87494-67-5Relevant academic research and scientific papers
2-Methyl Substituent Effects in the Antihomoaromatic Cyclopropinden-1-yl Cation
Friedrich, Edwin C.,Lucca, George De
, p. 4563 - 4567 (2007/10/02)
The rates and products of hydrolysis of the endo- and exo-2-methylcyclopropinden-1-yl 3,5-dinitrobenzoates in 80percent aqueous acetone have been determined.These are compared with similar data for the corresponding unsubstituted esters and for the 1-methyl-substituted and unsubstituted endo- and exo-2-bicyclohexyl 3,5-dinitrobenzoate model systems.This was done in connection with reports that toward acid-catalyzed epimerization in 50percent aqueous dioxane at 80 deg C 2-methyl substitution caused a 250-fold rate deceleration in the endo-cyclopropinden-1-ol system.For the endo 3,5-dinitrobenzoates the 2-methyl substituent did produce a rate decrease; however, this was only by a factor of about 1.2 at 80 deg C.In the 2-bicyclohexyl model system, the corresponding 1-methyl substitution caused approximately a 2-fold rate increase.
