GB1141079A - Acetylenic carbamates and thiocarbamates - Google Patents

Abstract

1,141,079. Acetylenic carbamates or thiocarbamates. J. WYETH & BROTHER Ltd. 13 Nov., 1967 [15 Dec., 1966], No. 56202/66. Heading C2C. Novel acetylenic carbamates and thiocarbamates of the formula wherein Ar is a phenyl, naphthyl, or heteroaryl radical, or a phenyl radical substituted by alkoxy, aralkyloxy, halogen, haloalkyl or alkyl; R<SP>1</SP> is H, prop-2-ynyl, aralkyl, one of the radicals specified for Ar or an alkyl radical which may be substituted by OH, OCONH 2 , or dialkylamino; R<SP>2</SP> is H or C 1-4 alkyl; R<SP>3</SP> and R<SP>4</SP>, which may be the same or different each represent an H, or alkyl, or R<SP>3</SP> and R<SP>4</SP> together with the nitrogen atom to which they are attached can form a heterocyclic ring which may contain a further heteroatom; and X is O or S 1 , are prepared by reacting the appropriate alcohol with a suitable carbamic or thiocarbamic acylating agent, i.e. one or more compounds capable of converting a CH 2 OH group into a -CH 2 0C.X.N(R<SP>3</SP>)R 4 group in one or more stages. 2,2 - Diphenyl -, (2 - benzyl - 2 - phenyl -, 2- (o - chlorophenyl) - 2 - phenyl -, 2 - (p - chlorophenyl) - 2 - phenyl -, 2 - phenyl - 2 - (21 - propynyl) -, and 2 - phenyl - 2 - propyl -,) 4- pyntyne- 1 -ols are obtained by reducing with lithium aluminium hydrid the corresponding methyl or ethyl esters, which are in turn prepared by reacting propargyl bromide with the sodium derivatives of ethyl 2,2-diphenylacetate, ethyl 1,2 - diphenylpropionate o - chlorophenylphenylacetate, obtained by treating o-chlorophenylacetonitrile with concentrated sulphuric acid and absolute ethanol, ethyl-2-(p-chlorophenyl) - 2 - phenylacetate, methyl phenylacetate, and ethyl 2-phenylpentanoate respectively. Ethyl 2 - hydroxymethyl - 2 - phenyl - 4 - pentynoat and 2 - phenyl - 2 - (2<SP>1</SP> - propynyl) - 1,3-propanediol are obtained by reducing diethyl 2 - phenyl - 2 - (2<SP>1 </SP>- propynyl) malonate with lithium aluminium hydride. Pharmaceutical compositions, having antiinflammatory, or depressant, convulsant and anti-convulsant activity contain the above novel carbamates and a pharmaceutical carrier.