Alkylation of Carboxylate Salts of Acidic Herbicides for Gas Chromatographic Analysis

The methyl esters of 2-methoxy-3, 6-dichlorobenzoic acid and three phenoxyacetic acids were prepared by the admixture of an excess of both methyl iodide and anhydrous alkali-metal carbonate to a solution of the carboxylic acids in acetone. The reaction was completed within the shortest period of time when cesium carbonate was used, and the reaction mixture was injected without further work-up into a gas chromatograph fitted with a flame ionization detector. Further reduction of reaction time was achieved by heating the mixture to 50°C and by ultrasonic treatment; this technique is also suitable for esterification of microliter quantities and obviates the need for a microrefluxer. Butylesters of 2, 4-D and 2, 4, 5-T were prepared in an analogous manner. The methyl esters of 2, 4-D and 2, 4, 5-T, and the butyl ester of 2, 4-D were obtained in better than 90% yield.