Patent GB-738598-A (GB)
Title: Dis-and polyazo dyestuffs and a process for their preparation
IPC: C09B45/24
Filed: 1953-01-15
Abstract: The invention comprises dyes of the formula <FORM:0738598/IV (c)/1> wherein R1 is a mononuclear or binuclear radical of the benzene series or a radical of the naphthalene series, the two nuclei of said binuclear radical of the benzene series being connected by a simple carbon linkage or an -NH-, -NH.CO-, -CONH- or -NH.CO.NH-bridge; each of R2 and R3 is a mononuclear or binuclear radical of the benzene series, or a radical of the naphthalene series, the two nuclei of said binuclear radical of the benzene series being connected by a simple linkage, or a -CH=CH-, -NH-, -NH.CO-, -CO.NH-, or -NH.CO.NH- bridge; the radicals R1, R2 and R3 being connected with the respective -N=N- groups by a simple linkage or a pyrazolone or acetoacetylamido radical; Me is copper or nickel; one Y is hydrogen, chlorine, bromine, or methyl, and the other Y is hydrogen; m is 0, 1, 2, 3 or 4 when the R2-N=N-R1-NH- radical is other than the radical of 2 - amino - 5 - hydroxy - 6 - (21 - hydroxy) - phenylazo - naphthalene - 7,51 - disulphonic acid or of 2-amino-5-hydroxy-6-(21-hydroxy - 31 - nitro) - phenylazonaphthalene - 7.51 - disulphonic acid or of 2-amino-5-hydroxy-7 - sulpho - 6 - (21 - hydroxy) - phenylazonaphthalene-51-sulphamide, and is 1, 2, 3 or 4 when the R2-N=N-R1-NH- radical is such a radical; n is 0 or 1; the radical A contains at least one metallisable grouping of the formula II <FORM:0738598/IV (c)/2> a being -OH, -COOH, -OCH3 or -OCH2.COOH; wherein A1 is a radical A or the radical of another aminoazo compound with the exception of radicals containing the grouping having the formula III <FORM:0738598/IV (c)/3> connected to the dicarboxylic acid radical by a -NH-bridge linked in position 4; and wherein radical A and A1 contain at most 6 azo groups and a sufficient number of groups to render the dyestuffs water-soluble, e.g. sulpho, carboxy, sulphamide, or substituted sulphamide groups. They are made by (1) condensing 2 mols. of an aminoazo compound of the formula IV [(R3-N=N-)nR2-N=N-R1-NH2] Mem1 (m1 being 0, 1 or 2) which contains at least once the grouping II which may be metallized, or 2 mols. of a mixture of two dissimilar such aminoazo compounds in any desired proportions or 2 mols. of a mixture of one such aminoazo compound and an aminoazo compound of any other composition with the exception of those which have an end-positioned radical of formula III with an amino group in 4-position, with 1 mol. of a dicarboxylic acid halide of the formula V <FORM:0738598/IV (c)/4> where Hal is chlorine or bromine, and X is hydrogen, chlorine, bromine or methyl, the reactants being so chosen that the product contains at most 6 azo groups and sufficient groups to render it water-soluble; (2) diazotizing or tetrazotizing a monoamine or diamine of the formula VI <FORM:0738598/IV (c)/5> (Z being -NH2, -NO2, or a readily reducible or saponifiable acylamino group) and coupling with a component of the formula VII [(R3-N=N-)nR2]Mem11 (m11 is 0 or 1), then converting Z (where it is nitro or acylamino) into amino by reduction or saponification, diazotizing, and coupling with a component of formula VII or of any other composition, reactants being chosen as under (1), it being noted that when in first