1611-82-1Relevant academic research and scientific papers
KOtBu as a single electron donor? Revisiting the halogenation of alkanes with CBr4 and CCl4
Emery, Katie J.,Young, Allan,Arokianathar, J. Norman,Tuttle, Tell,Murphy, John A.
supporting information, (2018/05/22)
The search for reactions where KOtBu and other tert-alkoxides might behave as single electron donors led us to explore their reactions with tetrahalomethanes, CX4, in the presence of adamantane. We recently reported the halogenation of adamantane under these conditions. These reactions appeared to mirror the analogous known reaction of NaOH with CBr4 under phase-transfer conditions, where initiation features single electron transfer from a hydroxide ion to CBr4. We now report evidence from experimental and computational studies that KOtBu and other alkoxide reagents do not go through an analogous electron transfer. Rather, the alkoxides form hypohalites upon reacting with CBr4 or CCl4, and homolytic decomposition of appropriate hypohalites initiates the halogenation of adamantane.
MECHANISMS OF FREE-RADICAL REACTIONS XXXI. FRRE-RADICAL HALOGENATION OF HEXANE BY TERT-BUTYL HYPOHALITES. REACTION MECHANISM AND SELECTIVITY OF TERT-BUTOXYL RADICAL
Dneprovskii, A. S.,Eliseenkow, E. V.,Kuznetsov, D. V.
, p. 241 - 246 (2007/10/02)
The free-radical halogenation of hexane by tert-butyl hypohalites was investigated.The ralative rate constant for the abstraction of hydrogen atoms by the tert-butoxyl radicals was determined.At the early stages of the "dark" free-radical chlorination of hexane by tert-butyl hypochlorite, initiated by trialkylborane, the abstraction of the hydrogen atoms is realized almost entirely by the tert-butoxyl radicals.
