The Use of Bromotrichloromethane in Chlorination Reactions

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.