The reactions of alkyl radicals. Part XIII. The additions of methyl, isopropyl, and t-butyl radicals to propyne and the isomerisation of alkenyl radicals

Abstract

The above addition reactions have been studied by the “aldehyde method,” and found to have the following Arrhenius parameters: [graphic omitted]

The system for the addition of t-butyl radicals to propyne was complex and yielded only approximate Arrhenius parameters. Additions of all three radicals occurred predominantly (>90%) at the terminal carbon atom in propyne. Isomerisation of the adduct alkenyl radicals was observed in the additions of isopropyl and t-butyl to propyne. Arrhenius parameters for the isomerisations of the radicals formed by the addition of isopropyl and t-butyl radicals to actylene and propyne have been derived by the application of the Rice–Ramsperger–Kassel theory of unimolecular reactions.