Ambident reactivities of methylhydrazines

Article abstract of DOI:10.1002/anie.201107315

Kinetics versus thermodynamics: Methyl groups increase the nucleophilic reactivity of the substituted position of hydrazines and reduce the nucleophilicity of the adjacent nitrogen center. As a result, the tertiary nitrogen atom of 1,1-dimethylhydrazine is 3000 times more reactive than the NH₂ group, but under thermodynamic control substitution of an NH ₂ proton occurs (see picture). Copyright