Patent GB-556358-A (GB)
Title: New monoazo dyestuffs
IPC: C09B29/30
Filed: 1941-12-29
Abstract: 556,358. Dyes and intermediates. KNIGHT, A. H., STEPHEN, W. E., and IMPERIAL CHEMICAL INDUSTRIES, Ltd. Dec. 29, 1941, Nos. 16717 and 16827. [Class 2 (iii)] Monoazo dyes, suitable for colouring animal fibres, e.g. wool or silk, and dyeing wool from an acid bath red or reddish brown shades, fast to severe washing and milling and to light, are obtained by diazotizing an amine of the general formula X - CO - NY - R - NH 2 , wherein R represents a m - or p-phenylene residue, which may be substituted, e.g. by methyl, methoxy or sulphonic groups, X represents a monochloro- or monobromo-alkyl (C 1  to C 3 ) group and Y represents H, unsulphonated alkyl (C 1  to C 6 ), cycloalkyl, aralkyl, alkoxyalkyl or aryl, and coupling with an N - acyl- 2 : 8 : 6 - aminonaphtholsulphonic acid of which the acyl group is formyl, alkoxyformyl; succinyl, benzoyl, arylsulphonyl, hydroaromatic sulphonyl, hydroaromatic carbonyl, aralkoxy - A, cycloalkoxy - A, aryloxy - A or alkoxy (C 1  to C 4 ) - A, where A represents acetyl, propionyl or butyryl; and the remaining H atom of the 2 - amino group may be replaced by alkyl, hydroxyalkyl or aryl. Specified diazo components are the N - ethyl, N - isopropyl, N - n - butyl, N - sec. butyl, N - cyclohexyl, N - # - ethoxyethyl, N - benzyl and N - - phenyl derivatives of 4 - amino - chloroacetanilide, the N - ethyl derivatives of 4 - amino - #- - chloro- and bromo-propionanilides, the 2 - N - ethyl derivatives of 4 - amino - 2 - N - chloroacettoluidide, 4 - amino - 2 - N - chloroacetanisidide and 4 - amino - 2 - N - # - chloro - or α or # - bromo - propiontoluidide, 4 - amino - 2 - N - benzyl - chloroacettoluidide, 4 - amino - 2 - N - benzyl - chloroacetanisidido, 2 - amino - 4 - N - ethyl - chloroacettoluidide, 5 - amino - 2 - N - cyclohexyl - chloroacettoluidide, 4 - amino - N - ethyl - or cyclohexyl - bromoacetanilide, 3 - amino N - benzyl - chloroacetanilide, the N - cyclohexyl derivatives of 4 - amino - # - chloro- or α - or # - bromo - proprioanilide, 3 - amino - N - benzyl - # - chloropropionanilide, 4 - amino - 2 - N - ethyl - α - bromobutyrtoluidide, 3 - amino - chloroacetanilide - 4 - sulphonic acid, 4 - amino - chloroacetanilide - 3 - sulphonic acid and 4 - amino - N - n - butyl - or cyclohexyl -.chloroacetanilide - 2 - sulphonic acid. Specified coupling components are the N - formyl, N - methoxy - or ethoxyformyl, N - succinyl, N - benzoyl, N - o - chlorobenzoyl, N - m - bromobenzoyl N- benzene - or p - - toluene - sulphonyl, N - tetrahydronaphthalene- 2 - 'sulphonyl, N - hexahydrobenzoyl, N - benzyloxyacetyl, N - cyclohexyloxyacetyl, N - phenoxyacetyl, N - o - or p - chlorophenoxyacetyl, N - p - methylphenoxyacetyl, N - 5 - chloro - 2 - methylphenoxyacetyl, N - # - phenoxypropionyl, N - methoxy - ethoxy - or n - butoxy - acetyl, N - α - methoxypropionyl, N - α - methoxy or γ - ethoxy - n - butyryl, N - phenyl - N - formyl, N - ethyl - N - - ethoxyformyl, N - methyl - N - succinyl, N - methyl- or ethyl - N - benzoyl, N - # - hydroxyethyl - N - benzoyl, N - y - hydroxypropyl - N - benzoyl, N - methyl - N - o - chlorobenzoyl, N - methyl - N - methoxyacetyl, N - #- hydroxyethyl - N - methoxyacetyl and N-phenyl-N-methoxyacetyl derivatives of 2 : 8 : 6 - aminonaphtholsulphonic acid. Examples relate to the production of the dyestuffs, (1) to (4), (1) 4 - amino - N - ethylchloroacetanilide, (2) 4 - amino - 2 - N - ethyl - chloroacettoluidide, (3) 4 - amino - N - cyclohexyl - chloroacetanilide, (4) 3 - amino - chloroacetanilide - 4 - sulphonic acid # N - methoxyacetyl - 2 : 8 : 6 - acid, (5) 4 - amino - N - ethylchloroacetanilide # N - phenoxyacetyl - 2 : 8 : 6 - acid, (6) 4 - amino - 2 - N - ethyl - chloroacettoluidide # N - benzyloxyacetyl - 2 : 8 : 6 - acid, (7) 4 - amino - 2 - N - ethyl - #- bromopropiontoluidide, 4 - amino - N - ethyl - # - chloropropionanilide or 4-amino-N-isopropylchloroacetanilide # N - methoxyacetyl - 2 : 8 : 6 - acid, (8) 4 - amino - 2 - N - ethyl - chloroacettoluidide # N - methyl - or N - # - hydroxyethyl N - methoxyacetyl - 2 : 8 : 6 acid, (9) 3 - amino - N - benzyl - chloroacetanilide# N - o - chlorophenoxyacetyl - 2 : 8 : 6 - acid, (10) and (11) 4 - amino - N - ethyl - chloroacetanilide # N - benzoyl - 2 : 8 : 6 - acid in presence of (10) sodium carbonate (11) sodium acetate, (12) 4 - amino - N - ethyl - # chloropropionanilide # N - benzoyl - 2 : 8 : 6 - acid in presence of sodium acetate, (13) 4 - amino - N - ethyl - # - chloropropionanilide # N -  methyl - or ethyl - N - benzoyl - 2 : 8 : 6 : acid or N - methyl - N - o - - chlorobenzoyl - 2 : 8 : 6- acid, (14) 4 - amino - N - cyclohexyl - chloroacetanilide # the N - ethoxyformyl, N - methyl- N - benzoyl or N - phenyl - N - formyl derivative of 2 : 8 : 6 - acid, (15) 4 - amino - 2 - N - - ethyl - chloroacettoluidide - the N - #-hydroxyethyl - N - benzoyl or N - γ - hydroxypropyl - N - benzoyl derivative of 2 : 8 : 6 - acid, (16) 4 - amino - N - phenyl - chloroacetanilide -)- N - succinyl 2 : 8 : 6 - acid, (17) 4 - amino - N - isopropyl or sec.-butyl - chloroacetanilide # N - p - toluenesulphonyl - 2 : 8 : 6- acid, (18) 4 amino - N - # - methoxyethyl - or # - ethoxyethyl - chloroacetanilide # N - benzoyl - 2 : 8 : 6 - acid, (19) 3 - amino - N - benzyl - chloroacetanilide # N - succinyl - 2 : 8 : 6 - acid. A table is also given showing the shades obtainable on wool with the dyestuffs from various combinations of components. Specifications 340,640, 424,354, 472,171, 544,409 and 553,204 are referred to. N - acyl - 2 : 8 : 6 - aminonaphtholsulphonic acids as above are obtained by reaction of 2 : 8 : 6 - acid or the appropriate N - alkyl-, N - hydroxyalkyl - or N - aryl derivative with the chloride or anhydride of the appropriate carboxylic or sulphonic acid. o - Chlorophenoxyacetyl chloride and cyclohexyloxyacetyl chloride are obtained by the action of thionyl chloride on o - chlorophenoxyacetic and cyclohexyloxyacetic (cf Specifications 413,728 and 414,121) acids respectively.