Patent GB-828698-A (GB)
Title: Improvements relating to disazo dyestuffs and their use
IPC: C09B35/02
Filed: 1956-03-21
Abstract: Diamines of formula <FORM:0828698/IV (b)/1> wherein B1 and B2 are o-phenylene radicals, possibly substituted by non-salt-forming groups, X1 and X2 are oxygen atoms or <FORM:0828698/IV (b)/2> wherein R is an alkyl radical containing at most 6 carbon atoms, an aralkyl, phenoxyalkyl or phenyl radical or hydrogen and -X1-A-X2-in the radical of an aliphatic, alicyclic, araliphatic, heterocyclic or aromatic diamine, diphenol or dinaphthol or of a hydroxyarylamine, are used as tetrazo components in the preparation of disazo dyes (see Group IV (c)) They are prepared by reacting o-nitrobenzene sulphonyl halides with a suitable diamine or dihydroxy or aminohydroxy compound, followed by alkylation at the amide nitrogen atom if desired, and reduction of the nitro group to an amino group.  The o-nitrobenzene sulphonyl halide may be substituted by halogen atoms or alkyl, alkoxy, phenoxy, acylamino or alkylsulphonyl groups.  In examples: (1) 2-nitrobenzene sulphonyl chloride is reacted with the condensation products of excess phenol and acetone, methyl ethyl ketone, 2-methyl-hexanone-4 cyclohexanone, acetophenone or 2-decalone and the nitro groups are reduced to amino, to give the 2-aminobenzene sulphonyl derivatives of 2:2-bis-(41-hydroxyphenyl)-propane or -decahydronaphthalene or -butane, 1:1 - bis - (41 - hydroxyphenyl) - cyclohexane or -1-phenylethane and 3:3-bis-(4-hydroxyphenyl)-5-methylhexane. Other compounds of the above formula specified in examples are the 2-aminobenaene sulphonyl derivatives of N:N1 - dibenzyl - 1:6 - hexamethylene diamine, 4 - 41 - bis - ethylamino - 2:21 - or 3:31 - dimethyldiphenyl, 4:41 - bis - ethylamino - diphenyl, N:N1 - bis - phenoxyethylethylene diamine, 2:21 - bis - N - benzylamino-ethyl ether or thioether, 1:1-bis-(41-ethylaminophenyl) - cyclohexane, 2:2 - bis - (41 - n - butylaminophenyl) - propane, 4:41-bis - ethylamino - diphenyl sulphide, 1:4-dihydroxybenzene, 3:3 - bis - (41 - hydroxyphenyl) - heptane, 4:41 - bis - methylamino-2:21 - dimethyldiphenyl, 4 - hydroxy - 1 - benzylamino - benzene, 2:21 - dihydroxy - 5:51 - dimethyldiphenylmethane, 4:41 - bisethylamino - diphenylmethane, 4:41 - dihydroxydiphenyl sulphone, 2:21 - bis - (31-methyl - 41 - hydroxyphenyl) - propane and 4:41 - bis - ethylaminodicyclohexyl - methane; the 4-methyl- or -methoxy-2-aminobenzenesulphonyl drivatives of 2:2-bis-(41-hydroxyphenyl) - propane; the 5 - acetylamino - 2 - aminobenzene sulphonyl derivatives of 2:2-bis - (41 - hydroxphenyl) - propane and 1:1-bis - (41 - hydroxyphenyl) - cyclohexane, and the 5 - chloro - 2 - aminobenzene - sulphonyl derivatives of 4:41 - bis - ethylamino - diphenylmethane and 2:21 - dihydroxy - 5:5-dimethyl-diphenyl-methane.ALSO:The invention comprises disazo dyestuffs of formula <FORM:0828698/IV(c)/1> wherein C1 and C2 are radicals of a 2-aminonaphthalene sulphonic acid coupled in the 1-position, B1 and B2 are o-phenylene radicals possibly substituted by non-salt-forming groups, X1 and X2 are oxygen atoms or <FORM:0828698/IV(c)/2> groups wherein R is an alkyl radical containing at most 6 carbon atoms, an aralkyl, phenoxyalkyl or phenyl radical or hydrogen, and -X1-A-X2- is the radical of an aliphatic, alicyclic, araliphatic, aromatic or heterocyclic diamine, diphenol or dinaphthol or of a hydroxyarylamine; or a salt of such a dyestuff. The dyes may be prepared by tetrazotizing a diacyl derivative of an o-aminobenzene sulphonic acid and an aliphatic, alicyclic, araliphatic, aromatic or heterocyclic diamine, diphenol dinaphthol and hydroxyarylamine and coupling it with 2 mols. of the same or with 1 mol. of each of two different 2-aminonaphthalene sulphonic acids coupling in the 1-position. The preferred tetrazo components are acyl derivatives of secondary amino groups and are prepared by reacting o-nitrobenzene sulphonic acid halides with secondary diamines, or preferably with primary diamines followed by alkylation at the amide nitrogen atom, and finally reducing nitro groups to amino.  