Sabrina Antonello and, Flavio Maran
Jun 2, 1998
Citations
0
Influential Citations
29
Citations
Journal
Journal of the American Chemical Society
Abstract
The voltammetric reduction of a series of phenyl-substituted 4-benzoyloxy-1-methylcyclohexyl bromides has been investigated in DMF. The reduction leads to the cleavage of the C−Br bond. On a thermodynamic ground, the direct reduction of the tertiary C−Br function is easier than that of the selected benzoates by at least 0.5 V. However, since the direct reduction of bromides is affected by a large activation overpotential, the electron is first located in the benzoate moiety. The rate constant for the following exergonic intramolecular dissociative electron transfer was determined by kinetic analysis of the cyclic voltammetry curves. The intermolecular rate constants for the reaction between the radical anions of methyl benzoates and 4-tert-butyl-1-methylcyclohexyl bromide were also determined and found to correlate very well with related literature data pertaining to tert-butyl bromide. The intramolecular rate constants were found to be more sensitive to variation of driving force than the corresponding i...