Synlett 2010(9): 1377-1380  
DOI: 10.1055/s-0029-1219832
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

The Halogenation of Aliphatic C-H Bonds with Peracetic Acid and Halide Salts

Yu He, Christian R. Goldsmith*
Department of Chemistry & Biochemistry, Auburn University, Auburn, AL 36849, USA
Fax: +1(334)8446959; e-Mail: crg0005@auburn.edu;
Further Information

Publication History

Received 3 February 2010
Publication Date:
15 April 2010 (online)

Abstract

Hydrocarbons react with molar concentrations of peracetic acid and halide salts to yield predominantly monohalogenated products under optimum conditions, with chlorination being more oxidatively efficient than bromination. The alkane halogenation proceeds at ambient temperature and does not require a heavy-metal catalyst. The observed reactivity is consistent with a radical mechanism, in which the peracid initially reacts with the halide ions to yield halogen-atom radicals, which ultimately oxidize the hydrocarbon. Although the reactivity proceeds slightly more efficiently in acetonitrile, the halogenation protocol works well in water.