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Photochemistry of 1-allyl-4-aryltetrazolones in solution; structural effects on photoproduct selectivity

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Abstract

The photochemistry of tetrazolones derived from the carbocyclic allylic alcohols cyclohex-2-enol and 3-methylcyclohex-2-enol and from the natural terpene alcohol nerol was investigated in solution with the aim of assessing the effect of solvent and of structural constraints imposed by bulky allylic moieties on photoproduct selectivity and stability. Photolysis of tetrazolones derived from nerol and cyclohex-2-enol afforded the corresponding pyrimidinones as major products through a pathway that appears to be similar to that proposed for other 1-allyl-4-phenyl-1,4-dihydro-5H-tetrazol-5-ones derived from acyclic and unhindered allylic alcohols previously investigated but photolysis of the tetrazolone derived from the bulkier 3–methylcyclohex-2-enol 4c leads to formation of a benzimidazolone, indicating that, in this case, cyclization of the biradical formed upon extrusion of N2 involves the phenyl substituent and not the allylic moiety. Theoretical calculations (DFT(B3LYP)/3-21G*) were conducted to support the interpretation of the experimental results and mechanistic proposals. Laser flash photolysis experiments were conducted with the aim of clarifying the nature of the intermediate involved in the primary photocleavage process.

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Authors and Affiliations

  1. CCMAR and Department of Chemistry and Pharmacy, F.C.T., University of Algarve, P-8005-039, Faro, Portugal

    Amin Ismael & M. Lurdes S. Cristiano

  2. Department of Chemistry, University of Coimbra, P-3004-535, Coimbra, Portugal

    Carlos Serpa

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  1. Amin Ismael
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  2. Carlos Serpa
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Correspondence to M. Lurdes S. Cristiano.

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Electronic supplementary information (ESI) available. See DOI: 10.1039/c2pp25210d

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Ismael, A., Serpa, C. & Cristiano, M.L.S. Photochemistry of 1-allyl-4-aryltetrazolones in solution; structural effects on photoproduct selectivity. Photochem Photobiol Sci 12, 272–283 (2013). https://doi.org/10.1039/c2pp25210d

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