Patent GB-1092134-A (GB)
Title: Production of carbamyl halides
Inventor: KOENIG KARL-HEINZ
IPC: C07C271/04
Filed: 1965-03-05
Abstract: The invention relates to disubstituted carbamyl halides of the formula <FORM:1092134/C2/1> in which R1 to R4 denote identical or different hydrogen atoms or alkyl, aralkyl or aryl radicals, or R2 and R3 when joined together form an alkylene radical (R2 and R3 having 2-5 carbon atoms) in which one methylene group may be replaced by an oxygen or sulphur atom or a group > NR7, in which R7 denotes an alkyl, cycloalkyl or phenyl radical, X denotes chlorine or bromine, Y denotes hydrogen or a radical -ZR5, Z denotes oxygen or sulphur, and R5 denotes an unsubstituted or substituted alkyl, alkenyl, alkynyl, aralkyl, aryl, alkaryl or cycloalkyl radical or a radical -(Z:)CR6, in which R6 denotes an unsubstituted or substituted alkyl, alkenyl, alkynyl, aralkyl, aryl, alkaryl or cycloalkyl radical.  The compounds are obtainable by reacting a carbamyl halide of the formula <FORM:1092134/C2/2> in which B denotes hydrogen or a chlorine or bromine atom, with a compound of the formula HZR5 or an alkali or alkaline-earth metal salt thereof at -40 DEG  to 120 DEG  C., optionally in an organic solvent.  Specified reactants of the second formula above include N-chloromethyl-methylcarbamyl chloride, N,N - bis(chloromethyl)carbamyl chloride, N - a  - chlorobenzyl - N - chloromethylcarbamyl chloride, N - (a  - chloromorpholyl)carbamyl chloride and N(a ,a 1 - dichlorothiomorpholyl)carbamyl chloride. A number of alcohols, phenols or mercaptans which may constitute the reactant HZR5 are specified.  Also specified are a number of carboxylic and thiocarboxylic acids which may be used when HZR5 has the value HZ(Z:)CR6.  In typical examples, (1) N-chloromethyl - N - methylcarbamyl chloride and sodium methylate yield N-methoxymethyl-N-methylcarbamyl chloride, (2) N-bis(chloro-methyl)carbamyl chloride and sodium methylate yield N,N-bis(methoxy methyl)carbamyl chloride, (3) N-(3,5-dichloro-3,5-dimethylmorpholyl)carbamyl chloride and sodium methylate yield N - (3,5 - dimethoxy - 3,5 - dimethylmorpholyl)carbamyl chloride, (4) N-(a -chloroethyl)-N-methylcarbamyl chloride and acetic acid yield N - (a - acetoxyethyl) - N - methylcarbamyl chloride, and (5) N-methyl-N-chloromethylcarbamyl chloride and methyl mercaptan yield N - methyl - N - methylthiocarbamyl chloride. Other specified products include N-methyl-N-(2-ethylhexoxymethyl carbamyl chloride, N-isopropoxymethyl-N-methylcarbamyl chloride, N - propynoxymethyl - N - methylcarbamyl chloride, N - (1 - methylpropyne - (2) - oxymethyl) - N - methylcarbamyl chloride, N - propeneoxymethyl - N - methyl carbamyl chloride, N - (b  - ethoxyethoxymethyl) - N - methylcarbamyl chloride, N - (b  - bromo-ethoxymethyl) - N - methylcarbamyl chloride, N - cyclohexoxymethyl - N - methylcarbamyl chloride, N - (b - phenylethoxymethyl) - N - methylcarbamyl chloride, N - (a  - methoxypiperidyl)carbamyl chloride, N - (a  - propionyl-oxymethyl) - N - methylcarbamyl chloride, N,N - bis(a  - acetoxymethyl)carbamyl chloride, N - (a  - acryloxymethyl) - N - methylcarbamyl chloride, N - acetothiomethyl - N - methylcarbamyl chloride, N - benzylthiomethyl - N - methylcarbamyl chloride, and N - (a  - methylthiomorpholyl)carbamyl chloride.