The aminolyses of anilinothioethers $(C_6H_5N(CH_3)CH_2SC_6H_4Z)$ in acetonitrile with benzylamines $(XC_6H_4CH_2NH_2)$ have been investigated. The rates are much lower in acetonitrile than in methanol (with aniline). The Bronsted ${eta}_X$ values are similar but ${eta}_Z$ values are smaller compared to those for the reactions in MeOH with anilines. The large negative ${ ho}_{XZ}({cong}-0.8$, after correction for fall-off) value is interpreted to indicate a frontside attack $S_N2$ mechanism, in which the two oppositely changed reaction centers in the TS, $-N^{{delta}+}{cdots}S^{{delta}-}-$, are in close vicinity increasing the interaction between nucleophile and leaving group. The inverse secondary kinetic isotope effects ($k_H/k_D$ < 1.0) are observed with deuterated benzylamines $(XC_6H_4CH_2ND_2)$.