Patent GB-486660-A (GB)
Title: Manufacture of dyestuffs
IPC: C09B62/08
Filed: 1936-11-06
Abstract: As diazo or coupling components in the manufacture of azo dyes, use is made of 5-pyrazolone derivatives substituted in the 1-position by a group -RXR1NHR11, where R and R1 are residues of the benzene series, R11 is hydrogen or the residue of an organic acid, and X is a simple linkage, an oxygen atom, a group -CH:CH-, -CH2-, -NHCO-, or -NHCONH-, or an amino-substituted heterocyclic ring containing carbon and nitrogen atoms, e.g. the residue of a 2 : 6-diamino-1 : 3 : 5-triazine ring, which may be substituted in the 4-position. If the dyes contain one or more free amino groups, they may be acylated or further diazotized and coupled with azo dye components.  Diazo compounds which may be coupled with the pyrazolones include diazobenzene, diazonaphthalene, diazotoluene, diazoanisole, diazophenetole, diazotized aminoazobenzene, the sulphonic acids of any of these, and o- or peri-hydroxy- or carboxy-diazo compounds, e.g. those from o-aminophenols, o-aminonaphthols and their sulphonic acids, 1 : 8-aminonaphtholsulphonic acids, and anthranilic acid; the dyes prepared from o-aminophenols or o-aminocarboxylic acids or their esters or ethers, or the dyes containing a salicylic acid or other lake-forming grouping, may be converted into complex metal compounds, particularly into copper, chromium, nickel, cobalt, iron or zinc compounds, in substance or on the fibre.  Coupling components which may be coupled with the diazotized pyrazolones (obtained when R11 is hydrogen) include p-cresol, resorcinol and 2-naphthol and their sulphonic acids, 1-naphthol sulphonic acids which couple in the 2-position, aminonaphthol sulphonic acids such as 2-amino-5-naphthol-7-sulphonic acid, 2-amino-8-naphthol-6-sulphonic acid, 1 - amino - 8 - naphthol - 4 : 6- and -3 : 6-disulphonic acid (acid or alkaline coupling), 2 : 3-oxynaphthoic acid, 1-acidylamino-8-naphtholsulphonic acids, and amines such as m-phenylenediamine, 2-naphthylamine and alkyl-2-naphthylamines and their sulphonic acids.  The dyes are useful for dyeing textiles consisting of or containing natural or regenerated cellulose, e.g. viscose or cuprammonium artificial silk; if the dyes contain suitable substituents, they may be diazotized on the fibre and coupled with a coupling component, or treated on the fibre with a diazo compound. In the examples: (1) 1-phenyl-(41-phenyl-411-acetylamino)-3-methyl - 5 - pyrazolone (Specification 486,747) is coupled with diazotized sulphanilic acid to yield a yellow dye for cotton; (2) 1-phenyl-(41-phenyl - 411 - amino) - 3 - methyl - 5 - pyrazolone (Specification 486,747) is coupled with diazotized aminoazobenzene-p-sulphonic acid; the product dyes cotton in yellow shades, which may be converted into orange to red shades by diazotization on the fibre and development with 1 - phenyl - 3 - methyl - 5 - pyrazolone or 2 - naphthol; (3) 1 - phenyl - (41 - phenyl - 411-amino)-3-methyl-5-pyrazolone is coupled with diazotized 2-chloraniline-4-sulphonic acid, and the product is diazotized and coupled with 2 - amino - 8 - naphthol - 6 - sulphonic acid; a brown cotton dye is obtained; (4) 1-phenyl-(41-phenyl-411-amino)-3-methyl-5-pyrazolone is coupled with diazotized 2-chloraniline-4-sulphonic acid, and the product is diazotized and coupled with the monoazo dye obtainable by acid coupling of diazotized 2 : 4-dichloraniline and 1 - amino - 8 - naphthol - 3 : 6-disulphonic acid; the product dyes cotton green; similar products are obtained if the 3-methylpyrazolone is replaced by the corresponding 3-carboxypyrazolone or if the benzidine residue in the pyrazolone is replaced by a tolidine or dichlorobenzidine residue; (5) diazotized dehydrothiotoluidine is coupled with 1-phenyl-(41-phenyl-411-amino)-3-methyl-5-pyrazolone, and the product is treated with phosgene; an orange dye for cellulose fibres is obtained.  Samples have been furnished, under Sect. 2(5), of products prepared as follows: (1) diazotized dehydrothio-p-toluidine monosulphonic acid is coupled with 1-phenyl-(41-phenoxy-411-amino)-3-methyl-5-pyrazolone, and the product is diazotized and coupled with 2 - amino - 5-naphthol-7-sulphonic acid; a red-brown dye is obtained; (2) 2 mols. of diazotized 2-aminobenzoic-4-sulphonic acid are coupled with 1 mol. of a dipyrazolone prepared by diazotizing 4-amino-41-nitrostilbene, converting the diazo compound into the corresponding hydrazine, condensing the latter with acetoacetic ester, reducing the nitro group, and condensing 2 mols. of the aminopyrazolone so obtained with 1 mol. of cyanuric chloride; a yellow dye is obtained; (3) diazotized dehydrothio-p-toluidine monosulphonic acid is coupled with 1-phenyl-(41-benzyl-411-amino)-3-methyl-5-pyrazolone, and the product is diazotized and coupled with 1-(41-sulphophenyl)-3-methyl-5-pyrazolone; a yellow-orange dye is obtained; (4) diazotized sulphanilic acid is coupled with the pyrazolone of sample 3, and the product is diazotized and