Chlorination of Olefins in Dimethylformamide with Intermediate Formation of Immonium Chlorides

✍ Scribed by A. de Roocker; P. de Radzitzky

• Book ID: 101760615
• Publisher: Wiley (John Wiley & Sons)
• Year: 2010
• Weight: 424 KB
• Volume: 79
• Category: Article
• ISSN: 0037-9646
• DOI: 10.1002/bscb.19700790904

✦ Synopsis

Abstract

Well defined intermediate immonium chlorides were isolated during the chlorination of olefines in N, N‐dimethylformamide. These immonium chlorides of general formula (CH~3~)~2~ [X‐CH(CHYCl)‐O‐CH=] N^+^.Cl^−^ react to 1,2‐dichloroalkane derivatives by thermal decomposition, to l‐chloro‐2‐alkyl formate deriatives by hydrolysis and to chlorohydrins by alcoholysis.

The 1‐chloro‐2‐alkyl formate derivatives are easily transformed into epoxy compounds.

The chlorination of styrene into 1,2‐dichloro‐l‐phenylethane gives a higher yield and a better selectivity in N, N‐dimethylformamide than in other solvents.

When bromine is used instead of chlorine, corresponding intermediate immonium bromides can also be isolated but with lower yields.