5581-55-5Relevant articles and documents
β-deuterium Isotope Effects on Amine Basicity, Inductive and Stereochemical
Perrin, Charles L.,Ohta, Brian K.,Kuperman, Joshua
, p. 15008 - 15009 (2007/10/03)
Secondary β deuterium isotope effects on acidity constants of ammonium ions are measured using a remarkably precise NMR titration method. Deuteration is found to increase the basicity of methylamine, dimethylamine, benzylamine, and N,N-dimethylaniline. The effect is attributed to a lowered zero-point energy of a CH bond adjacent to an amine nitrogen. The method permits a determination of the stereochemical dependence of the isotope effect in a locked piperidine, and it is found that deuteration is more effective when antiperiplanar to a lone pair. The values are consistent with a cos2 dependence on dihedral angle, with no detectable angle-independent inductive effect. Copyright