Patent GB-483324-A (GB)
Title: Improvements in or relating to the manufacture of basic substituted carboxylic acid amides
Filed: 1936-10-16
Abstract: n-Dodecylamine and betaine are heated with phosphorus trichloride, in the presence of pyridine and toluene, to yield the chloride of betaine dodecylamide, which is useful as an agent for dispersing oils, fats and waxes in aqueous liquids.ALSO:Carboxylic acids containing a quaternary ammonium group are converted into amides by reaction with organic compounds containing one or more primary or secondary amino groups in the presence of a dehydrating agent; instead of the free acids, their intramolecular salts or their salts with acids may be treated. Specified carboxylic acids are betaine and its homologues, trimethyl-m- or -p-benzobetaine (trimethyl-m- or -p-carboxyphenylammonium hydroxide), and the reaction products of dimethylaminoacetic acid or other carboxylic acid containing a tertiary nitrogen atom with alkyl or aralkyl halides, dialkyl sulphates, or alkyl esters of arylsulphonic acids; carboxylic acids containing a quaternary nitrogen atom as part of a heterocyclic ring are also mentioned.  Specified dehydrating agents are phosphorus halides and oxyhalides, and thionyl chloride.  The amino compounds may be of the aliphatic, aromatic, aliphatic-aromatic or heterocyclic series, and may contain inert substituents.  The reaction is preferably effected in the presence of a diluent, and this may be a tertiary amine, e.g. triethylamine, dimethylaniline or pyridine, when the amino compound used in the reaction forms mineral acid salts which are not hydrolyzed to any great extent in aqueous solution; amino compounds mentioned in this connection are alkylamines and aniline and its homologues.  In the examples: (1) n-dodecylamine and betaine are heated with phosphorus trichloride, in the presence of pyridine and toluene, to yield the chloride of betaine dodecylamide; the product is useful as an agent for making dyeings fast to water, as an assistant in stripping vat dyes, as an agent for dispersing oils, fats and waxes in aqueous liquids, and as a flotation assistant; (2) m-nitraniline and betaine chloride are heated with phosphorus oxychloride, in the presence of pyridine and toluene, to yield the chloride of betaine m-nitroanilide; the amino compound obtained by reducing this product is useful as a p  diazo or a coupling component in the manufacture of azo dyes, and in the latter case the dyes may be rediazotized and coupled again; (3) p-nitraniline and betaine chloride, brought to reaction as in example 2, yield products of similar properties; (4) 1-aminoanthraquinone and betaine chloride are heated in nitrobenzene with thionyl chloride to yield the chloride of betaine 1-anthraquinonylamide; products useful as basic dyes are obtained if the 1-aminoanthraquinone is replaced by aryl or aminoaryl derivatives of 1 : 4- or 1 : 5-diaminoanthraquinone, e.g. by 1 - amino - 4-phenylaminoanthraquinone or 1 : 4-di(p-aminophenylamino)anthraquinone; (5) 21 : 31-hydroxynaphthoyl - m - phenylenediamine and betaine chloride are heated with phosphorus trichloride in toluene and pyridine to yield the chloride of betaine - m - (21 : 31 - hydroxynaphthoylamino)anilide; the product may be used as a coupling component for making basic azo dyes, according to the process of Specification 438,025, or as a developer for direct dyeings diazotized on the fibre, according to the process described in Specification 439,135; alternatively cellulosic fibres may be dyed by treatment first with the product and then with a diazo compound, which may contain a sulphonic or carboxylic group (cf. Specification 439,135); (6) benzidine and trimethyl-m-carboxyphenylammonium chloride are heated with phosphorus tribromide, in the presence of toluene and triethylamine, to yield the di-methobromide of sym. bis(31-dimethylaminobenzoyl)benzidine; the product is useful for treating cellulosic fibres before or after dyeing with substantive dyes, to improve the fastness of the dyeings to water (cf. Specification 427,089).  The manufacture of amides by reaction of the specified acids with diphenylamine is mentioned.  A sample has been furnished under Sect. 2 (5), of piperidinoacetic acid piperidide iodobenzylate (the piperidide of N-benzyl-N-iodopiperidinoacetic acid), obtained by treating benzylpiperidinium-betaine chloride with piperidine, as in example 1, and precipitating the product with potassium iodide.ALSO:n-Dodecylamine and betaine are heated with phosphorus trichloride, in the presence of pyridine and toluene, to yield the chloride of betaine dodecylamide, which is useful as a flotation assistant.