The Gamma Radiolysis of Butyl Chlorides

Abstract

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Rearrangement in Alkyl Groups during Substitution Reactions

“…The isomerization of n-propyl chloride by 7-radiolysis (60Co source) is thought to involve the following freeradical mechanisms (189,190), and similarly the forma-CH,CHC1CH2 CH,CHCH2C1 ch,ch2ch2ci + CH,CHC1CH2 -> CH,CHCH2C1 + CH,CHC1CH, tion of sec-and isobutyl chlorides from n-butyl chloride by the action of 7-rays probably occurs with free-radical intermediates (36). Under the influence of n,7 ac-CH,CH2CH2CH2C1 ch,ch2ch2ch2 + 'Cl L rearrangement tivation n-, sec-, iso-, and ¿-butyl bromides all undergo isomerization by bromine shift in addition to other side reactions (124), while both n-and isopropyl bromides isomerize under neutron radiation.…”

REARRANGEMENT STUDIES WITH C14: XVI. REARRANGEMENTS INDUCED BY γ -IRRADIATION OF 2-PHENYLETHYL-1-C14 BROMIDE OR 2-p-METHOXYPHENYLETHYL-1-C14 BROMIDE

“…On the other hand, free-radical rearrangements have been postulated as the explanation for the yinduced isomerization of n-butyl to s-butyl, and i-butyl to t-butyl halides (7,8). The formation of 1-phenylethyl radical in the photolyses of 2-phenylethanol in a rigid medium a t low temperature was suggested as having resulted fro111 isomerization of the 2-phenylethyl radical (5).…”