THE CONVERSION OF META- AND PARA-SUBSTITUTED BENZALDOXIME ARENESULFONATES TO NITRILES

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Abstract
The meta- and para-substituted syn-benzaldoxime arenesulfonates were prepared from the reaction between the sodium salt of the oxime and the acid chloride in absolute ether. These oxime esters reacted in aqueous alcohol readily to yield the corresponding nitriles exclusively. The reaction rates can be correlated by a Hammett plot with a slope of −0.77. Several para-substituents tended to deviate from the line. Isotope study gives a kH/kD ratio of 4.51. The rate was found to be sensitive to the change in the ionizing power of the solvent, and to the change in the strength of the esterifying acid. The addition of lithium perchlorate gives rise to a normal salt effect. Sodium acetate brings about a basic elimination having a Hammett p value of + 0.44. A mechanism is proposed in the light of these results.