Patent GB-419010-A (GB)
Title: Manufacture and application of products useful as assisting agents in the textile and leather industries
IPC: C07D235/08
Filed: 1933-04-27
Abstract: Products which are stated to be emulsifying agents are obtained by treating with an alkylating or aralkylating agent an unsulphonated m -substituted cyclic amidine, which on the one hand is derived from an ortho or peridiamine and on the other hand is substituted at the m -carbon by an aliphatic residue containing at least three carbon atoms or by a hydroaromatic residue.  In a modification an unsulphonated ortho or peridiamine substituted in one amino group by an alkyl, aryl or aralkyl group or a corresponding nitro amine is condensed with an aliphatic carboxylic acid containing at least four carbon atoms or a hydroaromatic carboxylic acid or with an ester of such an acid, the nitro group in the case of a nitro-amine being simultaneously reduced.  In a further modification, an N-alkyl, N-aryl or N-aralkyl unsulphonated cyclic amidine substituted in the m -position by an aliphatic residue containing at least three carbon atoms or by a hydroaromatic residue is treated with an alkylating or aralkylating agent which is capable of combining by addition with a tertiary amine, or a salt thereof to give a quaternary ammonium salt. In examples: (1) m -heptadecylbenzimidazole is alkylated with methyl, ethyl or butyl chloride or ethyl bromide, ethyleneoxide or a -glycerinechlorhydrin; (2) a mixture of m -pentadecyl and m -heptadecyl benzimidazoles (obtained from ortho phenylenediamine and commercial stearic acid) is treated with dimethyl sulphate; (3) a m -substituted benzimidazole prepared from ortho phenylenediamine and coconut oil or a mixture of coconut, olive and hydrogenated fish oils is treated with a mixture of ethylene chlorhydrin and a -glycerine chlorhydrin; (4) commercial stearic acid is condensed with monomethyl-ortho-phenylenediamine; (5) a mixture of ortho nitromethylaniline and coconut oil is simultaneously reduced and condensed by treating with hydrogen and a nickel catalyst; 4-chlor- or 4-methyl-2-nitromethylaniline may be used in place of the nitromethylaniline; (6) m -heptadecyl-N-methyl (or ethyl) benzimidazole liberated from the hydrochloride by means of caustic soda is treated with ethyl chloride or methylchloride, a quaternary ammonium salt being formed; (7) m -heptadecyl benzimidazole is methylated with dimethyl sulphate and then with further quantites of the latter converted into the quaternary ammonium salt; similarly a mixture of benzimidazoles prepared from stearic and palmitic acids may be first benzylated and then converted into the quaternary salts; (8) m -propyl, undecyl and heptadecenyl-benzimidazoles are first benzylated and then converted into the quaternary ammonium chlorides; (9) m -heptadecenyl benzimidazole is treated with epichlorhydrin; (10) N-benzyl-m -heptadecylbenzimidazole hydrochloride is treated with ethylene oxide.  The cyclic amidines may be derived from ortho toluylene diamine, chlorinated ortho phenylenediamines or ortho or peri-naphthylene diamines by condensation with caproic, caprylic, capric, arachic, cerotic or naphthenic acids. Chlormethylnaphthalene, halogen alkylsulphonic acids and propylene oxide are mentioned as components for use in the conversion of the N-substituted cyclic amidines or their salts into quaternary ammonium salts.ALSO:Auxiliary agents, e.g. wetting, washing, emulsifying, and softening agents for use in the textile, leather and other industries are obtained by treating with an alkylating or aralkylating agent an unsulphonated m -substituted cyclic amidine, which on the one hand is derived from an ortho or peri diamine and on the other hand is substituted at the m -carbon by an aliphatic residue containing at least three carbon atoms or by a hydroaromatic residue.  In a modification, an unsulphonated ortho or peridiamine substituted in one amino group by an alkyl, aryl or aralkyl group or a corresponding nitro amine is condensed with an aliphatic carboxylic acid containing at least four carbon atoms or a hydroaromatic carboxylic acid or with an ester of such an acid, the nitro group in the case of a nitroamine being simultaneously reduced.  In a further modification, an N-alkyl, N-aryl or N-aralkyl unsulphonated cyclic amidine substituted in the m -position by an aliphatic residue containing at least three carbon atoms or by a hydroaromatic residue is treated with an alkylating or aralkylating agent which is capable of combining by addition with a tertiary amine, or a salt thereof to give a quaternary ammonium salt. In examples: (1) m -heptadecylbenzimidazole is alkylated with methyl, ethyl or butyl chloride or ethyl bromide, ethyleneoxide or a -glycerinechlorhydrin; (2) a mixture of m -pentadecyl and m -heptadecyl benzimidazoles (obtained from ortho phenylene-diamine and commercial stearic acid) is treated with dimethyl sulphate; (3) a m -substituted benzimidazole prepared from ortho phenylene-diamine and coconut oil or a mixture of coconut, olive and hydrogenated fish oils is treated with a mixture of ethylene chlorhydrin and a -glycerine chlorhydrin; (4) a product which precipitates dyestuffs containing sulpho groups is prepared by condensing commercial stearic acid with mono - methyl - ortho - phenylene-diamine; (5) a mixture of ortho nitromethyl-aniline and coconut oil is simultaneously reduced and condensed by treating with hydrogen and a nickel catalyst; 4-chlor-or 4-methyl-2-nitromethylaniline may be used in place of nitromethylaniline; (6) m -heptadecyl-N-methyl (or ethyl) benzimidazole liberated from the hydrochloride by means of caustic soda is treated with ethyl chloride or methyl-chloride, a quaternary ammonium salt being formed; (7) m -heptadecyl benzimidazole is methylated with dimethyl sulphate and then with further quantities of the latter converted into the quaternary ammonium salt; similarly a mixture of benzimidazoles prepared from stearic and palmitic acids may be first benzylated and then converted into the quaternary salts; the products render natural and regenerated cellulose dyed with direct dyestuffs fast to water; (8) m  - propyl, undecyl and heptadecenyl - benzimidazoles are first benzylated and then converted into the quaternary ammonium chlorides; (9) m -heptadecenyl benzimidazole is treated with epichlorhydrin; (10) N-benzyl-m -heptadecylbenzimidazole hydrochloride is treated with ethylene oxide; (11) wool is dyed with Neolan Violet R in the presence of heptadecyl-N : N-dibenzylbenzimidazolium chloride; (12) cotton yarn is dyed with Direct Sky Blue and after treated with heptadecyl-N-N-dibenzylbenzimidazolium chloride.  The cyclic amidines may be derived from ortho toluylene diamine, chlorinated ortho phenylenediamines or ortho or peri-naphthylene diamines by condensation with caproic, caprylic, capric, arachic, cerotic or naphthenic acids.  Chlormethyl-naphthalene halogen alkylsulphonic acids and propylene oxide are mentioned as components for use in the conversion of the N-substituted cyclic amidines or their salts into quaternary ammonium salts.