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Computational Theoretical Organic Chemistry pp 335–369Cite as

Triplet Oxiranes : Application of Quantum Mechanical Methods to the Study of the Reactions of Triplet Isomeric Oxiranes

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Part of the book series: NATO Advanced Study Institutes Series ((ASIC,volume 67))

Abstract

The thermal and photochemical reactions of simple oxiranes are reviewed. Molecular unrestricted Hartree-Fock calculations with geometry optimization have been carried out on eight triplet C3H6O isomers considered to be possible intermediates in the 0(3P) + propylene and in the Hg 6(3P1) sensitization of methyloxirane. The computed thermodynamic stabilities reveal that four of these species are available in the former while all eight are accessible in the latter reaction. The isomer CH(CH3)-CH2O (MO1) is more stable than OCH(CH3)- CH2 (MO2) giving a satisfactory explanation for the observation that propionaldehyde is the major carbonyl product in the O (3P) + propylene reaction. The energy surfaces E(θ1,θ2) for MO1 and MO2, and the energy hy-persurfaces E(θ1,θ2,θ3) for CH(CH3)-O-CH2 (MO3), acetone and propionaldehyde were generated and the surfaces analyzed for the location and relative energies of the critical points (minima, saddle points and maxima). The overall stereochemical finding was that MO1,MO2, and MO3 possess rather flexible structures. For acetone and propionaldehyde, the barriers to inversion at the carbonyl group are 2.7 and 4.2 kcal/mol, respectively.

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Authors and Affiliations

  1. Laboratoire de Chimie Physique Moléculaire, Faculté des Sciences CP 160, Université Libre de Bruxelles, 50 av. F.D. Roosevelt, B-1050, Brussels, Belgium

    George R. De Maré

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  1. George R. De Maré
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Editors and Affiliations

  1. Department of Chemistry, University of Toronto, Toronto, Ontario, Canada

    I. G. Csizmadia

  2. Centre de Mécanique Ondulatoire Appliquée, Centre National de la Recherche Scientifique, Paris, France

    R. Daudel

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© 1981 D. Reidel Publishing Company, Dordrecht, Holland

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De Maré, G.R. (1981). Triplet Oxiranes : Application of Quantum Mechanical Methods to the Study of the Reactions of Triplet Isomeric Oxiranes. In: Csizmadia, I.G., Daudel, R. (eds) Computational Theoretical Organic Chemistry. NATO Advanced Study Institutes Series, vol 67. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-8472-1_14

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  • DOI: https://doi.org/10.1007/978-94-009-8472-1_14

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  • Online ISBN: 978-94-009-8472-1

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