Photochemistry of alkenes in solution

P. J. Kropp
1970 Pure and Applied Chemistry  
The direct and sensitized photochemical behaviour of cyclic and acyclic olefins is compared. Under either set of conditions cyclo-hexenes and -heptenes undergo photoprotonation in hydroxylic media, perhaps via a trans intermediate. By contrast acyclic, exocyclic, and larger-ring cyclic olefins fail to undergo photoprotonation on either direct or sensitized irradiation. However, both cyclohexenes and cycloheptenes, as well as larger-ring cyclic and acyclic olefins, undergo slow isomerization to
more » ... ositional and skeletal isomers on direct irradiation in either protic or aprotic media. Unique behaviour has been observed for tetraalkyl-substituted olefins, which exhibit behaviour on direct irradiation in alcoholic solvents suggesting the intervention of a cation radical intermediate. Mechanistic implications of these various types of photochemical behaviour are discussed.
doi:10.1351/pac197024030585 fatcat:jyvijaoecvfjjmqvxldpzku3hq