Patent GB-736180-A (GB)
Title: Improvements in or relating to copper-containing polyazo dyestuffs
IPC: C09B35/08
Filed: 1953-07-06
Abstract: The invention comprises a dyestuff of formula <FORM:0736180/IV (c)/1> where R is an aromatic residue, preferably of the benzene or naphthalene series, and the enolized grouping <FORM:0736180/IV (c)/2> is part of the residue of an azo component.  The dyestuffs are made when 1 mol. of a tetrazo compound of a 3,31-dialkoxy-4,41-diamino-1,11-diphenyl is either coupled with 1 mol. of the appropriate azine and 1 mol. of an azo component containing a ketomethylene group or united with 1 mol. of an azo compound of formula <FORM:0736180/IV (c)/3> where R is as above and R1 is a residue of the benzene or naphthalene series, and 1 mol. of an azo component containing a methylene group, the resulting dyestuff being treated with an acid to form the azine ring and the dyestuffs obtained by these methods are coppered in conventional fashion.  The grouping <FORM:0736180/IV (c)/4> is preferably contained in <FORM:0736180/IV (c)/5> where R2 is a radicle of the benzene or naphthalene series and X is -CH3, -COOH or -CONH2 or in <FORM:0736180/IV (c)/6> where R2 is as above.  3,31-Dimethoxy- and - diethoxy - 4,41 - diamino - 1,11 - diphenyl are specified. Specified azines are 5-hydroxy-1,2-naphthophenazine-7-sulphonic acid, 5-hydroxy-41- or -51-methyl, -methoxy-, -chloro- or -carboxy-, -41-amino-51-carboxy-, -41-hydroxy-51-carboxy- and -41-carboxy-51-hydroxy-1,2, 11,21 - naphthophenazine - 7 - sulphonic acid, 5 - hydroxy - 41 - amino - 1,2,11,21 - naphthophenazine - 41,7 - disulphonic acid, 5 - hydroxy-1,2,11,21 - naphthophenazine - 41, and - 51,7-disulphonic acid, 5-hydroxy-1,2,91,101-naphthophenanthrazine - 7 - sulphonic acid, and 5,51-dihydroxy - 1,2,21,11 - dinaphthazine - 7,71-disulphonic acid. Specified compounds leading to final conversion to azines are: 5-hydroxy-2-phenylaminonaphthalene - 1,11 - azobenzene-31, -41, -311 and 411, 7-disulphonic acid 5-hydroxy-2-(311- and 411-methyl), (411-methoxy- and -chloro-)-phenylaminonaphthalene-1,11-azobenzene-41, 7-disulphonic acid, 5-hydroxy-2-(311-chloro - ) - phenylaminonaphthalene - 1,11-azobenzene - 31,7 - disulphonic acid, 5-hydroxy-2-(311-and 411-carboxy)-, (411-hydroxy-511 - carboxy) -, (411 - carboxy - 511 - hydroxy)-and (411 - amino - 511 - carboxy) - phenylaminonaphthalene - 1,11 - azobenzene - 7 - sulphonic acid, 5,51-dihydroxy-2,21-dinaphthylamine-1, 11-azobenzene-7,71-di- and 411,7,71-trisulphonic acid and 5-hydroxy-2-(411-amino)-phenylaminonaphthalene - 1,11 - azobenzene-411,7-disulphonic acid.  Specified components containing a ketomethylene group are 1-acetoacetylaminobenzene-3- and -4-sulphonic and carboxylic acids, 1 - acetoacetylamino - 4-hydroxy - 3 - carboxy, 3 - hydroxy - 4 - carboxy- or 2-methoxy-4-sulpho-henzene, 1-acetoacetylaminonaphthalene-3,6-, -3,8- or -4,8-disulphonic acid, 2-acetoacetylaminonaphthalene-4,8-, -5,7- or -6,8-disulphonic acid, 4-acetoacetylamino - 1,11 - azobenzene - 41 - sulphonic acid, the acetoacetic acid amides of dehydrothio - p - toluidine - mono - and di - sulphonic acids, 1 - phenyl - 3 - methyl - 5 - pyrazolone-31- and -41-sulphonic and carboxylic acids, -31-sulphonamide and -21,51-disulphonic acid, 1 - phenyl - 3 - carboxy - 5 - pyrazolone - 31-and -41-sulphonic acids and -31-sulphonamide, 1 - phenyl - 5 - pyrazolone - 31 - carboxylic acid amide, 1 - (21,51 - dichloro) - phenyl - 3 - methyl-5-pyrazolone-41-sulphonic acid, 1-(11-naphthyl)-3-methyl-5-pyrazolone-41-, 51-, 61-, 71-and 81-mono- and -31, 61-, -31-, 81- and 41-, 81-disulphonic acids, 1-(21-naphthyl)-3-methyl-5-pyrazolone-11-, 51-, 61- and 81-mono- and -31-, 61-, -41,81-, -51,71- and - -61,81-disulphonic acids.  Azine ring formation may be obtained by treating with concentrated sulphuric or phosphoric acids at room temperature or by heating with dilute mineral acid. Examples are provided illustrating the preparation of dyestuffs from certain of the above specified reagents additional components being 5-hydroxy-31-chloro - 1,2,11,21 - naphthophenazine - 7 - sulphonic acid, and 1-(31-sulphamido)-phenyl-5-pyrazolone-3-carboxylic acid amide.  The dyestuffs dye cotton and regenerated cellulose fibres in neutral gray shades.