CHEMICAL EFFECTS OF THE (n, γ) ACTIVATION OF BROMINE IN THE ALKYL BROMIDES: ISOMERIZATION IN THE BROMOBUTANES¹

Rearrangement in Alkyl Groups during Substitution Reactions

“…is also shown to occur without appreciable elimination and recombination of hydrogen chloride. Thus, in the presence of deuterium chloride, the isopropyl chloride formed contains no deuterium, although propylene and deuterium chloride combine under similar conditions (124).…”

“…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. The rearrangement iso-to n-propyl bromide occurs with high probability in epithermal reactions (47).…”