Free Radical Substitution in Aliphatic Compounds. Part IV. The Reaction of Trichloromethyl Radicals with Propane, n‐Butane and Iso‐Butane

Abstract

AbstractMixtures of bromotrichloromethane and the alkanes at circa 60 mm pressure have been irradiated in a Pyrex vessel with light from a medium pressure mercury lamp. The products, which consist solely of chloroform and monobromoalkanes, have been analysed. The reaction has been shown to be a chain process involving attack on the alkane by trichloromethyl radicals which abstract hydrogen atoms from the primary, secondary and tertiary positions in the order 1 : 80 : 2,300 at 190°.kk2/kp2 = 2.68 ± 1.48 exp (3.08 ± 0.46 k. cal/RT); kt2/k82 ≈︁ 5.25 × exp (5.5 k. cal/RT).