H. Muramatsu
Jul 1, 1962
Citations
0
Influential Citations
7
Citations
Journal
Journal of Organic Chemistry
Abstract
A study was made of the gamma radioinduced addition reaction of alcohols to perhalogeno olefins, such as 1,2,2-trichloro1 -fluoroethylene, 1,2- dichloro -1,2-difluoroethylene, and 1,1-dichloro-2,2--difluoroethylene. The general reaction is: CHR1R2OH + CFX = CX2 yields CHX2 CFXCR1R2OH, whe re X = F or Cl; R1 = H or CH3; R2 = H, CH3, or C2H5 . In preliminary experiments, benzoyl peroxide was found to be effective for the addition reaction, but benzoates of alcohols were produced as byproducts whose boiling products were similar to the 1: 1 adducts. The gamma radioinduced addition reaction of 1,2,2-trichloro-1- fluoroethylene and 1,2-dichloro1,2-difluoroethylene gave mainly 1: 1 adducts in appreciahle yields. 1,1-Dichloro-2,2-difluoroethylene reacted with alcohols under the influence of gamma radiation to form telomers. The yields and physical properties of the 1: 1 adducts, the new halogeno alcohols, are tabulated. The trend in gross reactivity observed in the addition of alcohols to 1,2- dichloro-1,2-difluoroethylene is as follows: (CH3)2CHOH> CH3(CH2)2OH, CH3CH2OH> C H3OH. Chemical reactions were used to determine the direction of the additions of alpha -hydroxyalkyl radicaly formed to 1,2,2-trichloro1-fluoroethylene and 1,1-dichloro-2,2- difluoroethylene. The results confirm the general rule for the addition of radicals to the olefins, that is, that the radicals add to the sidemore » having less steric hindrance.« less