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.