Reaction of alkoxyhydroperoxides with metal salts alkyl halide preparation

✍ Scribed by G. Cardinale; J.C. Grimmelikhuysen; J.A.M. Laan; F.P. van Lier; D. van der Steen; J.P. Ward

• Publisher: Elsevier Science
• Year: 1989
• Tongue: French
• Weight: 557 KB
• Volume: 45
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(01)89123-7

✦ Synopsis

A synthesis is described of alkyl chlorides by reaction of methoxy hydroperoxides, prepared from 1-alkenes by oronisation in methanol, with ferric chloride: RCH-CH,_*RCH(OOH)OCH,_*R= -?RCl. Yields of 1-chlorotetradecane were about 60%; those of other halides from 38 to 57%. INTRGDUCTION When alkenes are oxonised in alcoholic solution alkoxyhydroperoxides are f0rmed.l Their reactivity towards metal salts has been explained by postulating carbon-carbon bond splitting, followed by radical formation (Scheme 1). Much of the chemistry describing radical reactions in organic synthesis has been reviewed recently.* Depending on the nature and the oxidation state of the transition metal, and on the nature of the counter ion, a range of products may be formed from the intermediate radical shown in Scheme 1. We have described procedures for preparing chloro-acetals,3 olefinic acetals3 and esters4, chloro-esters, and hydroxy-acids and dicarboxylic acids5 in modest to good yields (Scheme 2). For simplicity of