Patent GB-723637-A (GB)
Title: Metalliferous polyazo dyestuffs and process for their preparation
IPC: C09B31/16
Filed: 1952-12-15
Abstract: The invention comprises dyestuffs of formula <FORM:0723637/IV (c)/1> where R1 and R2 are radicles of the benzene and naphthalene series, X is a simple linkage or a -CH=CH-, -NH.CO-, -CO.NH- or -NH.CO.NH- bridge, y is H, COOH or SO3H, v is H, OH, NH2, or an alkylated amino, cyclo-alkylated amino, arylated amino, or acylated amino group, w is H, -N=N- aryl or -N=N- pyrazolone substituent, w being o to v, b is a metal complex forming group and is o to -AZO11-, n is 0, 1 or 2 and where -OH is in the o-position and -N = N- in the p-position to -AZO11-, and -COOH is o to -AZO1-.  They may be made by coupling 1 mol. of a diazotized o-amino-carboxylic acid of the benzene or naphthalene series or a substituted derivative thereof with 1 mol. of a compound of formula <FORM:0723637/IV (c)/2> where z is an amino, nitro or easily saponifiable acylamino group, the nitro or acylamino groups being converted to an amino group, the resulting amino-azo compound being diazotized and coupled with 1 mol. of an amine of the benzene or naphthalene series capable of coupling in the p-position to the amino group and having a group capable of forming a metal complex in the o-position to the amino group, diazotizing the resulting dyestuff and coupling in the o-position to the hydroxyl group with 1 mol. of a compound of formula:  <FORM:0723637/IV (c)/3> Alternatively 1 mol. of diazo compound from <FORM:0723637/IV (c)/4> where a is a nitro or saponifiable acylamino group is coupled with 1 mol. of an appropriate amine the resulting amino-azo compound being coupled with a hydroxy naphthalene as above, the nitro or acylamino groups being converted into an amino group, the resulting amino-azo dyestuff condensed with diketene and the product coupled with 1 mol. of a diazotized o-aminocarboxylic acid of the benzene or naphthalene series.  When x is -NHCO- the dyestuffs may be made by coupling 1 mol. of a diazotized o-aminocarboxylic acid of the benzene or naphthalene series with 1 mol. of a compound of formula: <FORM:0723637/IV (c)/5> z, if necessary, is converted to an amino group, the aminoazo compound mixed with 1 mol. of a compound of formula:  <FORM:0723637/IV (c)/6> where Hal is Cl or Br, the nitro group is converted to an amino group, the resulting aminoazo compound is diazotized and coupled with 1 mol. of an amine of the benzene or naphthalene series with the desired coupling and complex forming characteristics and the disazo dyestuff thus formed is diazotized and coupled with the required hydroxynaphthalene compound.  The polyazo dyestuffs may be metallized by treatment with a metal-yielding agent. Specified acetoacetylamino compounds for use in the first process are 4-acetoacetylamino-41-nitro, -amino, -carbethoxyamino and oxalylaminostilbene - 2,21 - disulphonic acid, 4-acetoacetyl - amino - 41 - amino and carbethoxyaminodiphenyl, 4 - acetoacetylamino-41-amino, -oxalylamino and -carbomethoxyaminodiphenyl-31-sulphonic acid, 4-acetoacetylamino-1-(41-amino and -nitrobenzoyl)-aminobenzene, 4 - acetoacetylamino - 1 - (41 - aminobenzoyl)-aminobenzene-2-sulphonic and carboxylic acid, 4 - amino - 1 - (41 - acetoacetylaminobenzoyl)-aminobenzene and 2- and 3-sulphonic and 3-carboxylic acids thereof, 4-acetoacetylamino-41-amino and -nitro-1,11-diphenylurea and 4-acetoacetylamino - 41 - amino - 1,11 - diphenylurea-31-sulphonic acid the preparation of these compounds being in Group IV (b).  Specified o-aminocarboxylic acids are 2-aminobenzene-1-carboxylic acid and its 4-sulpho and 5-nitro and -sulpho derivatives and 2-aminonaphthalene-3-carboxylic acid. Specified amines capable of coupling in the p-position to the amino group and having a metal complex forming group in the o-position are 1-amino-2-methoxybenzene, 1 - amino - 2 - methoxy - 5-methylbenzene, 1 - amino - 2,5 - dimethoxybenzene, 1 - amino - 2 - methoxynaphthalene and its 6-sulphonic acid and 1-amino-2-ethoxynaphthalene and its 6-sulphonic acid.  