708681/IV(c)/2> (wherein one A represents NO2 and the other COO. alkyl) on primary or secondary mono- or di-amines of the benzene and naphthalene series, which may contain further substituents (e.g. alkyl, aryl, aralkyl, hydroxy, acylamino, azo, or carboxylic or sulphonic acid groups, or halogen atoms), followed by reduction of the nitro group and, if desired, saponification of the ester group before or after the reduction.  The ester group may also be saponified in the final dyestuffs, as a separate step or in the course of metallization.  Examples describe the preparation of the following dyestuffs: (1) 4 : 4\sv-di-(4"-amino-3"-carboxybenzoylamino)-diphenyl \sQ 1 - (4\sv-sulphophenyl) - 3-methyl - 5 - pyrazolone (2 mols), and its copper, nickel, lead and chromium complexes; (2) 4 : 4\sv-di-(4"-amino-3"-carboxybenzoylamino) - stilbene - 2 : 2\sv - disulphonic acid \sQ 1 mol. each of 1-(4\sv-sulphophenyl)- and 1-phenyl-3-methyl-5-pyrazolone; (3) 1-aminobenzene-2-carboxylic acid or its 5-sulphonic acid or 4-sulpho-(2\sv-carboxyphenyl)-amide --> 4-amino-4\sv-(3"-methyl-5"-pyrazolonyl-1")-stilbene-2 : 2\sv-disulphonic acid (acylated with 3-carbomethoxy-4- nitrobenzoyl chloride, saponified and reduced) --> acetoacetyl-o-anisidide, and its copper, nickel and cobalt complexes; (4) as in (3) except that the first component is 1-amino-2-carboxybenzene-4-sulphonic acid and the end component is 2-(p-acetoacetylaminophenyl)-6-methylbenzthiazole - 7 - sulphonic acid; (5) 1-aminobenzene- 2-carboxylic acid or its 4 - sulpho - (2\sv-carboxyphenyl)-amide --> 1 - (4\sv-(4"-amino-3"-carboxybenzoyl)-aminophenyl) -3-methyl-5-pyrazolone --> the compound obtained by monosulphonation of acetoacetyl-o-anisidide; (6) 1-amino-2-carboxybenzene-4- or 5-sulphonic acid or 4 - sulpho - (2\sv-carboxyphenyl)-amide --> 1-(4\sv-(3"-carboxy-4"-aminobenzoyl)-aminophenyl) -3-methyl-5-pyrazolone --> acetoacetyl-o-anisidide; (7) 1 : 8-dihydroxynaphthalene 3 : 6-disulphonic acid \sM dianisidine --> (alkaline) 2-(3\sv-amino-4\sv-carbomethoxybenzoylamino) -5-naphthol-7-sulphonic acid --> acetoacetanilide; (8) dianisidine \sQ 2-(3\sv-carbomethoxy-4\sv-aminobenzoylamino) -5-naphthol-7-sulphonic acid (2 mols) \sQ 1 - (4\sv-sulphophenyl)-3-methyl-5-pyrazolone (2 mols); (9) 3-carboxy-4-aminobenzanilide (2 mols) \sQ 4 : 4\sv-bis-(3"-methyl-5"-pyrazolonyl-1")-stilbene-2 : 2\sv-disulphonic acid; (10) 3-carboxy-4-aminobenzanilide --> 4-benzoylamino-4\sv-(3"-methyl-5"-pyrazolonyl-1") -stilbene-2 : 2\sv-disulphonic acid.  In example (11), cotton is dyed yellow with the product of (4) from a bath containing sodium sulphate, with after-coppering in a separate bath containing copper sulphate and acetic acid.  Lists are given of additional components, including diamines in which X in the general formula contains two benzene nuclei linked by -CONH-, -NHCONH-, -NH-, -CO-, -CH2- and -SO2-. Specifications 612,174 and 630,452 are referred to.