Patent GB-776265-A (GB)
Title: Manufacture of azo-dyestuffs of the pyrazolone and pyrazole series
IPC: C09B62/00
Filed: 1953-02-18
Abstract: 1 - Aryl - 3 - substituted - 5 - pyrazolones and 1 - aryl - 3 - substituted - 5 - aminopyrazoles in which the 3-substituent is methyl or carbalkoxy and the aryl group is phenyl substituted by a vinylsulphone group or by a b -hydroxyethylsulphone group or its sulphuric ester (and may be further substituted), are prepared by condensing a b -hydroxyethylsulphonyl-phenylhydrazine with ethyl acetoacetate, diketene, diacetonitrile or oxalacetic ester, and if desired esterifying the b -hydroxyethylsulphone group in the product, and treating the sulphuric ester with alkali to give a vinylsulphone group.  Specified products are: substituted 1 - phenyl - 3-methyl - 5 - pyrazolones; 41 - b  - hydroxyethylsulphonyl, 21 - methoxy - 51 - b - hydroxyethylsulphonyl, 21 - chloro - 51 - b  - hydroxyethylsulphonyl, 31 and 41 - vinylsulphonyl, 41 - b  - hydroxyethylsulphonyl sulphuric ester, 21-chloro - 61 - methyl - 41 - vinylsulphonyl, 21-methoxy - 51 - vinylsulphonyl and 21 - methyl-41 - b  - hydroxyethylsulphonyl sulphuric ester; also 1 - (41 - b  - hydroxyethylsulphonylphenyl)-3 - carbethoxy - 5 - pyrazolone and 1 - (41 - b -hydroxyethylsulphonylphenyl) - 3 - methyl - 5-aminopyrazole. Specification 712,037 is referred to.ALSO:The invention comprises azo dyestuffs of the formula <FORM:0776265/IV(b)/1> where R is phenyl or substituted phenyl, R1 is phenylene or substituted phenylene, X is methyl or carbalkoxy, Y is O or NH and Z is -SO2-CH : CH2 or -SO2-CH2 -CH2-OSO3H ;dyestuffs from 1-(31-vinylsulphonyl-phenyl)-3-methyl-5-pyrazolone are however excluded.  The dyestuffs are made by coupling diazotized RNH2 either with the appropriate pyrazole derivative or with the corresponding coupling component where Z is -SO2-CH2-CH2-OH, converting the dyestuff into its sulphuric ester, and if desired treating this with alkali to form the vinylsulphone group.  The products dye wool, polyamides, cotton, viscose and acetate rayon in yellow shades from a neutral or weakly alkaline bath; the metachrome process may also be used if a metallizable grouping is present.  In the examples (1) the following dyestuffs are prepared and converted into their sulphuric esters:-anthranilic acid --> 1-(41-b -hydroxyethylsulphonylphenyl)-3-methyl - 5-pyrazolone, o-chloraniline --> 1-(21-methoxy - 51 - b -hydroxyethylsulphonyl-phenyl)-3-methyl-5-pyrazolone, aniline --> 1-(21-chloro -51- b -hydroxyethylsulphonyl-phenyl)-3-methyl-5-pyrazolone or 1-(41-b -hydroxy-ethylsulphonylphenyl - 3 - carbethoxy -5-pyrazolone, 2-amino-4 : 6-dinitrophenol --> 1-(41-b -hydroxy-ethylsulphonylphenyl) -3-methyl-5-pyrazolone, and anthranilic acid --> 1-(41-b -hydroxyethyl-sulphonylphenyl) -3- methyl-5-aminopyrazole; (2) the dyestuff orthanilic acid --> 1-(41-b -hydroxyethyl-sulphonylphenyl) -3 - methyl-5-pyrazolone is converted into its sulphonic ester and the latter treated with caustic soda to form the 1-(41-vinylsul-phonylphenyl) compound; (3) the following dyestuffs are also prepared directly:-anthranilic acid --> sulphuric ester of 1-(41-b -hydroxyethylsulphonylphenyl) - 3 - methyl-5-pyrazolone and orthanilic acid --> 1-(41-vinylsulphonylphenyl)-3-methyl-5-pyrazolone; (4) the dyestuff 2-methoxy-aniline -5- (b -hydroxyethylsulphone) --> potassium salt of sulphuric ester of 1-(41-b -hydroxyethylsulphonylphenyl)-3-methyl-5-pyrazolone is prepared in methanol in the presence of anhydrous potassium acetate.  Other specified diazo components are 4-chloraniline-6-sulphonic acid and 4-chloro-6-trifluoromethylaniline.  Further pyrazolones are also mentioned.  Specification 712,037 is referred to.