Kinetics and equilibrium constants for reactions of alpha-phenyl-substituted cyclopropylcarbinyl radicals

Laser-flash photolysis methods were used to determine Arrhenius functions f or cyclizations of the 4.4-diphenyl-3-butenyl (2) and trans-4-phenyl-3-bute nyl (5) radicals to the 1,1-diphenylcyclopropylcarbinyl (1) and 1-phenylcyc lopropylcarbinyl (4) radicals. respectively. At 20 degrees C, the cyclizati on rate constants are 1.7 x 10(7) and 5.4 x 10(6) s(-1). Equilibrium consta nts for the two processes were estimated and evaluated with thermochemical data and via computational methods, and Arrhenius functions for the ring-op ening reactions of the cyclopropylcarbinyl radicals were calculated, The cy clization reactions of 2 and 5 are strongly enthalpy controlled. Production of radicals 1 and 2 from the corresponding tert-butylperoxy esters in the presence of Et3SnH gave diphenylcyclopropylmethane and 1.1-diphenyl-1-buten e from H-atom trapping of radicals 1 and 2 and 4-phenyl-1,2-dihydronaphthal ene which derives from the product radical formed by addition of the radica l moiety in 2 to the cis-phenyl group. Rate constants for the latter cycliz ation of 2 and for reactions of radicals 1 and 2 with Et3SnH were obtained from the indirect kinetic studies.