Patent GB-501131-A (GB)
Title: Manufacture of new azo dyestuffs
IPC: C09B35/28
Filed: 1937-07-14
Abstract: 501,131. Dyes. CLIFFE, W. H., and IMPERIAL CHEMICAL INDUSTRIES, Ltd. July 14, 1937, No. 19571. Samples furnished. (Class 2 (iii)] Disazo dyestuffs, containing sufficient sulphonic acid, sulphuric ester or other solubilizing groups to ensure their being soluble in water, are manufactured by tetrazotizing a diaminobenzoylaniline of the general formula in which R is an aralkyl group or a hydroxyalkyl group or sulphuric ester thereof, an alkoxyalkyl group or an acetoxyalkyl group, the alkyl radicle being ethyl, propyl or butyl, and in which either or both of the phenylene radicles may contain one or more substituents including short chain alkyl groups, and coupling with two molecular proportions of the same or different coupling components, e.g. phenols, naphthols, naphtholsulphonic acids, naphthylamines, naphthylaminesulphonic acids, aminonaphthols- or their sulphonic acids or N-substituted derivatives, arylpyrazolones or sulphonic or carboxylic acids thereof or acetoacetic arylamides. Alternatively, there may be employed a compound having the general formula given above except that one or other (but not both), of the amino groups is replaced by a'nitro group, this compound being diazotized and coupled with one molecular proportion of a coupling component, the nitro group then being reduced and the product diazotized and coupled with one molecular proportion of the same or a different coupling component. When R is a hydroxyalkyl group, the products may be subsequently converted to their sulphuric esters, e.g. by treatment with 80 per cent sulphuric acid. The products dye wool from a neutral or acid bath. In examples : (1) 3 : 3<1>diaminobenzoyl-N-#-hydroxyethylaniline is tetrazotized and coupled with two molecular proportions of 1-(4<1>-sulphophenyl-3-methyl-5-pyrazolone; the product dyes wool yellow shades; (2) the product of (1) is treated with concentrated sulphuric acid (similar shades); (3) the coupling component in (1) is replaced by 2-phenylamino- 8-naphthol-6-sulphonic acid; (4) 3 3<1>-diamino- 6<1>-methylbenzoyl - N - benzylanine is tetrazotized and coupled with two molecular proportions of 1-acetylamino-8-naphthol-3: 6-disulphonic acid (bluish-red shades); (5) the coupling component in (4) is replaced by 2-naphthol- 6: 8-disulphonic acid (orange shades); and (6) by 2-acetylamino-8-naphthol-6-sulphonic acid (scarlet shades); (7) 4: 3<1>-diaminobenzoyl-N- benzylaniline is tetrazotized and coupled with two molecular proportions of 2-naphthol-6 : 8-. disulphonic acid (orange shades); (8) 3: 4<1> diamino - 4 - methylbenzoyl -N - benzylanilide is tetrazotized and coupled with two molecular proportions of 1-(4<1>-sulphophenyl)-3-methyl-5- pyrazolone (yellow shades). A table gives the shades of further dyestuffs, the following additional coupling components being specified: 1-(2<1> : 5<1>-dichloro-4<1>-sulphophenyl)-3-methyl-5- pyrazolone, 2 - naphthol - 8 - sulphonic acid, 2- acetylamino - 5 - naphthol - 7 - sulphonic acid, 1- naphthol - 4 - sulplionic acid, 2 - N - # - hydroxyethylamino- 8 -naphthol- 6 -sulphonic acid and 1 - benzoylamino - 8 - naphthol - 4 : 6 - diswphonic acid. Diamino- or nitroaminobenzoyl-N-aralkylhydroxyalkyl- or -alkoxyalkylanilines are obtainable by condensing a mononitro-N-aralkyl-, hydroxyalkyl- or -alkoxyalkylarylamine of the benzene series with a nitroaroyl chloride of the benzene series and reducing one or both nitro groups. In examples: (1) N-#-hydroxyethylm-nitraniline is heated with m-nitrobenzoyl chloride, and the product is reduced with iron and hydrochloric acid in water or ethyl alcohol to 3 : 3<1> - diaminobenzoyl - N - # - hydroxyethylaniline ; (4) 2 - benzylamino - 4 - nitrotoluene similarly yields 3 : 3<1>-diamino-6<1>-methylbenzoyl- N-benzylaniline; (7) 3-nitro-N-benzylaniline and p-nitrobenzoyl chloride similarly yield 4 : 3<1> - diaminobenzoyl - N - benzylaniline; (8) 4-nitro-N-benzylaniline and 3-nitro-4-methylbenzoyl chloride similarly yield 3 : 4<1>-diamino-4- methylbenzoyl-N-benzylaniline. Diumino- or nitroaminobenzoyl-N-acetoxyalkylanilines are obtainable by condensing a mononitro - N - hydroxyalkylarylamine with a nitroaroyl chloride, heating the product with acetic anhydride and reducing one or both nitro groups. Samples have been furnished under Sect. 2 (5) of the following dyestuffs : (A) 2-naphthol-8- sulphonic acid # 3: 3<1>-diamino-6<1>-methylbenzoyl-N-benzylaniline # 1-naphthol-4-sulphonic acid; (B) 3:3<1>-diaminobenzoyl-N-#- ethoxyethylaniline (obtainable by condensing m-nitraniline with #-ethoxyethyl p-toluenesulphonate, condensing the produqt with m-nitrobenzoyl chloride and reducing) <#>#2-acetylamino-8-naphthol-6-sulphonic acid (2 mols.); (C) 3:3<1>-diaminobenzoyl-N-#-acetoxyethylaniline (obtainable by treating 3 : 3<1>-dinitro beuzoyl-N-#-hydroxyethylaniline with glacial acetic acid and-acetic anhydride in the presence of sodium acetate, and reducing)<#># 2-naphthol- 6: 8-disulphonic acid (2 mols.); (D) 1-naphthol- 4 -sulphonic. acid # 3<1>- nitro 4 - amino -6<1>- methylbenzoyl-N-benzylaniline (obtainable by condensing 2-benzylamino-4-nitrotoluene with p-nitrobenzoyl chloride and reducing one nitro group) (reduced) # 2-naphthol-6: 8-disulphonic acid.