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Synthesis 2011(2): 342-346  
DOI: 10.1055/s-0030-1258368
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

The Use of Bromotrichloromethane in Chlorination Reactions

Stephen G. Newman, Christopher S. Bryan, Didier Perez, Mark Lautens*
Department of Chemistry, University of Toronto, Toronto, ON, M5S 3H6, Canada
Fax: +1(416)9786083; e-Mail: mlautens@chem.utoronto.ca;
Further Information

Publication History

Received 12 November 2010
Publication Date:
15 December 2010 (online)

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Abstract

Carbon tetrachloride is no longer used as a common solvent due to its toxicity and harmful environmental impact. The synthesis of gem-dichloroalkenes from aldehydes by using triphenylphosphine typically requires carbon tetrachloride as a solvent. We report that stoichiometric bromotrichloromethane in acetonitrile can be used in place of solvent quantities of carbon tetrachloride in this transformation. Similarly, bromotrichloro­methane in dichloromethane can be used for the room-temperature Appel reaction of benzyl alcohols to form benzyl chlorides, which is commonly carried out in refluxing carbon tetrachloride.

Key words

olefination - aldehydes - halogenation - Appel reaction - benzyl halides

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11

CCl4 costs approximately $28/mol when buying 1 L, while CBrCl3 costs approximately $37/mol when buying 500 g. Prices in USD from Sigma-Aldrich, October 2010.

12

The impurity was inseparable by column chromatography. GC-MS analysis suggests the impurity is a mixture of the (E)- and (Z)-1-bromo-1-chloroalkene.