Competitive Unimolecular Decomposition in Chemically Activated Radical Systems. Propyl Rupture

Abstract

The study of the competitive unimolecular decomposition of chemically activated alkyl radicals is extended to cases of rupture of a propyl fragment vs a methyl or ethyl fragment. A study of the decomposition at room temperature of the octyl‐4, heptyl‐3, and 3‐methyl‐hexyl‐2 radicals, formed by addition of H atoms to trans‐octene‐4, trans‐heptene‐3, and 3‐methylhexene‐1, is reported. The value of D 0 °(n‐ Pr–H ) is deduced to be within −0.8 kcal of the value of D 0 °( Et–H ) . Comparison of the results are made with values obtained on a theoretical model for the absolute and relative rates; good agreement was found.