The Photochemistry of 2-Trifluoromethylnorbornene and 7-Trifluoromethylbicyclo[4.2.0]Oct-7-Ene. Definition of π,π* and π,R(3S) Reactivity in the Photochemistry of Substituted Norbornenes and Alkylcyclobutenes

Abstract

<p> 2-Trifluoromethylnorbornene has been synthesized from norbornene. The UV photoelectron spectra and optical UV absorption spectra of norbornene, 2-methylnorbornene and 2-trifluoromethylnorbornene have been studied, and indicate that the π,π* state is the lowest excited singlet state. Direct photolysis of 2-trifluoromethylnorbornene with 193 nm light yields 1-trifluoromethyl-2-norcarene (in 90% yield) by formal [1,3]-sigmatropic rearrangement. Chlorobenzene-sensitized photolysis affords the photoreduction products, exo-and endo-2-trifluoromethylnorbornane, decane isomers, and several products of higher molecular weight.</p> <p> By comparing the photochemistry of 2-trifluoromethylnorbornene to those previously reported for norbornene and 2-cyanonorbornene as well as on the basis of spectroscopic evidence, it is proposed that the π,π* state is the lowest energy excited singlet state in 2-trifluoromethylnorbornene. Trifluoromethyl substitution has the effect of significantly raising the energy of the π,R(3s) Rydberg state in simple alkenes without altering the high energy or the localized character of the π,π* state.</p> <p> 7-Trifluoromethylbicyclo[4.2.0]oct-7-ene (86) was synthesized from bicyclo[4.2.0]oct-7-ene (84). By comparing the UV photoelectron spectroscopy and optical spectra of 86, 84, 97, it is concluded that the π,π* state is the lowest excited singlet state in 86. Direct photolysis with 193 nm light yields three diene isomers derived from formal electrocyclic π,π* ring opening, and cyclohexene derived from fragmentation. Comparison of spectroscopic and photochemical results for this compound to those of bicyclo[4.2.0]oct-7-ene (84) and 7-methylbicyclo[4.2.0]oct-7-ene (97) indicate that ring-opening is non stereospecific and arises largely from the π,π* singlet state. Fragmentation arises largely from the Rydberg excited state.</p>