1293089 Cyclopropane carboxylic acid derivatives; hex-2,5-diyn-1-ol and halide derivatives ROCHE PRODUCTS Ltd 19 May 1971 [8 June 1970] 27583/70 Heading C2C The invention comprises cyclopropane carboxylic acid esters of the formula in which R represents a group of formula or -CH 2 -C#C-CH 2 -C#CH, in which R1, R2 and R3 each represent a hydrogen atom or a C 1 -C 4 alkyl group and the broken line denotes an optional bond. They may be prepared by either (a) reacting 2,2,3,3-tetramethyl-cyclopropane carboxylic acid chloride or bromide with an alcohol of the formula or of formula HO-CH 2 -C#C-CH 2 -C#CH; or (b) reacting an alkali metal salt, the silver salt or a tri-(C 1 -C 4 alkyl) amine salt of 2,2,3,3- tetramethyl-cyclopropane carboxylate with a halide of formula or of formula hal-CH 2 -C#C-CH 2 -C#CH in which "hal" is a halogen atom. Starting materials are prepared as follows:- (a) 2,2,3,3 - tetramethyl - cyclopropane carboxylic acid chloride is prepared by direct chlorination of the corresponding acid or by treatment of the acid with thionyl chloride; (b) the sodium salt of 2,2,3,3-tetramethyl-cyclopropane carboxylic acid is obtained by treating the acid with sodium hydroxide; and (c) the alcohol of formula HO-CH 2 -C#C-CH 2 - C#CH may be prepared by reacting propargyl alcohol with an alkyl magnesium halide, e.g. ethyl-magnesium bromide, treating the resulting complex with cuprous cyanide followed by propargyl chloride or bromide and decomposing the product by conventional techniques, for example by treatment with aqueous ammonium chloride. This alcohol may be treated with a halogenating agent, e.g. thionyl chloride or phosphorus tribromide to give the corresponding halide. The esters of the invention may be used as the active ingredients in insecticidal compositions. The compositions may contain conventional extenders, diluents, solvents, wetting agents or emulsifiers and may contain other insecticidal agents.
