35737-67-8Relevant articles and documents
Chemical Activation Study of the Reactions of Methylene with Oxetan and 3,3-Dimethyloxetan
Frey, Henry M.,Pidgeon, Ivy M.
, p. 1237 - 1248 (1983)
Methylene (singlet) formed by the photolysis of ketene (313 nm) reacts with oxetan to yield 2-methyl- and 3-methyloxetans by insertion in the C-H bonds and probably also tetrahydrofuran.These products are formed chemically activated and undergo unimolecular decomposition unless collisionally stabilized.Using perfluoropropane as the bath gas, the results obtained with 2-methyloxetan have been interpreted using RRKM theory and a step-ladder model with a most probable step size of ca. 9 kJ mol-1.Using 206 nm radiation yields methylene with excess energy, some of which is still present when it reacts, and results in the production of 2-methyloxetan with an average lifetime approximately one-half that of the energised molecule produced when 313 nm radiation is used.Similarly methylene reacts with 3,3-dimethyloxetan to yield chemically activated 3-ethyl-3-methyloxetan and 2,3,3-trimethyloxetan.A third compound tentatively identified as 3,3-dimethyltetrahydrofuran is also formed.The decomposition of these 3 molecules has been followed and in the case of the ethylmethyloxetan the average energy transferred in collision with 3,3-dimethyloxetan has been found to be ca. 6.5 kJ mol-1.Some deductions can be made about the Arrhenius parameters for the thermal decomposition of the (as yet unreported) trimethyloxetan and the dimethyltetrahydrofuran.
