1967 年 25 巻 10 号 p. 908-913
1-Chloropropane, 1, 1-dichloropropane, 1, 1, 1-trichloropropane, neohexane, and t-butyl chloride were photochlorinated at 40°C in the presence of 2, 2-dichloropro-pane, and relative amounts of the chlorinated products determined by g.l.c. The reactivities of C-H bonds toward hydrogen abstraction by the chlorine atom were compared with that of a C-H bond in 2, 2-dichloropropane. A linear free energy relationship was found to exist between the reactivities of methyl hydrogens and the Taft's σ constants for the substituents (CH3, CH2Cl, CHCl2, CCl3, CH2CMe3, CH2CH2Cl, CH2CHCl2, CH2CCl3, CMe3, CMe2Cl, CMeCl2). p=-0.85. Results show that the reactivities of methyl hydrogens are mainly affected by the polar nature of the substituents, and resonance stabilization of the incipient radical by hyperconjugations is of minor importance.