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Molecules. 2018 May 1;23(5). pii: E1055. doi: 10.3390/molecules23051055.

KOtBu as a Single Electron Donor? Revisiting the Halogenation of Alkanes with CBr₄ and CCl₄.

Author information

1
Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, UK. katie.polly.emery@gmail.com.
2
Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, UK. a.young@strath.ac.uk.
3
Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, UK. jude.arokianathar@strath.ac.uk.
4
Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, UK. tell.tuttle@strath.ac.uk.
5
Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, UK. John.murphy@strath.ac.uk.

Abstract

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.

KEYWORDS:

alkanes; dihalocarbenes; halogenation; hypohalite; potassium tert-butoxide

PMID:
29724009
DOI:
10.3390/molecules23051055
[Indexed for MEDLINE]
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