GB712745A - Improvements in or relating to the preparation of derivatives of organic amines - Google Patents

Abstract

A process for the preparation of N-dichloroacetyl derivatives of the type R5R6NCOCHCl2 and Cl2CHCONH-R7-NHCOCHCl2 comprises reacting with chloral cyanohydrin, or precursor therefor, in the presence of an acid binding agent, an amine of the type R5R6NH or NH2-R7-NH2 in which R5 and R6 are the same or different and may represent an alkyl, a hydroxyalkyl, a cycloalkyl or an aralkyl group, or together with the nitrogen atom to which they are attached may form a ring which may or may not contain another hetero atom and R5 may also represent a hydrogen atom (excluding the case where R5 represents a hydrogen atom and R6 represents the grouping <FORM:0712745/IV (b)/1> in which R1 and R2 are each a hydrogen atom or together constitute a -CHR4- group in which R4 represents a hydrogen atom or an alkyl group having not more than 4 carbon atoms or an aryl group and R3 represents a hydrogen atom or a nitro group), and wherein R7 is an alkane chain. The chloral cyanhydrin may first be treated with an acid-binding agent and the product so obtained used as the dichloracetylating agent. As a precursor for chloral cyanhydrin may be used chloral or chloral hydrate ih the presence of an alkali metal cyanide catalyst. As acid-binding agents there may be used inorganic or tertiary organic bases, excess amine, or an excess of alkali metal p cyanide catalyst. When chloral cyanhydrin itself is used, organic bases, e.g. triethylamine, are preferred; with chloral or chloral hydrate, inorganic bases, e.g. calcium carbonate, magnesium oxide and sodium carbonate, are preferred. Water, pyridine and dioxan are suitable solvents. Reaction temperatures of 0 DEG to 25 DEG C. using chloral cyanhydrin itself, and 60 DEG to 100 DEG C. using chloral or chloral hydrate in the presence of a catalyst are preferred. In examples, there are prepared (1) 1-dichloracetamido-n-butane by reacting n-butylamine, sodium cyanide and chloral hydrate in the presence of calcium carbonate; (2) dichloracetamido-cyclohexane (a) similarly to (1) and (b) by reacting cyclohexylamine and chloral cyanhydrin in the presence of triethylamine; (3) b -dichloracetamido-ethanol, from ethanol, similarly to (1); (4) 1 : 6-bis-dichloracetamidohexane; and (5) N-dichloracetyl morpholine are prepared from 1 : 6-hexamethylene diamine and morpholine by the method of (2b); (6) 2-dichloracetamido-1-phenylpropane by reacting 2-amino-1-phenylpropane, chloral hydrate and potassium cyanide in the presence of (a) calcium carbonate, (b) magnesium oxide, (c) sodium carbonate, or by reacting the 2-amino-1-phenylpropane with chloral cyanhydrin in the presence of (d) sodium hydroxide, (e) sodium carbonate, (f) pyridine and sodium carbonate. Specification 692,265 is referred to.