Insight into the hard-soft acid-base properties of differently substituted phenylhydrazines in reactions with dimethyl carbonate

Following the preliminary studies on the reactivity of the ambident nucleophile phenylhydrazine with dimethyl carbonate, investigations involving para-substituted phenylhydrazines were carried out in order to probe differences in the reactivity within this class of nucleophile. Phenylhydrazines substituted by electron withdrawing or donating substituents showed an increase in reactivity of the phenylhydrazine toward dimethyl carbonate. Under the basic conditions used, all phenylhydrazines displayed hard nucleophilicity, signifying that para-substitution on the phenyl ring has little effect on the hard-soft behavior of this class of nucleophile. This conclusion fits well within the results previously obtained using other para-substituted nucleophiles, i.e., phenols.