Proton transfer reactions between ortho-methyl substituted derivatives of 4-nitrophenylphenylcyanomethane and nitrogen bases in acetonitrile solvent
Equilibrium constants, rate constants, primary deuterium isotope effects, and activation parameters have been measured for the proton transfer reactions in acetonitrile solvent of 4-nitrophenylphenylcyanomethane and 2-methyl-4-nitrophenylphenyl-cyanomethane with tetramethylguanidine base and for the reactions of 2-methyl-4-nitrophenylphenylcyanomethane and 2,6-di-methyl-4-nitrophenylphenylcyanomethane with 1,5-diazabicyclo[5.4.0]undec-7-ene base. Introduction of the ortho-methyl groups in the substrate molecule caused significant reductions in the equilibrium and rate constants. The expected rise in the kinetic primary deuterium isotope effect was not observed when the first ortho-methyl group was introduced, but a 20% increase did accompany the introduction of the second ortho-methyl group. Enthalpy of activation measurements indicated that there was no increase in the proton tunnelling contribution to the isotope effect when the amount of steric hindrance is increased with ortho-methyl groups.