Patent GB-298518-A (GB)
Title: Process for the manufacture of polyazo dyestuffs
IPC: C09B31/16
Filed: 1927-07-06
Abstract: 298,518. Carpmael, A., (I. G. Farbenindustrie Akt.-Ges.). July 6, 1927. Azo dyes.-Relates to the manufacture of tetrakisazo dyes of the type R<1> # R<2> # R<3> # R<4> # X and of octakisazo dyes of the type R<1># R<2> # R<3> # R<4> # Z # R' # R<3> # R<2> # R<1> in which R' is an aromatic amine, R<2> is a diazotizable middle component of the naphthalene series, R<3> is a derivative of a sulphonated or unsulphonated 1- naphthylamine, coupled in p-position to the amino group and containing a free or substituted hydroxy group, R<4> is a derivative of 2 :5 : 7- aminonaphtholsulphonic acid containing a diazotizable amino group in the heteronuclear side chain (or a derivative thereof substituted also in the 1-position), and X and Z are coupling components selected from the following :-methyl ketol or a substitution product thereof, a pyrazolone, a derivative of a #-ketoaldehyde, 1 : 3- dioxyquinoline, a sulphazone of the formula or salicylic acid or a derivative thereof capable of coupling. The disazo dyestuff R<1> # R<2> # R<3> is diazotized and coupled with R<4>, and one molecular proportion of the resulting trisazo dyestuff is diazotized and coupled with X or two molecular proportions are diazotized and coupled with Z. The products dye cotton from a neutral or alkaline bath in clear green shades fast to light. The following examples are specified. (1) R<1> is aniline or its homologues or substitution products including its 3-sulphonic acid, 2 : 4- or 2 :5-disulphonic acid, 3-chloro-6- sulphonic acid, or 4-nitro-2 : 5-disulphonic acid, and 2-amino-1-methoxybenzene-4-sulphonic acid, or 2-amino-5-sulphobenzoic acid; R<2> is 1-aminonaphthalene or its 6- or 7-sulphonic acid; R<3> is 1-amino-2-ethoxynaphthalene-6-sulphonic acid, 1- amino-2-met,hoxy (or 2:7-dimethoxy) naphthalene, 1-amino-2-naphthoxy-#-propionic acid, the glycollic acid ether of 1-amino-2 : 7-dioxynaphthalene, or the sulphonic ester of 1-amino-2-oxyethoxynaphthalene; R<4> is 2-(4<1>-aminobenzoyl) amino - 5 - naphthol-7-sulphonic (or 1 : 7 - disulphonic) acid, 2-(4<1> [or 3<1>]-aminobenzoyl)amino-1- chloro-5-naphthol-7-sulphonic acid, 2-(4<11>-aminobenzoyl - 4<1>-aminobenzoyl)amino-5-naphthol-7-sulphonic acid, or the isomeric 3<11>-amino-4<1>- (or 3<1>) amino compounds, 3<1>-aminophenyl-1- : 2-naphthimidazol-5-oxy-7-sulphonic acid, 4<1> (or 3<1>)- aminophenyl-1 : 2-naphthothiazol - 5 - oxy - 7 - sulphonic acid, or the corresponding triazol derivatives, 3-amino-y-2 (5-oxy-7-sulpho)naphthylbenzimidazol, or 4'- (or 3<1>)-aminophenyl-2(5-oxy-7- sulpho)naphthyl urea; and X is methyl ketol or its sulphonic acid, sulphazone, salicylic acid, ocresotinic acid, 1 : 3-dioxyquinoline, 1-phenyl-3- methyl (or carboxy)-5-pyrazolone, or 1(2<1>[or 3<1> or 4<1>]-carboxy)phenyl-3-methyl-5-pyrazolone. (2) R<1> is 2-aminonaphthalene-4 : 8-disulphonic acid; R<2> is 1-aminonaphthalene; R<3> is 1-amino-2- methoxynaphthalene-6-sulphonic acid; R<4> is 