Patent GB-333573-A (GB)
Title: Process for the manufacture of substantive ª¤-carboxyazo dyestuffs containing copper
IPC: C09B35/08
Filed: 1929-05-10
Abstract: 333,573. Carpmael, A., (I. G. Farbenindustrie Akt.-Ges.). May 10, 1929. Diazo dyes and soluble copper compounds thereof.-Substantive o-carboxyazo dyestuffs containing copper are made (1) by causing an agent yielding copper, including metallic copper, to act on azo-dyestuffs obtainable from tetrazotized benzidine-3 : 31-dicarboxylic acid and two molecular parts of such aryl- or aroylaminonaphthol sulphonic acid in which the aryl- or aroyl residue is substituted by groups inducing solubility in water, (2) by effecting the dyestuff coupling in the presence of an agent yielding copper with the exception of a water-soluble complex nitrogenous copper compound, (3) by making up a dyebath with the o-carboxyazo dyestuff with the addition of the coppering agent. Reddish violet to blue shades are obtained. In examples the following dyestuffs are specified: (1) benzidine- 3 : 3<1>-dicarboxylic acid # 7'-sulpho-5'-hydroxy- 2<1>-naphthyl-4-aminophenoxyacetic acid (2 mols.) treated with copper sulphate ; other coupling components are 7'-sulpho-5'-hydroxy-2'-naphthyl- 4-aminophenylthioglycollic acid, 7<1>-sulpho-5<1>- hydroxy - 2<1> - naphthyl-4-amino-2-methyl (or 2- chloro)-phenoxy acetic acid, 7<1>-sulpho-5<1>-hydroxy- 2<1>-naphthyl-4-aminophenoxyacetic acid and other 7<1> - sulpho - 5<1>-hydroxy - 2<1>-naphthylamino-arylhydroxy acetic acids or arylthioglycollic acids or arylhydroxy-#-propionic acids such as those from 4- (or 3-) aminophenoxy-#-propionic acid, (2) the tetrazo compound is coupled with 2-(2'-methoxy- 5'-sulphophenylamino)-5-naphthol-7-sulphonic acid in solution with copper sulphate or similarly with 2-(4<1>-sulphophenylamino)-5-naphthol - 7 - sulpho acids or 7<1> - sulpho-5<1>-hydroxy-2<1>-naphthyl-4- aminobenzyl-#-sulphonic acid. (3) Cotton is dyed in a bath containing the dye benzidine-3: 3<1>-dicarboxylic acid # 2-(3<1>-carboxyphenylamino)-5- naphthol-7-sulphonic acid (2 mols.) and copper sulphate; the dyes containing as coupling components arylated J acids with a carbonamide group (CONH2) in the aryl residue may also be used. (4) The dyestuffs benzidine-3 31-dicarboxylic acid # 2(2<1>-carboxybenzoylamino)-5- naphthol-7-sulpho acid (2 mols.) or 7<1>-sulpho-5<1>- hydroxy-2<1>-naphthyl-4-aminophenylacetic acid (2 mols.) or 7<1> - sulpho - 5<1> - hydroxy-2'-naphthyl-4- aminohydrocinnamic acid (2 mols.) or 7<1>-sulpho- 51 - hydroxy - 2 - naphthyl-4-aminophenoxyacetic acid (1 mol) and 6<1>-sulpho-8-hydroxy-2<1>-naphthyl- 4-aminophenoxyacetic acid (1 mol.) or 7"-sulpho- 5" - hydroxy-2<1>-naphthyl-2<1>-amino-1 : 11-diphenylether-4-sulphonic acid (2 mols.) or 7<1>-sulpho-5<1>- hydroxy-2<1>-naphthyl-4-aminophenylglycerol or glycollic ether or the sulphuric acid ester of the latter (2 mols.) are treated with copper sulphate. Aryl- and aroylaminonaphtholsulphonic acids substituted in the aryl- or aroyl residues by groups inducing solubility in water are made generally by Bucherer's reaction. The following are made from 2 : 5-dioxynaphthalene-7-sulphonic acid, sodium bisulphite and the corresponding amine : 7 - Sulpho - 5<1>-oxy-2<1>-naphthyl-4-aminophenoxyacetic acid from 4-aminophenoxyacetic acid, 7<1>- sulpho - 5<1>-oxy-2<1>-naphthyl-4-aminophenylthioglycollic acid from 4-aminophenylthioglycollic acid, 7<1>-sulpho-5<1>-oxy-2<1>-naphthyl-4-amino-2-methyl (or 2-chloro)-phenoxyacetic acid from 4-amino-2- methyl (or 2-chloro)-phenoxyacetic acid, 2-(2<1>- methoxy-5<1>-sulphophenylamino)-5-naphthol-7- sulphonic acid from 2-anisidine-4-sulpho acid, 7<1>- sulpho - 5<1>-oxy - 2<1> - naphthyl-4-aminobenzyl-#- sulpho acid from 4-aminobenzyl-#-sulphonic acid, 2-(3<1>-carboxyphenylamino)-5-naphthol-7- sulphonic acid from 3-aminobenzoic acid, 7<1>-sulpho-5<1>-oxy- 2<1>-naphthyl-4-aminophenylacetic acid from 4- aminophenylacetic acid, 7<1> - sulpho-5<1>-oxy-2<1>- naphthyl-4-aminohydrocinnamic from 4-aminohydrocinnamic acid, 7<11> - sulpho - 5<11> oxy-2<11>- naphthyl-2<1>-amino-1 : 1<1>-diphenylether-4-sulphonic acid from 2-amino-1 : 11-diphenylether-4-sulphonic acid, 7<1>-sulpho-5<1>-oxy-2<1>-naphthyl-4-aminophenylglycerol or glycollic ether from 4-aminophenylglycerol or glycolic ether. Arylated J acids containing carbonamide residues in the aryl residue are made by treating J acid or 2 : 5-dioxynaphthalene-7-sulphonic acid with aminobenzonitriles e.g. 3-aminobenzonitrile and bisulphite. 2-(2<1>-Carboxybenzoylamino)-5-naphthol-7-sulphonic acid is made from J acid, phthalic anhydride and sodium acetate. 7<1> - Sulpho-5<1>-oxy-2<1>naphthyl-4-aminophenylglycollic ether sulphuric acid ester is made by treating the ether with sulphuric acid. 4--Aminophenylthioglycollic acid is made from p-nitrothiophenol and monochloracetic acid and reducing. 4-Aminophenylthioglycollic acid is made from 4- (or 3) nitrophenol and #-chlorpropionic acid and reducing. 4-Aminophenylglycollic ether is made from 4- nitrophenol and glycolmonohydrin and reducing.