OXIDATION OF AMINES WITH SULFONYL PEROXIDES .5. BASE-PROMOTED, IMINE-FORMING ELIMINATIONS IN N-BENZYL-O-ARYLSULFONYLHYDROXYLAMINES PRODUCED FROM BENZYLAMINES AND SULFONYL PEROXIDES

The reactions of substituted benzylamines with substituted arylsulfonyl peroxides give a series of O-sulfonylhydroxylamines, XC6H4CH2NHOSO2C6H4Y, which undergo base-induced elimination to the imine. By suitable choice of amine and peroxide, substituent effects on the benzylic position and on the leaving group were determined, kinetic deuterium isotope effects were measured, and activation parameters were obtained for imine-forming elimination. The results are best interpreted in terms of an elimination transition state in which leaving group loss is well ahead of benzylic proton removal. The present results are compared with other imine-forming eliminations and with olefin-forming eliminations. The respective transition states are well-accommodated by utilizing a More O'Ferrall-Jencks diagram to depict bonding changes from one system to another. © 1979, American Chemical Society. All rights reserved.