Studies of radiation-produced radicals and radical ions. Progress report, September 1, 1990--October 15, 1991
The radiolytic oxidation of anti-5-methylbicyclo[2.1.0]pentane gives the 1-methylcyclopentene radical cation as the sole rearrangement product H migration whereas oxidation of its syn isomer results in the highly selective formation of the 3-methylcyclopentene radical cation by methyl group migration. Since exactly the same stereoselectivity of olefin formation was observed in corresponding PET (photosensitized electron transfer) studies in the liquid phase, it is concluded that the rearrangement in this case also occurs through the intermediacy of radical cations. Clearly, the radical cation rearrangement must occur very rapidly (10{sup {minus}8}--10{sup {minus}9}s) under liquid-phase conditions at room temperature to compete with back electron transfer, and therefore the hydrogen (or methyl) migration is a fast process under these conditions. An intramolecular cycloaddition reaction was demonstrated in the radical cation rearrangement of 4-vinylcyclohexene to bicyclo[3.2.1]oct-2-ene. ESR studies show that the radiolytic oxidation of quadricyclane in Freon matrices under conditions of high substrate dilution leads to the bicyclo[3.2.0]hepta-2,6-diene radical cation as well as the previously reported norbornadiene radical cation, the former species predominating at sufficiently low concentrations.
- Research Organization:
- Tennessee Univ., Knoxville, TN (United States). Dept. of Chemistry
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG05-88ER13852
- OSTI ID:
- 10138895
- Report Number(s):
- DOE/ER/13852-192; ON: DE92011807
- Resource Relation:
- Other Information: PBD: [1991]
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
HYDROCARBONS
RADIOLYSIS
OXIDATION
PROGRESS REPORT
ELECTRON SPIN RESONANCE
RADICALS
CATIONS
PHOTOCHEMICAL REACTIONS
ELECTRON TRANSFER
400600
400500
400201
RADIATION CHEMISTRY
PHOTOCHEMISTRY
CHEMICAL AND PHYSICOCHEMICAL PROPERTIES