Reactivity of sulfonic acid group and estimation of its substituent-effect in T-for-H exchange reaction

Abstract

The hydrogen-isotope exchange reaction (T-for-H exchange reaction) between each solid material having two different kinds of functional groups and HTO vapor has been observed at several temperatures. Solid materials used were monosubstituted aminobenzenes. The rate constant (k) for each functional group was obtained by applying both the A"-McKay plot and the date obtained. Comparing these k values quantitatively leads to the followings: (1) the A"-McKay plot is useful in obtaining the reactivity of the compounds having two different kinds of functional groups; (2) as to m-aminobenzenesulfonic acid, the reactivity of the SO3H group is about 6.6-8 times larger than that of the NH2 group, and the temperature dependence of the reactivity of the SO3H group is also larger than the dependence of that of the NH2 one; (3) the reactivity of the NH2 group of some kinds of monosubstituted aminobenzenes may follow the Hammett rule; (4) the substituent constant (s) of SO3H group is estimated as follows: sm is 0.38, and sp is 0.64; (5) the substituent-effect of SO3H group is generally larger than that of other substituents; and (6) the subsutituent-effect unknown can be estimated by applying both the Hammett rule and A"-McKay plot.