Specified hydroxynaphthalenes are 1- and 2-hydroxynaphthalene, 1-hydroxynaphthalene-3, -4 and -5, sulphonic and -3,6 and -3,8-disulphonic acid, 2-hydroxynaphthalene-4, -6 and -7-sulphonic acid, 1-hydroxy-6-amino-, -6-N-methyl, -ethyl, -propyl, -cyclohexyl, -carbopropoxy, -phenyl, -31-methoxy and -41-methylphenyl, - (31 - and 41 - carboxyphenyl), - carbomethoxy, -carboethoxy, -acetyl and -benzoyl aminonaphthalene-3-sulphonic acid, 1-hydroxy - 6 - (41 - chloro) - benzoyl - and N-phenyl-, aminonaphthalene-3-sulphonic acid, 1-hydroxy - 6 - N - phenylaminonaphthalene-3,41-disulphonic acid, 1-hydroxy-6-amino- and 6 - benzoylaminonaphthalene - 3,5 - disulphonic acid, 1 - hydroxy - 7 - amino, - acetylamino and N - phenylaminonaphthalene - 3 - sulphonic acid, 1-hydroxy-8-amino and -acetylamino naphthalene-3,6-disulphonic acid, 1-hydroxy-6-N - phenylaminonaphthalene - 3,31 - disulphonic acid, 1 - hydroxy - 8 - amino, - butyrylamino, - propionylamino and -acetylaminonaphthalene - S - sulphonic, and - 3,6 - disulphonic acids, 2 - hydroxy - 6 - propionylaminonaphthalene - 4 - sulphonic acid, 1,8 - dihydroxynaphthalene - 3,6 - disulphonic acid, 1,6-dihydroxy - 5 - (2 - carboxy and 41 - nitro - 21-carboxybenzene - 11 - azo) - naphthalene - 3-sulphonic acid, 1,6-dihydroxy-5-(21-carboxy and -hydroxybenzene - 11 - azo) - naphthalene 3,51-disulphonic acid, 1,6- and 1,5-dihydroxy-5 - (21 - hydroxybenzene - 11 - azo) - naphthalene-3,41-disulphonic acid, 1,5-dihydroxy-6 - (21 - hydroxynaphthalene - 11 - azo) - naphthalene-3,61-disulphonic acid, 1,5-dihydroxy-6-(11 - hydroxynaphthalene - 21 - azo) - naphthalene-3,41-di- and 3,31,61-tri-sulphonic acid, 1,5 - dihydroxy - 6 - (11 - phenyl and -(311-chloro) - phenyl, - 31 - methyl - 51 - pyrazolone-41 - azo) - naphthalene - 3,411 - disulphonic acid, 1 - hydroxy - 6 - amino - 5 - (benzene-, 21 - carboxybenzene and 41 - nitro - 21 - carboxybenzene - 11 - azo) - naphthalene - 3 - sulphonic acid, 1 - hydroxy - 6 - amino - 5 - (benzene - 11 - azo) - naphthalene - 3,31 and 3,41-disulphonic acid and 2-hydroxy-6-(41-methyl)-benzylaminonaphthalene-4-sulphonic acid.  The hydroxynaphthalenes may be condensed in the metallized form with the diazotized aminodisazo dyestuff.  Specified amines for use as starting materials in the second method are 4-amino - 41 - nitro, - carbethoxyamino and acetylaminostilbene-2,21-disulphonic acid, 4-amino - 41 - acetylamino - and -41 - carbethoxyaminodiphenyl-3-sulphonic acid, 4-amino-(41-nitrobenzoyl1-aminobenzene and its 3-sulphonic acid, 4 - amino - (41 - carbethoxy - aminobenzoyl) - aminobenzene - 3 - sulphonic acid and 4-oxalylamino- and 4-carbomethoxyamino-(41 - aminobenzoyl) - aminobenzene.  Specified acetoacetylamino compounds for use in the third process are 4-amino-1-acetoacetylaminobenzene and its 3-sulphonic acid and 4-carbethoxyamino-, -oxalylamino and -nitro-1-acetoacetylaminobenzene.  Specified acid halogenides are 4-nitrobenzoylchloride and bromide.  The first process is preferably effected by coupling the diazo compound of the o-aminocarboxylic acid in a weakly acid or weakly alkaline medium with the acetoacetylamino compound, if necessary, after saponification of the acylamino group with acid or alkali or reduction of the nitro group with sodium sulphide.  The aminoazo compound is coupled in an alkaline or weak acid medium with the desired amine-preferably alkalinity is effected with sodium carbonate and acidity with acetic or formic acids.  The final condensation is preferably effected in the presence of a weakly alkaline substance, e.g. sodium or potassium bicarbonates, ammonia, pyridine or quinoline.  Metalisation is advantageously effected by heating the aqueous dyestuff paste or solutions with substances yielding metals in the presence of alkali salts of low molecular weight aliphatic carboxylic acids or heating in aqueous solution with complex metal salts.  Copper and nickel are specified metals.  The metallised dyestuffs dye cotton and regenerated cellulose in green to olive coloured shades.  Examples are provided illustrating the use of many of the above specified compounds in dyestuff preparations.ALSO:Compounds of formula <FORM:0723637/IV (b)/1> where X is either a simple linkage, -CH=CH-NHCO, -CO.NH or -NHCONH, y is H or a carboxylic or sulphonic acid group, and Z is an amino, nitro or acylamino group are made by reacting 1 mol. of diketene with 1 mol. of an amine of formula <FORM:0723637/IV (b)/2> in an aqueous solution or inert organic solvent at 20-60 DEG  C. Reaction is particularly easy when the ortho position to the NH2 group is unsubstituted.  The compounds are azo dyestuff intermediates (see Group IV (c)).  In example (3) 4-acetoacetylamino-41-amino-1, 11-diphenyl-31-sulphonic acid is made by condensing diketene with the sodium salt of 4,41-diamino - 1,11 - diphenyl - 31 - sulphonic acid in aqueous sodium carbonate solution.