Patent GB-544409-A (GB)
Title: New monoazo dyestuffs
Filed: 1940-08-05
Abstract: 544,409. Dyes. KNIGHT, A. H., and IMPERIAL CHEMICAL INDUSTRIES, Ltd. Aug. 5, 1940, Nos. 12584 and 12585. [Class 2 (iii)] Monoazo dyes, suitable for producing yellow to scarlet dyeings, fast to severe washing and milling, on wool and for dyeing also silk or leather, are obtained by diazotizing an amine of the general formula  X-CO-NY-R-NH  2  wherein R represents a phenylene residue, substituted or not, X represents a monochloro- or monobromo-alkyl radicle containing not more than 3 carbon atoms, Y represents H, an alkyl, aralkyl or cycloalkyl radicle containing not more than 7 carbon atoms or a phenyl radicle, substituted or not, the primary amino group being in m- or p-position to the X-CO-NY- group, 'and coupling with a pyrazolone, a naphthol or a naphtholsulphonic acid, the selection of the components being such that the product contains at least one sulphonic acid group. Specified diazo components are 3-amino-chloroacetanilide and its N-benzyl derivative, 4-amino-chloroacetanilide and its N-ethyl, N-isopropyl, N-n-butyl, N- sec-butyl, N-isobutyl, N-benzyl, N-phenyl, N-cyclohexyl and N-o- or p-methyl-cyclobexyl derivatives, 3-amino-chloroacetanilide-4-sulpnonic acid, 4-amino-2-N-ethyl- or N-benzylchloroacettoluidide, 4-amino-chloroacetanilide- 3-sulphonic acid, 4-amino-N-ethyl-bromoacetanilide, 4-amino-2-N-ethyl-p-chloro- or α- or #-bromo-propionyltoluidine and 4-amino-2-N- benzyl-chloroacetanisidide. Specified pyrazolone components are 1-phenyl-3-methyl-5- pyrazolone and its 2<SP>1</SP>-chloro-, 3<SP>1</SP>- and 4<SP>1</SP>-sulpbo-, 2<SP>1</SP>-chloro-5<SP>1</SP>-sulpho-, 2<SP>1</SP> : 5<SP>1</SP>-dichloro-4<SP>1</SP>-sulpho-, 6<SP>1</SP>-chloro-3<SP>1</SP>-methyl-4<SP>1</SP>-sulpho-, 4<SP>1</SP>-chloro-2<SP>1</SP>- sulpho-, 2<SP>1</SP>-methyl-5<SP>1</SP>-sulpho-, 21-chloro-41- metbyl-51-sulpho-, 2<SP>1</SP> : 5<SP>1</SP>-disulpho-, 4<SP>1</SP>-methoxy- or ethoxy-2<SP>1</SP>-sulpho- and 3<SP>1</SP>-carboxy derivatives, 1-(4<SP>1</SP>-sulpho)naphthyl-3-methyl-5-pyrazplone, 1-( 4<SP>1</SP>-sulpho )phenyl-5-pyrazolone-3- carboxylic acid and 1-phenyl-5-pyrazolone-3- carboxylic acid ethyl ester. Specified naphthol and naphtnolsulphonic acid components are 1- and 2-naphthols 1 : 3-, 1 : 4-, 1 : 5-, 2 : 6- and 2: 8-naphtholsulphonic acids and 1 : 3 : 6-, 2 : 3 : 6- and 2 : 6 : 8-naphtnoldisulphonic acids. Examples (1) to (9) relate to the preparation of the following pyrazolone dyestuffs, (1) 4-amino- N -etbyl-chloroacetanilide or 4-amino-2-N- ethyl-chloroacet-toluidide# 1-(2<SP>1</SP>:5<SP>1</SP>-dichloro-4<SP>1</SP>- sulpno)phenyl - 3 - methyl - 5 - pyrazolone, (2) 4 - amino - N - ethyl - chloroacetanilide#1 - (41 - sulpho)phenyl - 3 - methyl - 5 - pyrazolone, (3) 3 - amino - chloroacetanilide - 4 - sulphonic acid#1 - phenyl - 3 - methyl - 5 - pyrazolone or its 21-chloro-, 41-sulpho- or 2<SP>1</SP> : 5<SP>1</SP>-dichloro- 4<SP>1</SP>-sulpho-derivatives, (4) 3-amino-cnloro- 'acetanilide - 4 - sulphonic acid#1 - (4<SP>1</SP> - sulpho) phenyl - 5 - pyrazolone - 3 - carboxylic acid, (5) 4 - amino - chloroacetanilide# 