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The effects of H-bonding and sterics on the photoreactivity of a trimethyl butyrophenone derivative

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Abstract

The irradiation of ester 1 in methanol and chloroform does not yield any photoproducts, whereas the photolysis of 1 in dry argon-saturated benzene produces cyclobutanol 4, which is converted to lactone 5 by the addition of HCl. Laser-flash photolysis of ester 1 demonstrates that 1 undergoes intramolecular H-atom abstraction to form the biradical 2 (λmax ~ 310 nm, δ = 200 ns, benzene), which intersystem crosses to photoenols, Z- 3 (λmax ~ 380 nm, δ = 30–60 µs, benzene) and E- 3 (λmax ~ 380 nm, δ = 11 ms, benzene). Density functional theory calculations were performed to support the proposed mechanism for forming cyclobutanol 4 and to explain how steric demand facilitates photoenol E- 3 to form cyclobutanol 4 rather than lactone 5.

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Authors and Affiliations

  1. Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221, USA

    Qian Li, Jagadis Sankaranarayanan, Michael Hawk, Vivian T. Tran, Jessica L. Brown & Anna D. Gudmundsdottir

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  1. Qian Li
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  2. Jagadis Sankaranarayanan
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  3. Michael Hawk
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  4. Vivian T. Tran
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  6. Anna D. Gudmundsdottir
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Correspondence to Anna D. Gudmundsdottir.

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† Electronic supplementary information (ESI) available. See DOI: 10.1039/c2pp05330f

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Li, Q., Sankaranarayanan, J., Hawk, M. et al. The effects of H-bonding and sterics on the photoreactivity of a trimethyl butyrophenone derivative. Photochem Photobiol Sci 11, 744–751 (2012). https://doi.org/10.1039/c2pp05330f

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  • DOI: https://doi.org/10.1039/c2pp05330f

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