Patent GB-740660-A (GB)
Title: Improvements in or relating to azo dyestuffs
IPC: C09B43/16
Filed: 1953-10-02
Abstract: The invention comprises azo-dyes of the formula below and copper complexes thereof:- <FORM:0740660/IV(c)/1> where R1 denotes a mononuclear radical of the benzene series or a binuclear radical of said series, wherein both benzene nuclei are linked by a CH=CH- or -NH.CO-bridge, R-2COOH denotes a radical of the benzene series, wherein -COOH is ortho to -N=N, R1 is a mono- or bi-nuclear radical of the benzene series, R11 denotes a simple linkage or a radical of the formula <FORM:0740660/IV(c)/2> which may be substituted in the benzene nucleus by methyl or methoxy, Z denotes halogen, -OH, -NH2, or the residue of an amine, and wherein nucleus A may be monosubstituted by a sulphonic acid group in one of the positions 5, 6, 7 and 8, and may be mono- or di-halogenated in positions 6 and 7. They are made by condensing 1 mol. of a tri-halogen triazine, or a dihalogen triazine containing a substituent Z other than halogen, with 1 mol. of a compound of the formula:- <FORM:0740660/IV(c)/3> and with 1 mol. of a compound of the formula:- <FORM:0740660/IV(c)/4> (which may be coppered), or with 1 mol. of a compound:- <FORM:0740660/IV(c)/5> followed by coupling with 1 mol. of a diazotised ortho-aminocarboxylic acid of the benzene series.  Where a trihalogentriazine is used, the third halogen atom may be replaced by hydroxy, amine, or the residue of an amine, before or after the coupling step in the second process above.  In example, cyanuric chloride is condensed with the aminoazo compound 1-carboxy -2- aminobenzene -5- sulphonic acid - > 1-[411-amino-11 111-stilbenyl-(41)]-3-methyl - 5 - pyrazolone-21, 211 -disulphonic acid as such or as its copper complex, and with 1-amino - 4 - (41-amino)-phenylamino-anthraquinone-2-sulphonic acid or 1-amino-4- [41-(411-amino) - phenyl] - phenylamino anthraquinone-2- 311-disulphonic acid in either sequence, coppering if necessary. Also in examples, cyanuric chloride is condensed with the first of the two anthraquinone compounds and with the stilbenylpyrazolone, and coupling with diazotised 1-carboxy -2- aminobenzene -5- sulphonic acid may take place before or after condensation with aniline.  The products dye cotton and regenerated cellulose green shades.  A number of other combinations of starting materials are listed where (1) R1 is a stilbenyl disulphonic acid radical, R2 contains sulphonamide or various N-substituted sulphonamide groups, and various amines corresponding to Z may be used namely, -aniline, methylamine, ethanolamine, diethanolamine, sulphanilic acid, or Z may be hydroxy, amino, or chlorine; (2) R1 is phenylene or substituted phenylene, R2 contains sulphonic or sulphonamide groups, and amines used are aniline, methylamine, ethanolamine, p-aminoacetanilide, p-aminoazobenzene, 4-amino-41-hydroxy - 1 11-azobenzene - 31 - carboxylic acid, p-toluidine, p-chloraniline (3) R1 the radical from benzoylaminobenzene, R2 is the radical from 1-carboxy-2-amino-benzene-5-sulphonic, and methylamine or ethanolamine is used as amine.  1-Amino-4- [41-411 -amino benzoylamino] phenylaminoanthra quinone - 2 - sulphonic acids and 1-amino] 4- 41- [411(-4111-aminobenzoylamino)-phenyl -phenylamino anthraquinone-2- sulphonic acids are made by (a) condensing 1 - amino - 4 - halogen - anthra quinone-2-sulphonic acids with diaminobenzoylaminobenzenes or diaminobenzoylaminodiphenyls or by nitrobenzoylation and reduction from 1-amino-4-(p-amino phenylamino) or (p-aminodiphenylamino)-anthraquinone-sulphonic acids. Specification 657,753 is referred to.