component of formula VII, n is O and R2 contains NH2, the azo compound may be diazotized and coupled with a component R3H, either before or after the conversion of Z, and that when second component contains NH2, end product may be further diazotized and coupled with a component R3H or any other component; (3) coupling one mol. of a dihydroxy compound of the formula VIII <FORM:0738598/IV (c)/6> wherein the symbols R4 represent identical or different radicals containing a carbon atom capable of coupling and being mononuclear or binuclear radicals of the hydroxybenzene series or radicals of the hydroxynaphthalene series, or radicals of the benzene or naphthalene series which contain pyrazolone or acetoacetylamide radicals, the two nuclei of said binuclear radical of the benzene series being connected by a simple linkage, or an -NH-, -NH.CO-, -CO.NH-, or -NH.CO.NH- bridge, with two mols. of a diazo compound of an amine of the formula IX [(R3-N=N-)nR2-NH2]Mem11 (which is other than 1-hydroxy-2-aminobenzene-4-sulphonic acid or its 6-nitro derivative or amide) or with two mols. of the diazo compounds from two dissimilar amines of formula IX or from one such amine and one other amine, simultaneously or in any sequence, the reactants being chosen as under (1); (4) subjecting one mol. of a monohydroxy compound of formula <FORM:0738598/IV (c)/7> (a) to coupling with 1 mol. of a diazotized amine of formula IX, and (b) to diazotization (after conversion of Z to amine, if necessary) and coupling with a component of formula VII, reactants being chosen as under (1), it being noted that when in component VII, n is zero, and R contains NH2, further coupling may be effected, and that either diazotized amine IX or component VII may be replaced by any other amine or component.  The products may be metallized in substance or on the fibre.  In examples of method (1), 1 mol. fumaryl chloride is reacted with the following dyes: (1) 2 mols. of 1 - phenyl - 3 - methyl - 5 - pyrazolone - 4 - sulphonic acid \sM 2-amino-5-nitrobenzene-1-carboxylic acid (reduction of nitro group) --> m-toluidine; (2) 2 mols. of 1-phenyl-3-methyl-5-pyrazolone-41-sulphonic acid \sM 2-amino - 5 - (41 - nitro) - benzoylaminobenzene - I-carboxylic acid (reduction of nitro group) --> m-toluidine; (3) 2 mols. of 1-methoxy-2-amino-5-acetylaminobenzene-4-sulphonic acid --> 2 - hydroxynaphthalene - 6 - sulphonic acid (hydrolysis of acetylamino group); (4) 1 mol. of anthranilic acid --> 2-[41-(411-amino)-phenyl] - phenylamino - 5 - hydroxynaphthalene-7,311-disulphonic acid and 1 mol. 4-hydroxy - 41 - amino - 1,11 - azobenzene - 3 - carboxylic acid; (5) 1 mol. 1-phenyl-3-methyl-5 - pyrazolone - 41 - sulphonic acid \sM 2 - amino - 5 - nitrobenzene - 1 - carboxylic acid (reduction of nitro group) --> m-toluidine and 1 mol. 1-amino-3-carboxy-4-hydroxybenzene-5-sulphonic acid --> 1-amino-3-acetylaminobenzene; (6) 1 mol. 1-amino-3-carboxy-4-hydroxybenzene - 5 - sulphonic acid --> 1 - amino-3-acetylaminobenzene and 1 mol. 1-carboxy - 2 - aminobenzene - 5 - sulphonic acid --> 1 - (41 - amino) - phenyl - 3 - methyl - 5 - pyrazolone; (7) 1 mol. of dye used in (3) above and 1 mol. 1-hydroxy-2-amino-6-chlorobenzene-4-sulphonic acid --> 1-(41-amino)-phenyl-3-methyl-5-pyrazolone; (8) 2/3 mol. 