Journal of the American Chemical Society p. 2394 - 2400 (1986)
Update date:2022-08-05
Topics:
Mitsuhashi Tsutomu
Decompositions of (p-nitrophenyl)azo-tert-cumylmalonitrile in polar solvents were found to proceed via the heterolysis of a carbon-carbon bond to generate tert-cumyl cation and the conjugate base of (p-nitrophenyl)hydrazonomalononitrile.The major products arising from tert-cumyl cation are as follows: tert-cumyl methyl ether in methanol, the N-cumylpyridinium hydrazonide in pyridine, and α-methylstyrene in Me2SO and in DMF.The reactions in MeCN and in acetone afford a rearranged product, N-(tert-cumyl)(p-nitrophenyl)hydrazonomalononitrile, which gradually undergoes heterolysis as well.Decompositions of the azo compound and the rearragend product are faster in Me2SO than in methanol, being in conflict with the usual trend of solvent-ionizing power.This phenomenon is explained in terms of extensive charge dispersal of the leaving group anion wich prevents hydrogen bonding with a protic solvent molecule.It is pointed out that the behavior of the conjugate base of (p-nitrophenyl)hydrazonomalononitrile as the leaving group anion is closely connected with the function of FCCP (the p-CF3O derivative of the hydrazone) as one of the best uncouplers of phosphorylation in mitochondrial systems.
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