Photochemistry of 5-phenyl-1-pentene in the gas phase

Article abstract of DOI:10.1021/ja044504z

The photochemistry of the title compound has been studied in the gas phase using 254-nm irradiation. In addition to meta cycloadducts analogous to those observed in solution, population of S₁^vib in the gas phase gives several products, the relative amounts of which depend on quencher gas pressure but not on excitation wavelength. For example, in the absence of butane, the major photoproduct is compound 5. This product is formed by a [1,5] hydrogen shift in the primary photoproduct, compound 4. Compound 4 is an intramolecular meta cycloadduct that is generated in the gas phase with sufficient excess vibrational energy to undergo rearrangement unless quencher gas is present. Likewise, there is evidence that two other meta cycloadducts (2 and 3) are also formed with appreciable vibrational energy in the absence of a quencher gas. A unique intramolecular ortho cycloadduct is also formed from 1 but only within a narrow range of quencher gas pressures. This is a two-photon product, with the initial cycloadduct (11) ring opening to a cyclooctatriene (12) that photochemically closes to 6. The pressure dependence of this ortho cycloaddition may be due to a requirement for vibrational deactivation of 11 (Scheme 5) or a precursor species (Scheme 6). The overall chemistry is outlined in Scheme 7.