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    Engineering Reactions in Crystalline Solids:  Predicting Photochemical Decarbonylation from Calculated Thermochemical Parameters
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    Department of Chemistry, California State University Dominguez Hills, Carson, California 90747, and Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569
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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2002, 67, 11, 3749–3754
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    https://doi.org/10.1021/jo016371v
    Published April 26, 2002
    Copyright © 2002 American Chemical Society
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    Abstract

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    A detailed thermochemical analysis of the α-cleavage and decarbonylation reactions of acetone and several ketodiesters was carried out with the B3LYP/6-31G* density functional method. The heats of formation of several ground-state ketones and radicals were calculated at 298 K to determine bond dissociation energies (BDE) and radical stabilization energies (RSE) as a function of substituents. Results show that the radical-stabilizing abilities of the ketone substituents play a very important role on the thermodynamics of the α-cleavage and decarbonylation steps. An excellent correlation between calculated values and previous experimental observations suggests that photochemical α-cleavage and decarbonylation in crystals should be predictable from knowledge of excitation energies and the RSE of the substituent.

    Copyright © 2002 American Chemical Society

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    †

     California State University Dominguez Hills.

    ‡

     University of California, Los Angeles.

    *

     To whom correspondence should be addressed. E-mail:  (L.M.C.) [email protected].

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    Stereoscopic views and X-ray data tables for compound 5, Cartesian coordinates, energies (HF), and zero-point vibrational energies (ZPE) for all ketodiesters and radicals in this study. This material is available free of charge via the Internet at http://pubs.acs.org.

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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2002, 67, 11, 3749–3754
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jo016371v
    Published April 26, 2002
    Copyright © 2002 American Chemical Society
    Request reuse permissions

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