The tetrazo compounds may also be derived by similar reactions from dihydroxy and hydroxy-amino-aromatic compounds (see Group IV (b)). Specified amino and hydroxy compounds from which the tetrazo components may be obtained include ethylene diamine, 2 : 21-bisaminoethyl ether or sulphide, 4 : 41-diaminodicyclohexylmethane, 4 - aminobenzylamine, 1 : 3 - or 1 : 4 - diaminobenzene, 1 : 4 - or 1 : 5 - di-aminonaphthalene, piperazine, bis-aminophenyl sulphoxides, sulphones, ketones and ureas, 1 : 3 - or 1 : 4 - dihydroxybenzene, 1 : 5 -, 2 : 6-and 2 : 7 - dihydroxynaphthalene, bis - hydroxyphenyl ethers, thioethers, sulphoxides and sulphones, p - aminophenol, 2 - or 4-amino - 31 - or - 41 - hydroxydiphenyl ether and 2- or 4-amino-41-hydroxydiphenyl sulphide.  The benzene rings of the acyl radicals in the tetrazo components may be substituted by halogen atoms or alkyl, alkoxy, phenoxy, acylamino or alkylsulphonyl groups.  The tetrazo components are preferably tetrazotized either in inert organic solvents such as methanol, ethanol, ethylene glycol monomethyl or monomethyl ether, acetic or formic acids, in the presence of mineral acids with sodium nitrite or in concentrated sulphuric acid with nitrosyl sulphuric acid.  Specified coupling components, other than those specified in examples, are 2-amino or -methylamino-8-naphthol-3 : 6-disulphonic acid, 2 - methylamino - naphthalene-5 -, - 6 - or - 7 - sulphonic acid and 2 - ethylamino - naphthalene - 5 - sulphonic acid.  The disazo dyes in the form of their alkali metal salts, dye wool in red shades.  In Examples the following diamines are tetrazotized and coupled with one, or a mixture of two, of the 2-aminonaphthalene compounds also listed below. Tetrazo components specified are: the bis-o-aminobenzenesulphonyl derivatives of N : N1-dibenzyl - or - diphenoxy - ethyl - 1 : 6 - hexamethylene diamine, 4 : 41 - bis - ethylamino-2 : 21 - or - 3 : 31 - dimethyldiphenyl, 4 : 41 bisethylamino - diphenyl, 1 : 1 - bis - (41 - hydroxyphenyl) - cyclohexane, - 1 - phenylethane or decahydronaphthalene, 2 : 2 - bis (41 - hydroxyphenyl) - propane or - butane, 3 : 3 - bis (41-hydroxyphenyl) - 5 - methylhexane, N : N1-bis - phenoxyethyl - ethylene p  diamine, 2 : 21-bis - N1 - benzylamino - ethyl ether or sulphide, 1 : 1 - bis (41 - ethylaminophenyl) - cyclohexane, 2 : 2 - bis (41 - n - butylaminophenyl) - propane, 4 : 41 - bis - ethylaminodiphenyl sulphide, 1 : 4-dihydroxybenzene, 3 : 3 - bis (41 - hydroxyphenyl) - heptane, 4 : 41 - bis - methylamino-2 : 21 - dimethyldiphenyl, 4 - hydroxy - 1-benzylamino - benzene, 2 : 21 - dihydroxy - 5 : 51 dimethyldiphenylmethane, 4 : 41 - bis - ethylamino - diphenylmethane, 4 : 41 - dihydroxy-diphenyl sulphone, 2 : 2 - bis (31 - methyl - 41-hydroxyphenyl) - propane and 4 : 41 - bis-ethylamino - dicyclohexylmethane; the 4-methyl - or - methoxy - 2 - aminobenzene - sulphonyl derivatives of 2 : 2 - bis (41 - hydroxyphenyl) - propane; the 5 - acetylamino - 2-aminobenzene - sulphonyl derivatives of 2 : 2-bis (41 - hydroxyphenyl) - propane and 1 : 1-bis (41 - hydroxyphenyl) - cyclohexane; and the 5 - chloro - 2 - aminobenzenesulphonyl derivatives of 4 : 41 - bis - ethylaminodiphenylmethane and 2 : 21 - dihydroxy - 5 : 51 - dimethyl - diphenyl methane.  Coupling components specified are 2-amino- or -ethylamino-8-naphthol - 6 - sulphonic acid, 2 - ethylaminonaphthalene - 6 - or - 7 - sulphonic acid, 2-aminonaphthalene - 5 -, - 6 - or - 7 - sulphonic acid, 2 - amino - 5 - methoxy - or - ethoxynaphthalene - 7 - sulphonic acid and 2 - aminonaphthalene-3 : 6-disulphonic acid.