METHYL SUBSTITUENT EFFECTS UPON THE CHEMISTRY OF 2-BICYCLO[4.1.0]HEPTYL 3,5-DINITROBENZOATES

The rates and products of kinetic control in hydrolyses of the unsubstituted and 2-, 6-, and anti-7-methyl-substituted 2-bicyclo[4.1.0]heptyl 3,5-dinitrobenzoates in 80% aqueous acetone have been determined. These are compared with similar data for the 1-methyl-substituted 3,5-dinitrobenzoates reported by Wiberg and Chen. Also, they are compared with the results of our previously reported perchloric acid catalyzed alcohol acetolysis studies for the same systems where the products of thermodynamic control and the percentages of cyclo-propylcarbinyl-cyclopropylcarbinyl cation rearrangement occurring prior to their formation were investigated. Several important conclusions regarding the detailed reaction pathway for cyclopropylcarbinyl-cyclopropylcarbinyl cation rearrangement in the 2-bicyclo[4.1.0]heptyl system have been derived from these comparisons. © 1979, American Chemical Society. All rights reserved.