Eliminations from (E)-O-arylbenzaldehyde oximes promoted by hydroxide in 60% aq. Dimethyl sulphoxide. Mechanism and transition-state characteristics of nitrile-forming eliminations

Abstract

Reactions of the (E)-O-arylbenzaldehyde oximes (1; Ar = 2,4-dinitrophenyl), (2; Ar =p-nitrophenyl), and (3; Ar = phenyl) with OH– in 60% aq. DMSO have been investigated. The eliminations are quantitative, producing only benzonitriles and aryloxides. The observation of second-order kinetics, k2OD–/k2OH–= 1.15–1.84, and βlg=–0.59 is consistent with an E2 mechanism. The Hammett ρ and k2OD–/k2OH– values increased with poorer leaving groups. For a given substrate the k2OD–/k2OH– value remained (within experimental error) roughly constant, in spite of changes in the β-aryl substituents. These changes in transition state parameters can be interpreted in terms of the differing nitrite-forming transition states involved.