Patent GB-304298-A (GB)
Title: Process for the manufacture of new azo dyestuffs and chromed derivatives thereof
IPC: C09B45/16
Filed: 1928-05-22
Abstract: 304,298. Compagnie Nationale de MatiÞres Colorantes et Manufactures de Produits Chimiques du Nord RÚunies Etablissements Kuhlmann- Jan. 19, 1928, [Convention date]. Azo dyes, having a mordant character and capable of being converted into soluble chromium compounds by treatment with agents yielding chromium, are obtained by coupling diazotized oaminophenols or o-aminonaphthols or substitution products thereof with pyrazolones derived from primary amines of the benzene series substituted in the benzene nucleus by the group -NH.SO2.X in which X is a phenyl radicle which may be further substituted. The products dye wool in an acid bath yellow to red shades, and the fastness of the dyeings is increased by afterchroming. The chromium compounds dye animal fibres in an acid bath level shades ranging from bright orange to bluish red and very fast to washing, milling, and light. The following examples are specified :-(1) The dyestuff 4-nitro-2-aminophenol # 1-(3<1>-phenylsulphamido) phenyl-3- methyl-5-pyrazolone dyes wool yellow shades which become yellowish orange on after-chroming. (2) The dyestuff 2-aminophenol-4-sulphonic acid # 1-(3<1>-p-tolylsulphamido) phenyl-3- methyl-5-pyrazolone dyes wool golden yellow shades which become reddish orange on afterchroming. (3) The dyestuff 4-chloro-2-aminophenol-6-sulphonio acid # 1-(3<1>-p-tolylsulphamido) phenyl-3-methyl-5-pyrazolone dyes wool yellowish brown shades which become yellowish red on after-chroming. (4) The dyestuff 1 : 2- aminonaphthol-4-sulphonic acid # 1-(3<1>-ptolylsulphamido) phenyl-3-methyl-5-pyrazolone dyes wool orange shades which become bluish red on after-chroming. (5) The dyestuff-4-nitro-2- aminophenol)#1-(3<1>-phenylsulphamido)phenyl- 3-methyl-5-pyrazolone is boiled under reflux with an aqueous liquor containing caustic soda and freshly-precipitated chromium hydroxide; the product dyes animal fibres in an acid bath bright orange shades fast to fulling and light. (6) The dyestuff 4-chloro-2-aminophenol-6-sulphonic acid # 1-(3<1>-p-tolylsulphamido) phenyl-3-methyl-5- pyrazolone is boiled under reflux with an aqueous solution containing chromium formate and sodium acetate; the product dyes animal fibres in an acid bath level red shades, fast to fulling, washing, and light. (7) The dyestuff 1 : 2-aminonaphthol-4-sulphonic acid # 1-3<1>-p-tolylsulphamido) phenyl-3-methyl-5-pyrazolone is heated with an aqueous solution containing chromium formate and sodium acetate; the product dyes animal fibres bright bluish red shades fast to fulling and light. A table is also given showing the shades of the dyeings on wool with the following dyestuffs and their chromium compounds :- 4-nitro-2-aminophenol # 1-(3<1>-phenylsulphamido) phenyl- or 1-(2<1>-methyl-4<1>-phenylsulphamido) phenyl-3-methyl-5-pyrazolone; 2-aminophenol-4-sulphonic acid, 4-chloro-2-aminophenol- 6-sulphonic acid, 1 : 2-aminonaphthol-4-sulphonic acid, 1:2-aminonaphthol-4:6-disulphonic acid, or 1 : 2-aminonaphthol-4-sulphonic acid (nitrated diazo compound) # 1-(3<1>-p-tolylsulphamido) phenyl-3-methyl-5-pyrazolone; 4-chloro-2-aminophenol-6-sulphonic acid # 1-(2<1>-methyl-5<1>-ptolylsulphamido) phenyl-3-methyl-5-pyrazolone; .5-nitro-2-aminophenol # 1-(3<1> - p - tolylsulphamido) phenyl-3-carboxy-5-pyrazolone ; 1:2- aminonaphthol-4-sulphonic acid#1-(4<1>-methylp-tolylsulphamido)-p-tolyl-3-methyl-5-pyrazolone. The Specification as open to inspection under Sect. 91 (3) (a) comprises also the use as starting materials of amines of the benzene series group - NH.SO2.X as defined above in which either benzene nucleus is substituted by OCH3, OC6H5, C1, or SO3H. This subject-matter does not appear in the Specification as accepted. Pyrazolones of the type specified above are obtainable by condensation of the appropriate aminoarylpyrazolone with the appropriate arylsulphochloride, or by condensation of the hydrazine from the appropriate aminoarylsulphamide base with acetoacetic or oxalacetic ester. The following examples are specified :-(1) 1-(3<1>-ptolylsulphamide) phenyl-3-methyl (or 3-carboxy)- 5-pyrazolone is obtained by reduction with sodium sulphite, such reduction being completed by means of zinc dust and acetic acid, of the diazo compound from 1-amino-3-p-tolylsulphamidobenzene, and condensation of the resulting hydrazine with acetoacetic (or oxalacetic) ester. (2) 1-(3'- p-tolylsulphamido) phenyl-3- methyl-5-pyrazolone is obtained by condensation of 1-(3<1>-amino) phenyl-3-methyl-5-pyrazolone with p-toluenesulphonic chloride in presence of powdered chalk. (3) 1-(2<1>-methyl-4<1>-p-tolylsulphamido) phenyl-3- methyl-5-pyrazolone is obtained by condensing 2- nitro-4-toluidine with p-toluenesulphonic chloride, reducing the nitro group and converting the resulting amine into the pyrazolone. (4) 1-(4<1>- methyl-2<1>-p-tolylsulphamido) phenyl-3-methyl-5- pyrazolone is obtained by condensing 1-(2<1>-amino- 4<1>-tolyl)-3-methyl-5-pyrazolone with p-toluenesulphonic chloride. 1-Amino-3-p-tolylsulphamidobenzene is obtained by reducing the product of condensation of m-nitraniline and p-toluenesulphonic chloride. 1-(2<1>-Amino-4<1>-tolyl)-3-methyl-5-pyrazolone is obtained by reducing the product of reaction of 2-nitro-4-tolylhydrazine and acetoacetic ester.