Unstable intermediates. Part 120.—Electron spin resonance study of γ-irradiated t-butyl chloride: coupling to β-chlorine atoms

Abstract

Two radicals were detected by e.s.r. spectroscopy after exposure of t-butyl chloride (¹H and ²H) to γ-rays at 77 K. One, the t-butyl radical, is well known, but the other, Me₂Ċ—CH₂Cl, probably formed by loss of a methyl hydrogen atom followed by a 1,2-chlorine shift, is novel and shows the following features. These results suggest not only that the radical is locked in a conformation in which maximum overlap between the carbon 2p-orbital of the radical and the C—Cl σ-bond is achieved, but also that considerable distortion involving movement of the chlorine atom towards the radical centre has occurred.