Theoretical Studies on the Aminolysis of Ester: Effects of the Catalysis and Substituent to the Reaction of Methyl Indole-3-acetate with Ammonia

摘要

A comprehensive exploration of the aminolysis mechanism for methyl indole-3-acetate with ammonia is carried out by employing the B3LYP/6-311++G(d,p),M06-2X/6-311++G(d,p) and MP2/6-311 ++G(d,p)//M06-2X/6-311++G(d,p) levels.Two alterative reactionchannels of the concerted and addition/elimination stepwise processes including the uncatalyzed,base-catalyzed reactions are taken into consideration.Subsequently,the substituent effects and solvent effects in methanol are also evaluated at the M06-2X/6-311++G(d,p) level.The calculated results indicate that the calculated values of M06-2X level are quite close to those of MP2,the stepwise pathway has more advantages to the concerted one for all of the reaction processes and the catalyst facilitates the proton migration and decreases the energy barriers as well.It is shown that the most preferred mechanism is the based-catalyzed stepwise process,the substituent of NH2 group slightly accelerates all the aminolysis reaction processes,and the solvent effect does not remarkably change the mechanism of the reaction.