72852-97-2Relevant articles and documents
Convenient Synthesis of Vinylcyclopropanes by Intermolecular Trapping of Thermally Generated Perchlorovinylcarbene
Weber, Walter,Meijere, Armin de
, p. 2450 - 2471 (2007/10/02)
Tetrachlorocyclopropene (1) is ringopened above 150 deg C to give perchlorovinylcarbene (2), which is intermolecularly trapped by olefins with high efficiency.The olefin configuration is retained in the products, 1-chloro-1-(trichlorovinyl)cyclopropanes 7, 11, and 14, respectively.With n-hexane and adamantane 17 - 19 as well as 21 and 22 are obtained by C-H insertion.For 21 olefins with different degrees of substitution and types of substituents the isolated yields range from 24 to 88 percent, in most cases above 60 percent.Acrylonitrile (9 percent) and substituted acrylonitriles (17 percent) give lower yields, acrylates, however, react well.The torsional barriers of the chloro(trichlorovinyl)cyclopropane derivatives 14 are unusually high (17.4 - 18.6 kcal/mol) for vinylcyclopropane systems.Products 7 can be reductively dechlorinated to vinylcyclopropane hydrocarbons 23, ethylidenecyclopropanes 24 being observed as by-products.