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid --> 4.41 - diamino - 3,31 - dimethoxy - 1,11 - diphenyl --> 1,8-dihydroxynaphthalene-3,6-disulphonic acid, and 1 1/3 mol. 4-hydroxy-41-amino - 1,1 - azobenzene - 3 - carboxylic acid; (9) 2 mols. 2-amino-5-nitrobenzene-1-carboxylic acid --> 1 - phenyl - 3 - methyl - 5 - pyrazolone-41-sulphonic acid (reduction of nitro group); (10) 2 mols. 1-carboxy-2-aminobenzene-5-sulphonamide --> 1-(41-amino)-phenyl-3-methyl-5-pyrazolone; (11) 1 mol. 1-carboxy-2-aminobenzene - 5 - sulphonic acid --> 1 - (41 - amino) - phenyl - 3 - methyl - 5 - pyrazolone and 1 mol. 2-aminobenzene-1-carboxylic acid --> 1 - (41 - amino) - phenyl - 3 - methyl - 5 - pyrazolone; (12) 1 mol. 1-carboxy-2-aminobenzene-5-sulphonic acid-(21-carboxy)-phenylamide --> 1 - (41 - amino) - phenyl - 3 - methyl - 5 - pyrazolone and 1 mol. 2-amino-5-nitrobenzene-1-carboxylic acid --> 2-acetoacetylamino-1-carboxylic acid (reduction of nitro group); (13) 1 mol. anthranilic acid --> 2-amino-5-hydroxynaphthalene - 7 - sulphonic acid and 1 mol. 4 - hydroxy - 41 - amino - 1,11 - azobenzene - 3 - carboxylic acid; (14) 1 mol. 1 - hydroxy - 2 - amino - 6 - chlorobenzene - 4 - sulphonic acid --> 2-amino-5-hydroxynaphthalene-7-sulphonic acid (copper complex) and 1 mol. 1-hydroxy-2-amino-6-chlorbenzene-4-sulphonic acid --> 1-amino-3-methoxybenzene (copper complex); (15) 1 mol. 1-hydroxy-2-aminobenzene-4,6-disulphonic acid --> 2-amino - 5 - hydroxynaphthalene - 7 - sulphonic acid and 1 mol. of 1-amino-2-hydroxynaphthalene - 4 - sulphonic acid --> 2 - amino - 5 - hydroxynaphthalene - 7 - sulphonic acid; (16) 1 mol. of 1-hydroxy-2-amino-6-chlorobenzene-4-sulphonic acid --> 2-amino-5-hydroxynaphthalene-7-sulphonic acid and 1 mol. 1-amino-2-hydroxynaphthalene-4-sulphonic acid --> 2-amino-5-hydroxynaphthalene-7-sulphonic acid; (17) 2 mols. 1-carboxy-2-aminobenzene-5-sulphonic acid --> 4-acetoacetylamino-41-carbethoxyaminostilbene-2, 21-disulphonic acid (with prior saponification of the carbethoxyamino group).  In an example of method (2), 1 mol. fumaric dichloride is condensed with 2 mol. 2-nitro - 5 - aminobenzene - 1 - carboxylic acid, followed by reduction of the nitro group, tetrazotization, and coupling with 1-phenyl-3-methyl-5-pyrazolone-41-sulphonic acid.  In examples of method (3), fumaric acid di-[5-hydroxy-7-sulphonaphthyl-(2)]-amide is (1) coupled with diazotized 1 - hydroxy - 2 - amino - 6 - chlorobenzene - 4 - sulphonic acid and then with diazotized 4,4 - diamino - 3,31 - dimethoxy - 1,1 - diphenyl --> 1-hydroxynaphthalene-3,8-disulphonic acid; (2) coupled with 2 mols. of diazotized 2-hydroxy-3,51-dicarboxy-41-amino-1,11 - diphenylurea - 5 - sulphonic acid; (3) coupled with diazotized 4-nitro-41-aminostilbene - 2,21 - disulphonic acid --> 1 - methoxy - 2 - amino - 4 - methylbenzene; (4) coupled with diazotized 1 - hydroxy - 2 - amino - 6 - chlorbenzene-4-sulphonic acid and diazotized anthranilic acid; (5) coupled with diazotized 1-hydroxy - 2 - amino - 6 - chlorobenzene - 4 - sulphonic acid and diazotized 1-carboxy-2-aminobenzene - 5 - sulphonic acid; (6) coupled with diazotized 1 - hydroxy - 2 - amino - 6 - chlorbenzene - 4 - sulphonic acid and diazotized 1 - hydroxy - 2 - aminobenzene - 4,6 - disulphonic acid; (7) coupled with diazotized o-aminophenol and diazotized 1-carboxy-2-aminobenzene-5-sulphonic acid; (8) coupled with diazotized 1-methoxy-2-aminobenzene-4-sulphonic acid and d