Catalysis of the ethanolysis of N-methyl-N-nitroso-p-toluenesulfonamide by alkali metal ions

Abstract

The goal of this study was to report on the catalytic effects by alkali-metal ions in the ethanolysis of N-methyl-N-nitroso-p-toluenesulfonamide (MNTS). We confirmed that the nucleophilic attack at the sulfur center was the only reaction pathway. The reactions of MNTS with metal ethoxides (MOEt) were discussed on basis of a kinetic scheme considering simultaneous reaction of free ethoxide and ion-paired ethoxide with the substrate. The trend for ion-paired ethoxide reactivity was clear and showed an increase on increasing the size of the ion (Cs+>K+>Na+>Li+). For evaluate the free ethoxide reactivity we performed additional experiments in the presence of the complexing agents 18-crown-6 ether (18-C-6) and 2,5,8,11,14-pentaoxapentadecane (glyme). The results obtained were discussed in terms of the interaction of the metal ions with the ground state and the transition state. © ARKAT-USA, Inc.