31734-55-1Relevant academic research and scientific papers
Gas-Phase Kinetics of Pyrolysis of 3,3-Dimethylcyclopropene and Its 1-Trimethylsilyl Derivative The Effect of Silyl Substitution on Cyclopropene Isomerisation
Walsh, Robin,Untiedt, Sven,Stohlmeier, Michael,Meijere, Armin de
, p. 637 - 642 (2007/10/02)
The gas-phase pyrolysis of 3,3-dimethylcyclopropene (1) in the temperature range of 185-225 deg C gives 3-methyl-1-butyne (2) (91percent) and isoprene (3) (9percent).The gas-phase pyrolysis of 3,3-dimethyl-1-trimethylsilylcyclopropene (4) in the temperature range of 195-235 deg C gives 3-methyl-1-trimethylsilyl-1-butyne (5) (99percent) and trans-3-methyl-1-trimethylsilyl-1,3-butadiene (6) (1percent).Both rearrangements are homogeneous, first-order, unimolecular reactions with the following pressure-independent Arrhenius parameters. Rather surprisingly, the trimethylsilyl group deactivates cyclopropene with respect to its isomerisation.Possible mechanisms are discussed. - Keywords: Cyclopropene, 3,3-dimethyl-1-trimethylsilyl-/ Cyclopropene, isomerisation/ Gas-phase kinetics/ Ring-opening of 3,3-dimethylcyclopropene/ Vinylcarbene intermediates
