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Photochemistry of 1-allyl-4-aryltetrazolones in solution; structural effects on photoproduct selectivity
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Abstract(s)
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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Citation
Ismael, Amin; Serpa, Carlos; Cristiano, M. Lurdes S. Photochemistry of 1-allyl-4-aryltetrazolones in solution; structural effects on photoproduct selectivity, Photochemical & Photobiological Sciences, 12, 2, 272-283, 2013.
Publisher
Royal Society of Chemistry