PHOTOCHEMICAL ADDITION OF 2,2,2-TRIFLUOROETHANOL TO BENZONITRILE AND P-, M-, AND O-METHYLBENZONITRILE

doi:10.1021/JA982712J

Paper

PHOTOCHEMICAL ADDITION OF 2,2,2-TRIFLUOROETHANOL TO BENZONITRILE AND P-, M-, AND O-METHYLBENZONITRILE

Published Dec 1, 1998 · J. Foster, A. Pincock, J. Pincock

Journal of the American Chemical Society

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10

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Abstract

Irradiation of benzonitrile in 2,2,2-trifluoroethanol (TFE) with 254-nm light from low-pressure mercury lamps results in the formation of four addition products, the stereoisomers of 6-cyano-2-(2,2,2-trifluroethoxy)bicyclo[3.1.0]hex-3-ene, 22−25. The proposed mechanism begins by formation of the 6-cyanobicyclo[3.1.0]hex-3-en-2,6-diyl biradical/zwitterion from S1 followed by both endo and exo protonation by TFE at C6. Deuterium labeling demonstrated that the resulting 6-cyanobicyclo[3.1.0]hex-3-en-2-yl cation underwent a rapid degenerate 1,4-sigmatropic rearrangement with inversion of configuration at the migrating carbon before being trapped by the nucleophilic solvent. Irradiation of p- and m-methylbenzonitrile in the same way gave six major addition products. Three of them, 32, 33, and 35 were 6-cyano-2-(2,2,2-trifluoroethoxy)-4-methylbicyclo[3.1.0]hex-3-enes and the other three, 32, 33, and 35, were 6-cyano-2-(2,2,2-trifluoroethoxy)-2-methylbicyclo[3.1.0]hex-3-enes. The proposed mechanism is again by T...

Study Snapshot

Irradiation of benzonitrile with 2,2,2-trifluoroethanol produces six major addition products, including 6-cyano-2-(2,2,2-trifluoroethoxy)-4-methylbicyclo[3.1.0]hex-3-enes and 6-cyano-2-(2,2,2-

PopulationOlder adults (50-71 years)

Sample size24

MethodsObservational

OutcomesBody Mass Index projections

ResultsSocial networks mitigate obesity in older groups.

PHOTOCHEMICAL ADDITION OF 2,2,2-TRIFLUOROETHANOL TO BENZONITRILE AND P-, M-, AND O-METHYLBENZONITRILE

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