Photochemical Ring Openings are Complete in Picoseconds: A Time-Resolved UV Resonance Raman Study

  • P. J. Reid
  • S. J. Doig
  • R. A. Mathies
Conference paper
Part of the Springer Proceedings in Physics book series (SPPHY, volume 68)

Abstract

A classic electrocyclic ring-opening reaction is the photoconversion of 1,3-cyclohexadiene (CHD) to cis-hexatriene (cis-HT)[1]. Our time-resolved resonance Raman studies have shown that the timescale for cis-HT formation is 8 ± 1 ps[2]. To determine if the kinetics of CHD are representative of other photochemical ring-opening reactions, we have studied the photoconversions of 1,3,5-cyclooctatriene (COT) to octatetraene and of α-phellandrene (α-PHE) to 3,7-dimethyl-1,3,5-octatriene.[3] COT is known to photochemically ring open with a disrotatory motion of the methylene portion of the ring as opposed to the conrotatory ring opening of CHD[4]. α-PHE is a substituted 1,3-cyclohexadiene in which one of the carbons undergoing conrotatory rotation has a hydrogen substituted for an isopropyl group.[5]

Keywords

Cyclohexane Isopropyl Octatetraene Octatriene 

References

  1. 1.
    R.J. de Kock, NG. Minnard, E. Havinga: Rec. Trav. Chim. Pays-Bas 79, 922 (1960)CrossRefGoogle Scholar
  2. 2.
    P.J. Reid, S.J. Doig, R.A. Mathies: Chem. Phys. Lett. 136, 163 (1989)CrossRefADSGoogle Scholar
  3. 3.
    P.J. Reid, S.J. Doig, R.A. Mathies: J. Phys. Chem. 94, 8396 (1990)CrossRefGoogle Scholar
  4. 4.
    T. Goldfarb, L. Lindquist: J. Am. Chem. Soc. 89, 4588 (1967)CrossRefGoogle Scholar
  5. 5.
    J.E. Baldwin, S.M. Krueger: J. Am. Chem. Soc. 91, 6444 (1969)CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 1992

Authors and Affiliations

  • P. J. Reid
    • 1
  • S. J. Doig
    • 1
  • R. A. Mathies
    • 1
  1. 1.Department of ChemistryUniversity of CaliforniaBerkeleyUSA

Personalised recommendations