Patent GB-751386-A (GB)
Title: Improvements relating to tetrakisazo dyestuffs and their use
IPC: C09B45/24
Filed: 1954-03-01
Abstract: The invention comprises dyestuffs of formula:-<FORM:0751386/IV(c)/1> where R1 and R11 are residues of a monoo poly-nuclear diazonium compound of the benzene series containing an OH group o to a COOH group, R2 and R12 are aryl compounds of the benzene or naphthalene series having the azo groups in p position and a metal complex forming group o to the azo group bound to the naphthalene residue and R3 is a bridging member linking the N atoms of the phenylamino groups with the aid of a lubricant residue of an at least dibasic carbon containing acid.  They may be made by coupling in an alkaline medium, advantageously in the presence of tertiary nitrogen base 2 mols of the same or different diazonium compounds of amines of formula R1-N = N-R2-NH2 with 1 mol of the appropriate coupling component.  Specified starting components for R1 and R11 are 5-amino-2-hydroxybenzene-1-carboxylic acid and derivatives thereof substituted by halogen, methyl or sulphonic acid groups although polynuclear components especially 31- or 41-aminobenzoyl derivatives of aminosalicylic acid the benzoyl radicle of which may be substituted e.g. with halogen, alkoxy or alkyl substituents yield more valuable dyestuffs. Particularly favourable starting components are those of formula <FORM:0751386/IV(c)/2> where X is H, Hlg, Me or SO3H and one Y is an amino group the other being H, Hlg, Me, MeO or EtO.  Specified components for R2 or R12 are 5-methyl-2-hydroxy- and -methoxy-aniline, 2, 5-dimethoxy-aniline, and preferably 2-methoxy-, ethoxy- and -carboxymethoxy-1-amino-naphthalenes and their 6- and 7-sulphonic acids.  Particularly favourable aminomonoazo components are those of formula <FORM:0751386/IV(c)/3> where Y is H, Hlg, Me or MeO X is as above and one 2 is H and the other H or SO3H.  Specified for R3 are = CO, = CS, and cyanine, oxalic, succinic, pimelic, adipic, sebacic, fumaric, dimethyl ether dicarboxylic thiodiglycollic, iso- and terephthalic acid residues and dicarbonic acid half ester residues of aliphatic diols, e.g. of ethylene glycol, 1, 2- and 1, 3-dihydroxypropane, 1, 4- and 2, 3-dihydroxybutane, b , b 1-dihydroxy diethyl ether and sulphide and o , o 1 dihydroxy-triethylene diether.  The coupling components are made by reacting 2-(41-aminophenylamino)-5-hydroxynaphthalene -7-sulphonic acid, advantageously as an alkali metal salt aqueous solution, with the acid halides corresponding to R3. Advantageously when using cyanuric chloride the third halogen thereof is replaced by ammonium or primary or secondary amines. The dyestuffs dye cellulose fibres in blue to green-blue shades which are fixed by coppering.  Coppering may be effected in conventional fashion in substance or advantageously on the fibre. In examples dyestuffs are made using the following components corresponding to R1 and R11:-5-(31- and 41-aminobenzoylamino)-, -(31methyl -41- aminobenzoyl-amino)-, -(41-methyl -31- amino-benzoyl and -(41-chloro- or -methoxy -31- aminobenzoylamino) -2- hydroxybenzene -1- carboxylic acid, 5-(31-aminobenzoylamino)-2-hydroxy -3- chloro- or -3- or -4- methylbenzene -1-carboxylic acid, 5-(41methyl-31-amino - benzoylamino)-, -(31methyl -41-aminobenzoylamino) and -(41-aminobenzoylamino) -2- hydroxy -3- methylbenzene -1- carboxylic acid, 5-(31- and -41-aminobenzoylamino)- and -(41-methyl-31-aminobenzoylamino)-2-hydroxybenzene -3-sulphonic acid -1- carboxylic acid, 5-amino 2-hydroxy benzene -1- carboxylic acid and 5-amino -3- and -4- methyl and -3- chloro-2-hydroxybenzene -1- carboxylic acid, and the following components corresponding to R2 and R12:-1-amino -2- naphthylglycollic acid and the 6 and 7 sulphonic acids thereof, 1-amino -2- methoxy- and -ethoxy-naphthalene -6- and -7- sulphonic acids, 1-amino-2, 5-dimethoxy-benzene, 1-amino -5- methyl -2- methoxy- and -2-hydroxy-benzene and 1-amino -2-methoxybenzene, middle components being prepared from 2(41-aminophenylamino) -5-hydroxy-naphthalene -7- sulphonic acid and benzene-1, 4- and -1, 3-dicarboxylic acid chloride ethylene- and di- and triethylene glycol, 1, 3-dihydroxypropane and 1, 2- and 1, 4-n-dihydroxybutane dichlorocarbonic acid esters, phosgene, oxalic, bebacic, succinic, adipic, diglycollic, dithioglycollic and fumaric acid dichlorides and cyanuric chloride the third chlorine atom of which is replaced by reaction with ammonia, methyl- and diethyl-amines aniline, p-toluidine and 5-amino -2-hydroxy benzene -9- carboxylic acid.