Patent GB-786670-A (GB)
Title: Improvements in or relating to metallizable polyazo dyestuffs
IPC: C09B45/24
Filed: 1955-06-29
Abstract: The invention comprises dyestuffs of formula <FORM:0786670/IV (b)/1> where one X is H and the other SO3H, y is H or SO3H, R1 and R2 are benzene residues in which -azois p to -N=N- and which contain a COOH or MeO group in o-position to -N=N-and W1 and W2 are residues of compounds of formula <FORM:0786670/IV (b)/2> where Z is OH or COOH and V is an alkyl, cycloalkyl, aralkyl or aryl residue which may be substituted.  Nucleus A may contain substituents such as halogen, nitro, alkylsulphonyl, sulphonic acid, sulphonamide and N-alkyl, dialkyl and mononuclear aryl derivatives thereof and mononuclear arylazo groups.  They are made when 1 mol. of a compound of formula <FORM:0786670/IV (b)/3> where both R's are the appropriate benzene residues one containing an amino group in p-position to -N=N- the other an amino group or a nitro or acylamino group in p-position to -N=N- is either tetrazotized (when both R's contain amino groups) and coupled with 2 mols. of the necessary aminoazo compound or compounds or (when R is NO2 or acylamino) diazotized and coupled with 1 mol of the required aminoazo compound, the NO2 or acylamino groups in the product being converted to an amino group and the tetrakisazoamino compound thus obtained diazotized and coupled with 1 mol. of an appropriate aminoazo compound.  The first coupling is preferably effected in a sodium carbonate medium and the second in the presence of an organic base.  The starting disazo compound is made by coupling an appropriate 1 - amino - 8 - naphthol - mono- or disulphonic acid first in an acid medium with 1 mol. of a diazo compound of an amine of formula <FORM:0786670/IV (b)/4> where s is COOH or MeO and t is NO2 or acylamino and then in an alkaline medium with 1 mol. of a diazo compound which is of the same general formula as that of the first coupling and transforming at least one substituent t into an amino group either by reduction or saponification.  Formyl, acetyl, oxalyl and carbomethoxy- and carboethoxy-amino groups are specified acylamino groups.  The aminomonoazo compounds are made by diazotizing appropriate 2 - amino - 1 - hydroxy- or -carboxy - benzenes and coupling in an acid medium with the required J-acids.  2 - Amino - 1 - hydroxy and -carboxy-benzenes mentioned are 2-aminophenol and benzoic acid and their 4- or 5-alkylsulphonyl derivatives, sulphonic acids, -sulphonamides which may be methylated, ethylated, dimethylated and diethylated on the N-atom of the sulphonamide group, -sulphonic acid phenylamides and their derivatives halogenated, alkylated or alkoxylated on the nucleus of the phenylamide group, -sulphonic acid-(31-carboxy-41 - hydroxy) - phenylamide, 2 - amino - 1 - hydroxy-4-chloro- and -nitro-benzenes and their 5-sulphonic acids, 2-amino-1-hydroxy-6-nitro-, -chloro- and -bromo - benzene - 4 - sulphonic acids and the corresponding isomers obtained when the groups in the 4- and 6-positions are exchanged, 2 - amino - 1 - hydroxy- and -carboxy-5-nitro-benzene, 2-amino-1-hydroxy-4-chloro-5- and 6-nitrobenzenes, 3-amino-4,41-dioxy - 1,11 - azobenzene - 31 - carboxylic acid and 3 - amino - 4 - hydroxy - 1,11 - azobenzene-31-sulphonic acid, N-substituents indicated for the J-acid components are methyl, ethyl, propyl, hydroxyethyl, cyclohexyl, phenyl, (21-, 31- and 41-methyl)-, (31- and 41-chloro-)-, 41-amino- and -carboxy-, (31 - carboxy - 41 - hydroxy)- and (31- and 41-sulpho- and sulphamido)-phenyl, -benzyl and 411-amino-11,111-diphenyl).  The dyestuffs dye cellulosic fibres by a one- or two-bath coppering process in grey shades.  Examples are provided illustrating the preparation of dyestuffs from certain of the above indicated reactants and their use in dyeing cellulosic fibres in the products obtained. R1 and R2 are derived from 2-amino-1-methoxy- or -carboxy - 5 - amino-, -acetylamino- or -nitrobenzenes and 2 - amino - 1 - methoxy - 5 - carbomethoxy - aminobenzene, the 2 - amino - 1 - hydroxy- or -carboxy-benzenes used are 2-amino - 1 - hydroxy - 4- and -5 - sulphonic acid amides, 2 - amino - 1 - hydroxybenzene - 4 - sulphonic acid methyl-, ethyl-, -21-hydroxyethyl- and -propyl-, 31-methoxypropyl- and phenyl - amides, 2 - amino - 1 - phenol - 5 - sulphonic acid and its di-21-hydrazethylamide, 2-amino-5-nitro-benzoic acid and -phenol, 2-amino - 1 - hydroxy - 4 - methylsulphonylbenzene, 2 - amino - 1 - hydroxy - 4 - nitro - benzene and 2-amino-1-hydroxy-6-carboxybenzene-4-sulphonic acid and N-substituents for the J-acid components used additional to those listed above are 31-sulphonamido and -methylsulphonyl and 21-chloro-phenyl groups.  Specification 657,753 is referred to.