The effect of steric crowding on an E2 transition state

Abstract

The mechanism of the reaction of 9-(4-substituted benzyl)fluorene-9-trimethylammonium ions with ethoxide is a normal E2 process. The magnitude of the primary hydrogen–deuterium isotope effect at 60 °C increased with increasing electron-donating ability of the 4-substituent, i.e., 4.15, 5.10, 5.34, 5.65, 5.75, and 5.91 for the 4-CF3, 4-Br, 4-Cl, 4-H, 4-CH3, and 4-OCH3 substituents, respectively. The magnitude of the nitrogen isotope effect at 70 °C decreased with increased electron-donating power of the 4-substituent, i.e., [(k14/k15)–1]100 = 1.24, 0.95, 0.92, 0.91, and 0.80 for the 4-CF3, 4-F, 4-H, 4-CH3, and 4-OCH3 substituents, respectively. A small Hammett ρ value of +1.33 was observed for the reaction. It is concluded that the reaction proceeds via a transition state where the proton is more than one-half transferred to base. It is further concluded that for a reaction in which the 4-substituents decrease the rate, both carbon–hydrogen and carbon–nitrogen bond rupture is more advanced in the transition state. This variance with Hammond's postulate is discussed in the light of steric crowding at the transition state.