Selective chlorination of alkanes and hydrogenation of chlorofluoroethane with high G-values in the radiolysis of their liquid mixture: high resolution NMR study

It was found that γradiolysis of n-alkanes (Cn = 6-8) and cyclohexane in CFCl2CF2Cl and CF3CCl3 in the liquid phase produces corresponding monochlorinated alkanes with a high G-values (≥600). This chlorination occurred selectively at the positions C2 and C3, and the yield of 1-chlorohexane was <4% of the sum of the former. The selective hydrogenation of CFCl2CF2Cl was also found with a yield as high as that of the chlorination of the alkanes. The role of positive charge transfer from the solvent to the alkane with a high G-value, and that of the bond energy difference between the primary and secondary C-H bonds in the selective chlorination and hydrogenation are suggested. (author)