Reactions of fluoroalkyl radicals generated electrochemically. Part 1. Additions of trifluoromethyl radicals to olefinic and acetylenic bonds

Abstract

Trifluoromethyl radicals, generated by the electrolysis of trifluoroacetic acid in acetonitrile–water–sodium hydroxide reacted with olefins CH2CHX (X = C3H7, C4H9, C5H11, CO2CH3, CN, and CH2CO2CH3) to give a mixture of products of the type CF3CH2CH2X, CF3CHCHX, CF3CH2CH(CF3)X, and (CF3CH2CHX)2. Where X = CO2CH3 trimeric products were also isolated. With hex-1-yne, electrolysis of trifluoroacetic acid gave a mixture of Z- and E-CF3CHCHC4H9 and E-CF3CHC(CF3)C4H9. In contrast cyclopentene produced only cyclopentyl trifluoroacetates.