coupled with 2-amino-5-naphthol-7-sulphonic acid; an orange-red dye is obtained; (5) diazotized sulphanilic acid is coupled with a pyrazolone obtainable by condensing 1 - (41-aminophenyl) - 3 - methyl - 5-pyrazolone with p-nitrobenzoyl chloride and reducing the nitro group; the dye so obtained is diazotized and coupled with the copper compound of the dye from diazotized 2-aminophenol-4-sulphonic acid and resorcinol; a brown dye is obtained; (6) diazotized dehydrothio-p-toluidine monosulphonic acid is coupled with the pyrazolone of sample 5, and the product is diazotized and coupled with 1-(41-sulphophenyl-3-methyl-5-pyrazolone; a yellow dye is obtained; (7) diazotized sulphanilic acid is coupled with the pyrazolone of sample 5, and the product is diazotized and coupled with 2-amino-5-naphthol-7-sulphonic acid; a red-brown dye is obtained; (8) diazotized sulphanilic acid is coupled with a pyrazolone obtainable by condensing phosgene with 1 mol. each of 1-(41-aminophenyl)-3-methyl-5-pyrazolone and p-phenylenediaminesulphonic acid; the product is diazotized and coupled with 2-amino-5-naphthol-7-sulphonic acid; an orange-brown dye is obtained; (9) diazotized dehydrothio-p-toluidine monosulphonic acid is coupled with the pyrazolone of sample 8, and the product is diazotized and coupled with 1-(41-sulphophenyl)-3-methyl-5-pyrazolone; a yellow dye is obtained; (10) diazotized sulphanilic acid is coupled with a pyrazolone obtained by condensing 1 mol. of cyanuric chloride successively with 1 mol. of p-phenylenediaminesulphonic acid and 1 mol. of 1 - (31 - aminophenyl) - 5-pyrazolone-3-carboxylic acid; the product is diazotized and coupled with 2-amino-5-naphthol-7-sulphonic acid; a brown-red dye is obtained; (11) diazotized dehydrothio - p - toluidine monosulphonic acid is coupled with the pyrazolone of sample 10, and the product is diazotized and coupled with 1-(41-sulphophenyl) - 3 - methyl - 5 - pyrazolone; an orange-yellow dye is obtained; (12) diazotized 2-aminobenzoic acid is coupled with the pyrazolone of sample 10, and the product is diazotized and coupled with the copper compound of the dye from diazotized 2-aminophenol-4-sulphonic acid and resorcinol; a yellow-brown dye is obtained; (13) diazotized 2-aminobenzoic acid is coupled with a pyrazolone obtainable by condensing 1 mol. of cyanuric chloride successively with 1 mol. of p-phenylenediaminesulphonic acid and 1 mol. of 1-(41-aminophenyl)-3-methyl-5-pyrazolone; the product is diazotized and coupled with the copper compound of the dye from diazotized 2-aminophenol-4-sulphonic acid and resorcinol; a brown dye is obtained; (14) diazotized 2-aminobenzoic-4-sulphonic acid is coupled with the pyrazolone of sample 13, and the product is diazotized and coupled with the copper compound of the dye from diazotized 2-aminophenol-4-sulphonic acid and resorcinol; (15) diazotized sulphanilic acid is coupled with the pyrazolone of sample 13, and the product is diazotized and coupled with 2-amino-5-naphthol-7-sulphonic acid; a red dye is obtained; (16) diazotized 2-aminobenzoic-4-sulphonic acid is coupled with 1-(41-phenyl-411-amino)-3-methyl-5-pyrazolone, and the product (2 mols.) is condensed with phosgene; a yellow dye is obtained; (17) diazotized dehydrothio-p-toluidine monosulphonic acid is coupled with the pyrazolone of sample 16, and the product (2 mols.) is condensed with phosgene; an orange-yellow dye is obtained; (18) diazotized 2-aminobenzoic-4-sulphonic acid is coupled with the pyrazolone of sample 16, and the product (2 mols.) is condensed with cyanuric chloride; a yellow dye is obtained; (19) diazotized 2-aminobenzoic-4-sulphonic acid is coupled with the pyrazolone of sample 16, and the product (1 mol.) is condensed with a product obtained by condensing 1 mol. of cyanuric chloride with 1 mol. of 41-amino-1 : 11-azo-4-oxybenzene-5-carboxylic acid; a yellow dye is obtained; (20) diazotized 2-aminobenzoic-4-sulphonic acid (2 mols.) is coupled with a dipyrazolone obtainable by condensing 2 mols. of the pyrazolone of sample 16 with 1 mol. of cyanuric chloride; the product is identical with sample 18; (21) diazotized sulphanilic acid (2 mols.) is coupled with a dipyrazolone obtained from the dipyrazolone of sample 20 by replacing the residual chlorine atom by a phenylamino group by reaction with aniline; a yellow dye is obtained; (22) diazotized 2-aminobenzoic-4-sulphonic p  acid is coupled with 1-phenyl-(41-phenyl-411-amino)-3-methyl-5-pyrazolone, and the product is diazotized and coupled with the dye from 1 mol. each of diazotized 2 : 5-dichloraniline and 1 - amino - 8 - naphthol - 3 : 6-disulphonic acid; a green dye is obtained; (23) diazotized 2-aminobenzoic acid is coupled with the pyrazolone of sample 22, and the product is diazotized and coupled with the copper compound of the dye from diazotized 2-aminophenol-4-sulphonic acid and resorcinol; a brown dye is obtained; (24) diazotized sulphanilic acid is coupled with 1-phenyl-(41-phenyl-411-amino) -5-pyrazolone-3-carboxylic acid