GB613807A - Processes for the production of amino compounds - Google Patents

Abstract

Bis-beta-amino propionitriles containing the skeleton <FORM:0613807/IV(b)/1> where R is a divalent organic radical, are prepared by reacting an a b -unsaturated nitrile with a diamine in which both amino groups are primary, the reactants being used in the proportion of substantially two moles. of the unsaturated nitrile to one mole. of diamine. The unsaturated nitriles should be free from substituents which react with amino groups. The reactants may be simply mixed, at room temperature, with or without a diluent, for example water, and the mixture allowed to stand for one or two hours; if desired, the mixture may be warmed. The bis-beta-aminopropionitrile may be reduced by treatment with hydrogen, preferably by catalytic hydrogenation using a nickel catalyst in the presence of ammonia, so yielding the corresponding tetramines containing two primary and two secondary amino groups. The amino propionitriles may also be hydrolysed to the corresponding dicarboxylic acids; in alkaline media, salts of these acids result, from which the free acids may be obtained by acidification; by hydrolysing with an acid reagent in an alcoholic medium the corresponding dicarboxylic esters are obtained, mention being made in this connection of alkyl and aralkyl esters. In examples: (1) acrylonitrile is reacted with a mixture of ethylene diamine and water and the resulting ethylene-bis-beta-aminopropionitrile recovered by distillation; (2) the crude product of (1) before the distillation step is mixed with ethanol saturated with ammonia and hydrogenated in the presence of a Raney nickel catalyst to yield N : N1 - bis - gamma - aminopropyl - ethylene diamine, and reference is made to its hydrate and tetrabenzoyl derivative; (3) acrylonitrile is reacted with hexamethylene diamine to yield hexamethylene - bis - beta - amino propionitrile which on reduction as in (2) above yields N : N1-bis - gamma - aminopropyl hexamethylene diamine; (4) acrylonitrile is reacted with hexamethylene diamine and the product hydrolysed to give hexamethylene bis-beta-amino propionic acid. Other starting materials specified are methacrylonitrile and crotonitrile, and trimethylene diamine, tetramethylene diamine, pentamethylene diamine, para-phenylene diamine, 1 : 4 - diamino - hexane and gamma - gamma1-diamino propyl ether which is prepared by reacting ethylene cyanohydrin with acrylonitrile and reducing the resulting dinitrile. The nitriles and the corresponding tetramine, free acids or the esters thereof may be employed in the production of polymers, for example, as described in Specification 610,311. According to the Provisional Specification, the esters of the above-described diamino-dicarboxylic acids may be reduced to yield amino alcohols. A sample has been furnished under Sect. 2 (5) of para-phenylene bis-beta-amino propionitrile prepared by reacting para-phenylene diamine with acrylonitrile in glacial acetic acid.