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)


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]


Ring Opening Difference Spectrum Formation Time Positive Peak Left Half 
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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

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