Patent GB-243758-A (GB)
Title: Manufacture of azo-dyestuffs and process of dyeing wool, therewith
Filed: 1925-11-27
Abstract: 1-Sulphoaryl - 5-pyrazolone - 3-carboxylic alkyl esters are obtained from the hydrazones from sulphoarylhydrazine sulphonic acids and oxaloacetic esters either by heating in aqueous solution, or by allowing to stand in cold aqueous solution made slightly alkaline with sodium carbonate.  The benzene solution of the sodium salt of oxaloacetic ester as obtained in its manufacture may be directly used, the paste of the hydrazine sulphonic acid being added directly thereto, and the benzene subsequently distilled off.  Examples are given of the production of 1-(41-sulphophenyl)-5-pyrazolone-3-carboxylic acid ethyl and methyl esters, and 1-(21-methyl-61-chloro-41-sulphophenyl) - 5-pyrazolone-3-carboxylic acid ethyl ester.  The 2-methyl-6-chlor-4-sulphophenylhydrazine used in preparing the last-named body is obtained by sulphonating 3-chlor-2-aminotoluene and converting the product into the hydrazine by the usual method. Azo dyes are obtained by coupling the above-described pyrazolones with diazo compounds or by esterifying the dyestuffs from diazo compounds and 1-sulphoaryl-5-pyrazolone-3-carboxylic acids.  The products dye wool in level yellow to red shades which may be developed by after-chroming when the dyestuff is derived from the diazo compound of an anthranilic acid or an o-aminophenol.  The following amines are mentioned as diazo components:- o-, m-, or p-toluidine, m- or p-chloraniline, chlortoluidines, xylidines, o-, m-, or p-aminobenzoic methyl or ethyl ester, nitroaminobenzoic ester, m-aminobenzoic anilide, m-aminoanisic anilide, o-aminophenol and its substitution products; aniline sulphonic acids and their homologues and substitution products such as o-aniline sulphonic acid, metanilic acid, chlor- and nitroaniline sulphonic acids, toluidine and xylidine sulphonic acids; mono- and di-aminotriphenylmethane, diaminodiphenyldimethylmethane, di-amino-di-o-tolyldimethylmethane, 2 : 21-toluidine, 2 : 21-dichlorbenzidine, diaminodiphenylamine. Examples are given of the production of dyestuffs from (1) m-aminobenzaldehyde, o-chloraniline, sulphanilic acid, 5-nitro-2-aminobenzoic acid, or picramic acid and 1-(41-sulphophenyl)-5- pyrazolone-3-carboxylic ethyl ester; (2) aniline, or 6-chloraniline-3-sulphonic acid, and 1-(21-methyl-61-chloro-41-sulphophenyl) -5-pyrazolone-3-carboxylic ethyl ester.  The 1-(21 : 51-dichloro-41-sulphophenyl)-, 1-(21-chloro-51-sulphophenyl)-, 1-(21-sulphophenyl)-, and the 1-(21-oxy-31-carboxy-51-sulphophenyl) -5-pyrazolone-3-carboxylic esters are also mentioned as coupling components.  Reference has been directed by the Comptroller to Specifications 765/97 and 3373/08.ALSO:Wool is dyed in level yellow to red shades by means of dyestuffs containing a carboxylic ester group, obtained by coupling diazo compounds with a 1-sulphoaryl-5-pyrazolone-3-carboxylic alkyl ester, or by esterifying the dyestuffs from diazo compounds and the corresponding pyrazolone sulphocarboxylic acids.  The following amines are mentioned as diazo components:-o-, m-, or p-toluidine, m- or p-chloraniline, chlortoluidines, xylidines, o-, m-, or p-aminobenzoic methyl or ethyl ester, nitroaminobenzoic ester, m-aminobenzoic anilide, m-aminoanisic anilide, o-aminophenol and its substitution products; aniline sulphonic acids and their homologues and substitution products, such as o-aniline sulphonic acid, metanilic acid, chlor- and nitro-aniline sulphonic acids, toluidine and xylidine sulphonic acids; mono- and di-aminotriphenylmethane, diaminodiphenyldimethylmethane, diaminodi-o-tolyldimethylmethane, 2 : 21-tolidine, 2 : 21-dichlorbenzidine, and diaminodiphenylamine. Examples are given of dyestuffs from (1) m-aminobenzaldehyde, o-chloraniline, sulphanilic acid, 5-nitro-2-aminobenzoic acid or picramic acid and 1-(41-sulphophenyl) - 5pyrazolone - 3 - carboxylic ethyl ester; and (2) aniline or 6-chloraniline-3-sulphonic acid and 1-(21-methyl-61-chlor-41-sulphophenyl) -5-pyrazolone-3-carboxylic ethyl ester.  The 1-(21 : 51-dichlor-41-sulphophenyl)-, 1-(21-chlor-51-sulphophenyl)-, 1-(21-sulphophenyl)-, and the 1-(21-oxy-31-carboxy-51-sulphophenyl) -5-pyrazolone - 3 - carboxylic esters are also mentioned as coupling components.  Reference has been directed by the Comptroller to Specifications 765/97 and 3373/08, [both in Class 2, Acids and salts, Organic &c.].