Patent GB-744229-A (GB)
Title: Improvements in or relating to azo dyestuffs
IPC: C09B35/28
Filed: 1953-12-22
Abstract: The invention comprises dyestuffs of formula:-<FORM:0744229/IV(c)/1> where x is hydrogen, alkyl, alkoxy or -SO3H; one y is -OH, the other being -OH, -OCH3 or -COOH; Z is hydrogen, halogen or -SO3H; "alkyl" is alkyl of 1 to 3 carbon atoms; y-R is a radical of the benzene, naphthalene, or pyrazolone series, the y of y-R being ortho to the respective azogroup; and n=1 or 2.  The dyestuffs are prepared by coupling advantageously in alkaline medium one mol of the diazo compound from:- <FORM:0744229/IV(c)/2> wherein y, x and "alkyl" are as defined above, with one mol of <FORM:0744229/IV(c)/3> wherein Z is as defined above and A is azylamino, and if desired coppering the resultant dyestuff in substance or on the fibre. Compound (II) may be replaced by the corresponding coppered compound.  Alternatively, one mol of the diazo compound from <FORM:0744229/IV(c)/4> wherein x, z and "alkyl" are as defined above and y1 stands for -OH, -OCH3 or -COOH is coupled advantageously in alkaline medium, possibly containing organic bases such as pyridine, phenol, naphthol or pyrazolone which couples ortho to hydroxy.  The dyestuffs are coppered by known methods.  The dyes, coppered in substance or on the fibre, yield yellowish to bluish red shades, on cotton and regenerated cellulose.  In examples (1-27) an aminomonoazo dyestuff (obtained by acid coupling of a diazotized ortho-hydroxy-aminobenzene (A) with a 1-methoxy-3-aminobenzene or a 6-methyl or -methoxy derivative thereof, acylation of the resultant aminomonoazo compound with 3-methyl-4-nitrobenzene-1carboxylic acid chloride and reduction of the nitro to amino) is diazotized and coupled with a 2-acylamino-5-hydroxynaphthalene-7- sulphonic acid (B); reactants specified are (A) 1-hydroxy-2-aminobenzene, 1 - hydroxy - 2 - aminobenzene-4-sulphonic acid or -sulphonamide, 1-hydroxy-2amino-4-methylsulphonylbenzene, 1 -hydroxy-2-amino-6-chloro- or acetylamino- or benzoylamino-benzene-4-sulphonic acid and 1-hydroxy-2-aminobenzene-4-sulphonic acid-(21-carboxy)-phenyl-or-methyl-or-(21-hydroxy) -ethyl-or-phenyl-or-dimethyl - or - (N-methyl)-phenyl-amide; (B) 2-benzoylamino-or-carbethoxyamino-or-(41 - fumarylamino-or-acetylamino or-amino)-benzoylamino-or-acetylamino-or-(21-carboxy) - benzoylamino - or - sulphoacetylamino - 5 - hydroxynaphthalene - 7 - sulphonic acid, 1 - chloro-2-benzoylamino- or - acetylamino - 5 - hydroxynaphthalene-7-sulphonic acid and 2-acetylamino-or-carbethoxyamino-or - benzoylamino-or-(41-amino) - benzoylamino - 5 - hydroxynaphthalene - 1 : 7 - disulphonic acid: (29-54) a diazomonoazo intermediate (obtained by coupling a tetrazotised 1-(41-amino-31-methyl) - benzoylamino-3-hydroxy-or-carboxy-4-aminobenzene with a 2-acylamino-5-hydroxynaphthalene - 7 - sulphonic acid (C) is coupled with a phenol, naphthol or pyrazolone derivative (D) coupling ortho to hydroxy; reactants specified are (C) 2-acetylamino-or-carbethoxyamino-or-benzoylamino-or-(21 -chloro)-benzoylamino-or-sulphoacetylamino - 5 - hydroxynaphthalene-7-sulphonic acid, 1-chloro-2-carbethoxyamino - 5 - hydroxynaphthalene - 7 - sulphonic acid and 2-acetylamino-or-carbethoxyamino-or-benzoylamino-5-hydroxynaph thalene-1 : 7-disulphonic acid; (D) 3-methyl-5-pyrazolone, 1-phenyl-or-[41-(411-amino) - phenyl] - phenyl - or - (31 - or 41 - chloro)-phenyl-3-methyl-5-pyrazolone, 1-[41-(411-acetylamino) - phenyl] - phenyl - 3 - methyl-5-pyrazolone, 1-phenyl-3-methyl-5-pyrazolone-31-or-41-sulphonic acid, 1-(41-hydroxy)-phenyl-3-methyl-5-pyrazolone-31 - carboxylic acid, 1-phenyl-3-methyl-5-pyrazolone-31-sulphonamide, 1 : 3-dihydroxybenzene-4-carboxylic acid, 2-hydroxynaphthalene, 2-hydroxynaphthalene-3-carboxylic acid amide, 1- or 2-hydroxynaphthalene-4-sulphonic acid, 1-hydroxynaphthalene-3 : 8-disulphonic acid, 2-acetylamino-or-carbethoxyamino-or-benzoylamino - or - (31 - methyl-41-amino) - benzoylamino - or - (41-fumarylamino)-benzoylamino - 5 - hydroxynaphthalene-7-sulphonic acid and 2-benzoylamino-5-hydroxynaphthalene - 1 : 7 - disulphonic acid : (55-67) an aminomonoazo dyestuff (obtained by coupling a diazotised 2-amino-1-carboxy-or-hydroxy-5 - nitrobenzene with a 1-methyl-or-1 : 3-dimethyl-4-hydroxybenzene reducing the nitro to amino, acylating the aminomonoazo compound with 3-methyl-4-nitrobenzene-4-carboxylic acid chloride and again reducing nitro to amino) is diazotised and coupled with a 2-acylamino-5-hydroxynaphthalene-7-sulphonic acid from among those described under (B) above: (68-79) an aminoazo dyestuff (obtained by coupling diazotised 1-methoxy-2-amino-5-nitrobenzene-4-sulphonic acid with a phenol or naphthol (E) coupling ortho to the hydroxy group, reducing the nitro to amino, acylating the aminoazo compound with 3-methyl-4-nitrobenzene-1-carboxylic acid chloride and again reducing nitro to amino) is diazotised and coupled with a 2-acylamino-5-hydroxynaphthalene - 7 - sulphonic acid from among those described under (B) above with the addition of 2-fumarylamino - 5 - hydroxynaphthalene - 7 - sulphonic acid; reagents (E) specified are 2-hydroxynaphthalene, 2-hydroxynaphthalene-4-or-6-sulphonic acid 1-hydroxy-naphthalene-4-sulphonic acid, 2-acetylamino- or - (41 - fumarylamino) - benzoylamino - 5 - hydroxynaphthalene-7-sulphonic acid and 1-methyl-4-hydroxybenzene: (80-82) 2 - carboxy-phenylazo ,(11)-[41-(311-methyl-411 aminobenzoylamino)-51-methyl-21-hydroxybenzene] is diazotised and coupled with 2-benzoylamino-or-(41-amino)-benzoylamino-5 - hydroxynaphthalene - 1 : 7 - disulphonic acid or with 2-(41-amino-31-methyl)-benzoylamino - 5 - hydroxynaphthalene - 7 - sulphonic acid.  Specification 657,753 is referred to.