Patent GB-515099-A (GB)
Title: Manufacture of new dyestuffs
IPC: C09B45/14
Filed: 1938-05-23
Abstract: 515,099. Dyes. SOC. OF CHEMICAL INDUSTRY IN BASLE. May 23, 1938, Nos. 15310 and 15311. Convention dates, May 22, 1937, and April 27, 1938. [Classes 2 (iii) and 15 (ii)] Azo dyes are made by combining a compound of the general formula in which R1 is a benzene nucleus to which the group -NHX- is linked in a' position other than an o-position to the arylthiazole residue, R2 is the residue of a 1-phenyl-5-pyrazolone linked to X in 4<1>-or 31-position of the phenyl residue and X = -CONH- or -(triazine residue)-NH-, with a diazo compound substituted in o-position to the diazo group by a COOH group or by a group which can be converted into a COOH group, and converting the product so obtained into a complex metal compound in substance or on the fibre, the said 'group in o-position to the diazo group (if it is not a COOH group) being converted into a COOH group before or simultaneously with the metallization. They yield yellow to orange and brown shades on cellulose or regenerated cellulose. In the examples (1) the urea from dehydrothiotoluidine-mono-sulphonic acid and 1-(3<1>- or 41-aminophenyl)-5- pyrazolone-3-carboxylic acid is coupled with diazotized 1-amino-4-sulphobenzene-2-carboxylic acid or anthranilic acid and the dyestuff treated with ammoniacal copper sulphate ; the coupling component may also be the tertiary condensation product from cyanuric chloride and 1-(4<1>- or 31-aminophenyl)-3- methyl- or 3-carboxy-5-pyrazolone, dehydrothiotoluidine monosulphonic acid and aniline, (2)-(4) examples of dyeing processes. Other components specified are the condensation products from 3<1>- or 4<1>-aminoaryl-5-pyrazolones and Á-aminophenylarylthiazoles ; 1- aminobenzene-4-nitro-2-carboxylic acid, anthranilic acid ethyl ester. Specification 299,331, [Class 2 (iii)], is referred to. The Specification as open to inspection under Sect. 91 comprises the manufacture of azo dyes by combining a Á-phenylarylthiazole in which the Á-phenyl nucleus is linked to a 5-pyrazolone nucleus with a diazo compound substituted in o-position to the diazo group by a group which in combination with the enolizable CO-group of the pyrazolone is capable of yielding complex metal compounds, or by a substituent which can be converted into such a group, and converting the product so obtained into a complex metal compound. Additional components specified are 1-amino- 4-chlor-2-phenol, 1-amino-4-nitro-2-phenol, 1-amino-2-phenol-4-sulphonic acid or 4:6- disulphonic acid, 1-amino-2-chlorbenzene-4- sulphonc acid, 1-amino-2-methoxybenzene- 4-sulphonic acid, 1-amino-2-naphthol-4- sulphonic acid, 2-amino-1-naphthol-4: 8- disulphonic acid ; the condensation products from acetoacetic esters or oxalacetic esters and the hydrazine from dehydrothiotoluidine, the condensation 'products from 1-phenyl-3- methyl-5-pyrazolone-31- or 41-carboxylic acid and dehydrothiotoluidine or dehydrothioxylidine and sulphonic acids of such compounds, compounds resulting from the combination of amino-5-pyrazolones and Á-aminophenylarylthiazoles by means of compounds containing at least two reactive halogen atoms. In examples (1) 1-phenyl-3-methyl-5-pyrazole-4<1>-carboxylic acid is condensed with dehydrothiotoluidinemonosul-phonic acid by means of pyridine, dimethyl-aniline and phosphorus trichloride, the product coupled with diazotized 1-amino-4-sulpho-benzene-2-carboxylic acid and the dyestuff treated with' ammoniacal copper sulphate ; the coupling component may also be made by condensing p-nitrobenzoyl chloride with dehydrothiotoluidine monosulphonic acid, reducing, diazotizing, converting to the hydrazine and condensing with ethylacetoacetate, (2) similar to (1) using dehydrothiotoluidine instead of the sulphonic acid and chlorbenzene instead of pyridine and dimethylaniline ; the copper compound may also be produced on the fibre, (3) diazotized dehydrothiotoluidine is reduced with stannous chloride, the hydrazine obtained condensed with ethyl acetoacetate to form the pyrazolone which is coupled with diazotized 1-amino-4-sulphobenzene-2- carboxylic acid or 2-aminophenol sulphonic acid and the dyestuff coppered in substance or on the fibre, (4) 6-sulpho-1 : 2-naphtho-Á- (3<1>-amino)-phenylthiazole is condensed with p-nitrobenzoyl chloride, the product reduced with NaHS, diazotized, reduced to the hydrazine, condensed with ethyl acetoacetate and the pyrazolone obtained coupled with diazotized 2-amino-4-sulphobenzene-l-carboxylic acid and the dyestuff coppered ; anthranilic acid or an o-aminophenol or a sulphonic acid thereof may also be used. This subject-matter does not appear in the Specification 'as accepted.