Patent GB-1130394-A (GB)
Title: N,n disubstituted carbamyl halides and preparation thereof
Inventor: KOENIG KARL-HEINZ
IPC: C07D211/34
Filed: 1966-02-08
Abstract: 1,130,394. Substituted carbamyl halides. BADISCHE ANILIN- & SODA-FABRIK A.G. 8 Feb., 1966 [9 Feb., 1965], No. 5403/66. Heading C2C. Compounds of the formula wherein R<SP>1</SP> to R<SP>4</SP> may be identical or different and denote hydrogen atoms, alkyl radicals or aryl radicals and R<SP>1</SP> and R<SP>3</SP> or R<SP>2</SP> and R<SP>4</SP> together may denote an alkylene radical having two to five carbon atoms in which one methylene group may be replaced by an oxygen atom, a sulphur atom or the group N-R<SP>8</SP> in which R<SP>8</SP> denotes an alkyl radical, a cycloalkyl radical or the phenyl radical, X denotes a chlorine or bromine atom, and Y denotes a hydrogen atom or the radical A, and A may denote the radical in which R<SP>5</SP> denotes hydrogen, alkyl, or cycloalkyl; R<SP>6</SP> denotes hydrogen, alkyl, aryl, carbalkoxy, alkylcarbonyl, cyano or nitro; R<SP>7</SP> denotes carbalkoxy, alkylcarbonyl, cyano or nitro; or R<SP>6</SP> and R<SP>7</SP> taken together with the carbon to which they are attached represent a C 5  to C 8  membered carbocyclic ring which has a carbonyl group in the α-position to the carbon atom bearing R<SP>6</SP> and R<SP>7</SP>, or A may denote the nitrilo, thiocyanato or isocyanato group, or an acetylene radical and preparation thereof by reacting a halogeno-substituted carbamyl halide of the formula wherein R<SP>1</SP> to R<SP>4</SP> and X have the meanings given above and Z is a hydrogen, chlorine or bromine atom with cyanic, thiocyanic, hydrocyanic or isocyanic acid; a compound containing the acetylene group in which a hydrogen atom is attached to one carbon atom of the carbon triple bond; or with a compound of the formula wherein R<SP>5</SP> to R<SP>7</SP> have the meanings given above, or the alkali metal, e.g. sodium, potassium or lithium, salts thereof at a temperature of from - 40‹ to + 150‹ C. optionally in the presence of an organic solvent or suspension agent. N - Methyl - N - [#,# - di - (carbethoxy)- ethyl]-, N-(#-nitroethyl)-N-methyl-, N-methyl- N - (# - carbomethoxy - # - cyano - ethyl)-, N- cyanomethyl-N-methyl- and N-methyl-N- propyn-2-ylcarbamyl chlorides are obtained by reacting N-methyl-N-chloromethyl-carbamyl chloride with diethyl malonate, nitromethane, methyl-cyanoacetate, gaseous hydrocyanic acid and sodium acetylide respectively. N-(#- Carboxyethyl - # - ketomethyl - ethyl) - N - methyl, and N-methyl-N-thiocyanomethylcarbamyl chlorides and N-methyI-N-(α-ketocyclohexyl - methyl) - carbamyl bromide are obtained by treating the appropriate N-bromomethyl-N-methyl-carbamyl halide with ethyl sodium acetoacetate, potassium thiocyanate or cyclohexanone. 2 - (Dicyanomethyl) - -morphol - 1-yl carbamyl chloride is obtained by reacting 2-chloro-morphol-l-yl carbamyl chloride with malodinitrile. 2 - (α - Cyanobenzyl) - piperid- 1-yl carbamyl chloride is obtained by treating 2-chloropiperid-l-yl carbamyl chloride with benzyl cyanide. N,N-bis-(thiocyanatomethyl)- carbamyl chloride is obtained by reacting N,N - bis - (chloromethyl) - carbamyl chloride with potassium thiocyanate.