3<1>- aminophenyl-1 : 2-naphthimidazol-5 - oxy - 7 - sulphonic acid; and X or Z is 1-(4<1>-carboxy)phenyl- 3-methyl-5-pyrazolone, or another of the pyrazolones enumerated in Example 1, or the pyrazolone or dipyrazolone obtained from the hydrazine of aniline-2 (or 3 or 4)-sulphonic acid, benzidine, dehydrothiotoluidine sulphonic acid, 5- amino-salicylic acid, 3-amino-5-sulphosalicylic acid, or 2: 5: 7-aminonaphtholsulphonic acid, or the condensation product from p-aminobenzaldehyde (1 mol.) and o-cresotinic acid (2 mols.). (3) R' is aniline-2 : 4-disulphonic acid, R<2> is 1-aminona.phthalene, R<3> is 1-amino-2-acetoxynaphthalene- 7-sulphonic acid, 1-amino-5-oxy (or acetoxy) naphthalene or its 6-sulphonic acid, or 1-amino- 8-oxy (or acetoxy) naphthalene-6-sulphonic acid; R<4> is 2-(3<1>-aminobenzoylamino-5-naphthol-7-sulphonic acid; and X or Z is acetoacetanilide or its 4-carboxylic acid, acetoacet-2-toluidide, acetoacet- 2-chloranilide, acetoacet-4-anisidide, acetoacet-5- nitro-4-chloro-2-anisidide, di-(acetoacet)-toluidide, benzoyl .acetanilide, or another derivative of a #- ketoaldehyde such as 1 : 3-diketohydrindene. The acetyl group, if present in the trisazo dyestuff, is split off before the final coupling. 4-Nitraniline-2 5-disulphonic acid is cbtained by direct nitration of aniline-2 : 5-disulphonic acid. 1-Amino-2-naphthoxy-#-propionic acid is obtained by treating 2-naphthol with #-chloropropionic acid in presence of an agent for combining with acid, nitrating and reducing the nitro group. 1-Amino-2- : 7-dioxynaphtalene glycollin acid ether is obtained by treating 2 : 7-dioxynaphthalene (1 mol.) with chloracetic acid (2 mols.) in presence of an agent for combining with acid, nitrating, and reducing the nitro group. 1-Amino - 2 - oxyethoxynaphthalene sulphonic ester is obtained by nitration of the sulphonic ester of 2-oxyethoxynaphthalene, prepared as described in Specification 265,940, and reduction of the nitro group. 2-(4<1>[ or 3<1>]-Aminobenzoyl)amino - 1 - chloro-5- naphthol-1-sulphonic acid is obtained by treating 2-amino-1-chloro-5-naphthol-7-sulphonic acid with 4 (or 3)-nitrobenzoyl chloride in presence of an agent for combining with acid, and reducing the nitro group. 4- (or 3<1>)-Aminophenyl-2 (5-oxy-7-sulyho)naphthyl urea is obtained by condensing 4-(or 3)-nitro. phenylurea or 4 (or 3)-nitrophenylisocyanate with 2 : 5 : 7-acid, and reducing the nitro group. 1-Amino-2-methoxynaphthalene-6-sulphonic acid is obtained by methylating 2-naphthol-6-sulphonic acid by means of dimethyl sulphate or methyl chloride, nitrating, and reducing the nitro group. 1-Amino-5-acetoxynaphthalene, its 6-sulphonic acid, and 1-amino-8-acetoxynaphthalene - 6 - sulphonic acid are obtained by treating 1 : 5-aminonaphthol, its 6-sulphonic acid, and 1 : 8-aminonaphthol-6-sulphonic acid respectively with acetic anhydride in alkaline solution at a low temperature. Acetoacet-5-nitro-4-chloro - 2 - anisidide is obtained by heating 5-niti-o-4-chloro-2,-anisidine with acetoacetic ester either alcne or in an indifferent solvent.