Kinetics of intramolecular and intermolecular ...
|Title||Kinetics of intramolecular and intermolecular reactions of benzylchlorocarbene|
|Author(s)||Michael T. H. Liu, R. G. Chapman, R. Bonneau|
|Journal||Journal of Photochemistry and Photobiology A-Chemistry|
|Abstract||Photolysis of 3-chloro-3-benzyldiazirine in tetramethylethylene gives E- and Z-beta-chlorostyrenes and cyclopropane. Relative rate studies show that the styrenes to cyclopropane ratio increases with increasing diazirine concentration. This permits the determination of the ratio k(D)/k(i) = 8 where k(D) is the rate constant for the reaction of carbene with diazirine and k(i) is the rate constant for the 1,2-hydrogen atom shift of carbene. Laser flash photolysis yields the first absolute rate constant for the reaction of a chlorocarbene with diazirine and a value of 7.7 for k(D)/k(i).|
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