- Thermal isomerisations, XXIV. Gas phase kinetics of the pyrolysis of some 3,3-dimethyl-1-alkyl-cyclopropenes: Some surprising substituent activation effects and the intramolecular trapping of vinylidene intermediates
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The gas phase pyrolyses of four 3,3-dimethyl-1-alkylcyclopropenes were studied for which the 1-alkyl substituents are ethyl- (6), isopropyl- (7), 1′-butyl- (8) and 1′-isoamyl- (9). Rate data over a 50°C temperature range were obtained and Arrhenius parameters are reported both for overall reactions and individual pathways for all compounds. Tests confirm all reactions to be unimolecular and homogeneous. For 8 and 9, noteworthy products are cyclopentenes, whose presence demonstrates the involvement of vinylidene intermediates. The substantial product yields of 2,4-alkadienes together with dramatic rate enhancement effects of these 1-alkyl substituents (relative to 1-methyl) are explained by the involvement of vinylcarbene intermediates in this pathway. Minor, transient products from 6, 8 and 9 are probably isomeric cyclopropenes. This suggests further pathways for vinylidene intermediates, whose reactivity pattern is briefly reviewed. VCH Verlagsgesellschaft mbH, 1996.
- Hopf, Henning,Plagens, Andreas,Walsh, Robin
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p. 825 - 835
(2007/10/03)
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- New Evidence for the Involvement of Alkylidene Carbenes in the Thermal Isomerisation of Cyclopropenes
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The detection of 1-(2'-propyl)-3-methylcyclopentene amongst the products of gas-phase thermal isomerisation of 1-(1'-butyl)-3,3-dimethylcyclopropene provides unambigous evidence for the intermediacy of an alkylidene carbene.
- Hopf, H.,Plagens, A.,Walsh, R.
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p. 1467 - 1468
(2007/10/02)
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