Chemically activated 1,1-dimethylcyclopropane from photolysis of isobutene–neopentane–diazomethane–oxygen mixtures

A study of the structural isomerization rate of chemically activated 1,1-dimethylcyclopropane from singlet methylene addition to the double bond of isobutene is reported. Singlet methylenes were produced from the 4358- and 3660-Å photolysis of diazomethane in the presence of added oxygen. Theoretical rates calculated via RRKM theory are in excellent agreement with experiment for calculations utilizing activated complex structures and critical energies consistent with known thermal Arrhenius parameters, and excitation energies consistent with previous determinations of ΔH(CH₂) + E*(CH₂) = 116.1 and 112.6 kcal/mole for diazomethane photolyses at 3660 and 4358 Å, respectively.