1 - (4<SP>1</SP>-sulpho) phenyl - 3 - methyl - 5 - pyrazolone, (6) 4 - amino - N - cyclohexyl - chloroacetanilide# the 2<SP>1</SP> - chloro - 51 - sulpho-, 31 and 41 - sulphoderivatives of 1 - phenyl - 3 - methyl - 5 - pyrazolone, (7) 4 - amino - N - isopropyl - chloroacetanilide# 2<SP>1</SP> - chloro 5<SP>1</SP> - sulpho) phenyl - 3 - methyl - 5 - pyrazolone, (8) 3 - amino - N - benzyl - chloroacetanilide# 1 - (4<SP>1</SP> - chloro - 2<SP>1</SP> - sulpho)phenyl - 3 - methyl - 5 - pyrazolone, (9) 4 - amino - N - phenyl - chloroacetanilide# 1 - (2<SP>1</SP> : 5<SP>1</SP> - dichloro - 4<SP>1</SP> - sulpho) phenyl - 3 - methyl - 5 - pyrazolone. A table is given showing the shades obtainable on wool wita the pyrazolone dyestuffs. Examples (10) to (44), from various other combinations of components. Examples (45) to (54) relate to the. preparation of the following dyestuffs, (45) 4 - amino - 2 - N - ethyl - α - bromopropionyl -toluidine# the 4<SP>1</SP> - sulpho - or 2<SP>1</SP> : 5<SP>1</SP> - dichloro - 4<SP>1</SP> - sulpho - derivative of 1 - phenyl - 3-methyl-5-pyrazolone. (46), (47)'and (48) 4- amino - N - ethyl - chloroacetanilide# 2 : 6 : 8 - naphtholdisulphonic, 1 4-naphtholsulphonic and 1 : 3 : 6-naphtholdisulphonic acids respectively, (49) 4-amino-2-N-ethyl-chloroacettoluidide# 2 : 6 : 8- or 2 : 3 : 6-naphtholdi - sulphonic acid, (50) 4-amino-N-ethyl-bromoacetanilide# 2 : 6 : 8-naphtholdisulphonic acid, (51) 3- or 4-amino-chloroacetanilide# 1.: 3 : 6- naphtholdisulphonic acid, (52) 4-amino-N-cyclohexyl-chloroacetanilide# 2 : 6- or 2 : 8-naphtholsulphonic or 2 : 6 8-naphtholdisulphonic acid, (53) 4 - amino - N - isopropyl - chloroacetamide# 1 : 4- or 1 : 5-naphtholsulphonic or 2 : 6 : 8-naphtholdisulphonic acid, (54) 3-amino- N - benzyl - chloroacetanilide# 1 : 4-naphtholsulphonic acid. A further table is given showing the shades obtainable on wool with the naphtholsulphonic acid dyestuffs from various combinations of components. Examples (72) and (73) relate to the preparation of the dyestuffs, (72) 4-amino-2-N-ethyl-α- or #-bromopropionyl - toluidine# 1 : 4 - naphtholsulphonic or 2 : 6 : 8 - naphtholdisulphonic acid, (73) 4 - amino - chloroacetanilide - 3 - sulphonic acid# 1- or 2-naphthol or 2 : 6 : 8-naphtholdisulphonic acid. Specifications 216,971, 281,713, 313,110, [all in Class 2 (iii)], 340,640 and 472,171 are referred to. Amines of the above general formula in which Y represents alkyl, aralkyl; cycloalkyl or phenyl, substituted or not, are obtained :by reducing the nitro group in the products of re-action of an appropriate halogenacyl halide with the appropriate nitro-secondary amine in an inert solvent such as dry toluene. 3- Amino-chloroacetanilide-4-sulphonic acid is obtained by re-action of chloroacetyl chloride with 1 : 3-diaminobenzene-4-sulphonic acid. Diazotized 3- and 4-amino-chloroacetanilides are obtained by the action of nitrous acid or 3- and 4-chloroacetaminophenyl sulphamates, which are obtained by re-action of chloroacetyl chloride on 3- and 4-aminophenylsulphamates respectively in glacial acetic acid containing saturated aqueous sodium acetate.