The effect of substituents and operating conditions on the electrochemical fluorination of alkyl phenylacetates in Et3N·4HF medium

Selective electrochemical fluorination of alkyl phenylacetates (Ph–CH2–COOR, where R is methyl, ethyl, n-propyl, n-butyl, i-propyl and sec-butyl) under galvanostatic conditions were reported in Et3N·4HF medium. Preparative electrolysis experiments were carried out both in pre-electrolysed dry Et3N·4HF and the same electrolyte medium without pre-electrolysis. Very little hydrolysed fluorinated products were obtained in pre-electrolysed medium where as significant quantities of hydrolysed products leading to fluorinated phenylacetic acid were obtained from Et3N·4HF without pre-electrolysis. Under optimum experimental conditions up to 87% selectivity of monofluoro ester could be achieved. Difluoro alkyl phenylacetate, monofluoro and difluoro phenylacetic acids were the other predominant side products obtained. The hydrolysis appears to be initiated by tautomeric transformation of proton after the initial electro oxidative formation of the cation radical. 19F as well as 1H NMR spectroscopy have been employed to identify the minor constituents formed during the electro oxidative process.

Under optimum galvanostatic experimental conditions alkyl phenylacetates undergo selective electrochemical fluorination to give monofluoro derivative with selectivity upto 87%. Difluoro derivatives and fluorinated phenylacetic acids are the other predominant side products.Figure optionsDownload as PowerPoint slide