Patent GB-755450-A (GB)
Title: Improvements in or relating to polyazo dyestuffs
IPC: C09B35/362
Filed: 1954-03-19
Abstract: The invention comprises dyestuffs of formula:-<FORM:0755450/IV(c)/1> where <FORM:0755450/IV(c)/2> is the residue of a naphthol compound of formula:- <FORM:0755450/IV(c)/3> where n is 0, 1 and 2, y is H, OH or an amino group which may be alkylated, cycloalkylated, aralkylated, arylated or acylated, or the residue of a naphthol sulphonic acid of formula:- <FORM:0755450/IV(c)/4> where one Z is OH and the other an -N=N-pyrazolone or -N=N-aryl residue containing a metallizable group in an ortho position to -N=N-, or the residue of a metal complex compound of such a naphthol sulphonic acid, <FORM:0755450/IV(c)/5> is the residue of a middle component of the benzene or naphthalene series, m is 1, 2 or 3, x is H or an alkylated, cycloalkylated, aralkylated, arylated or acylated amino group, and wherein the -OH groups and "alkoxy" are in ortho position to the respective azo groups and -azois in the para position to the respective azo group. The invention also includes copper and nickel complexes of the above dyestuffs.  The dyestuffs may be made by the alkaline coupling of a diazo compound of 1-aminobenzene-2carboxylic acid substituted in the 4 position with a group capable of conversion to an amino group with the desired naphthol sulphonic acid, converting the said 4-substituent into an amino group, diazotizing, advantageously by an indirect method, coupling, e.g. in an acetic or formic acid medium, with an appropriate ortho-alkoxy-aminomiddle component diazotizing and coupling, advantageously in a weakly alkaline medium and optionally in the presence of an organic base, with the necessary naphthol or naphthol sulphonic acid or metal complex thereof, and, if required, the polyazo dyestuff thus obtained is treated with a copper- or nickel-yielding agent.  Alternatively a 4-aminobenzene-2-carboxylic acid substituted in the 1-position with a group convertible to an amino group may be coupled with the above middle and final components before conversion of the 1-substituent and the aminodisazo compound thus obtained is diazotized and coupled with an appropriate naphthol and the product metallized if desired, the conditions of diazotization and coupling being as in the previous method except that the final coupling is advantageously effected in a weakly alkaline medium, optinally in the presence of an organic base. When the middle component is a 1-amino-2-alkoxynaphthalene-6-sulphonic acid coupling is advantageously effected in an alkaline medium, 4-substituted 1-amino-benzene-2-carboxylic acids specified are 1-amino-4-nitro-, -acetylamino-, -oxalylamino-, -benzoylamino-, and carbo-methoxy- and ethoxyamino - benzene - 2 - carboxylic acids.  Specified naphthol sulphonic acids containing the group (SO3H)m are 1-naphthol-3-, -4- and -5- mono-, -3, 6- and -3, 8- di- and 3, 5, 7- and -3, 6, 8- tri-sulphonic acids, 2-naphthol-4-, -6- and -8- mono-, -3, 6- and -6, 8- di- and -3, 6, 8- tri-sulphonic acids, 2-methyl-, -ethyl-, -propyl-, -cyclohexyl-, -benzyl-, -phenyl-, (31 or 41-carboxy-, or 41-methoxy-)-phenyl-, acetyl-, -propionyl-butyryl-, -benzoyl- and -carbo-methoxy- or -ethoxy - amino - 5(8) - hydroxy - naphthalene - 7(6) - sulphonic acid, 2-acetyl- or -benzoylamino -5- hydroxynaphthalene -1, 7-disulphonic acid, 1-acetyl- or benzoyl-amino-8-hydroxynaphthalene -4- mono- and -3, 6- disulphonic acids and 2-acetyl- or benzoyl-amino -6- hydroxynaphthalene -8- sulphonic acid.  Specified middle components are 1 - amino - 2 - methoxy - or - ethoxy - benzene, -naphthalene, - naphthalene - 6 - sulphonic acid and - 5 - methyl - or - acetylamino - ben - zene and 1 - amino - 2, 5 - dimethoxy - or - diethoxy - benzene.  Specified naphthols containing y or sulphonic acids containing z used in both preparations are those containing (SO3H)m (except trisulphonic acids) and 1 - and 2 - naphthol, 1 - amino - 8 -hydroxynaphthalene - 4 - sulphonic acid, 2 - amino - 5(8) - hydroxynaphthalene - 7 (6) - sulphonic acid, 2 - amino - 5 - hydroxynaphthalene - 1, 7 - disulphonic acid, 1 - (21 - carboxybenzene - 11 - azo and - 41 - nitro - 21 - carboxybenzene - 11 - azo) - 2, 5 - dihydroxynaphthalene - 7 - sulphonic acid, 1 - (21-carboxy - and -hydroxy - benzene - 11 - azo) - 2, 5 - hydroxynaphthalene - 7, 51 - disulphonic acid, 1 - (21 - hydroxybenzene - 11 - azo) - 2, 5 - dihydroxynaphthalene - 7, 41 - disulphonic acid, 1, 5 - dihydroxy - 2 - (21 - hydroxy - benzene and - naphthalene - 11 - azo) - naphthalene - 7, 41 - disulphonic acid, 1, 5 - dihydroxy - 2 - (21 - hydroxynaphthalene - 11 - az - naphthalene - 7, 61 - disulphonic acid, 1, 5 - dihydroxy - 2 (11 - hydroxynaphthalene - 21 - azo) - naphthalene - 7, 41 - di - and 7, 31, 61 - trisulphonic acid and 1, 5 - dihydroxy - 2 (11 - phenyl - 31 - methyl -51 - pyrazolone - 41 - azo) - naphthalene - 7, 411 - disulphonic acid.  Naphthol compounds which may be obtained as metal complexes may be coupled in their metallized form with the diazotized amino - dis - or mono - azo compounds.  Specified 4 - aminobenzene - 2 - carboxylic acids are 1 - nitro -, acetylamino - , oxalylamino - , - benzoylamino - and -carbomethoxy - or - ethoxyamino - 4 - aminobenzene - 2 - carboxylic acid.  Metallization is effected in the usual way.  The dyestuffs dye cotton and regenerated cellulose in blue grey shades.  Examples and a Table are provided illustrating the use of certain of the above specified components in the preparation of dyestuffs, an additional end component used being 1 - (21 - carboxybenzene - 11 - azo) - 2, 5 - dihydroxynaphthalene - 7, 41 - disulphonic acid.