A theoretical study of hemiacetal formation from the reaction of methanol with derivatives of CX3CHO (X = H, F, Cl, Br and I)

Abstract

A theoretical study of the hemiacetal formation reaction between methanol and CX3CHO (X = H, F, Cl, Br, and I)has been carried out using density functional theory and Becke, three-parameter, Lee–Yang–Parr/6-311++G(d,p)computational methods. The stationary points of the reaction between the isolated molecules and the reactioncatalyzed by an additional methanol molecule have been characterized. Because the final products present a stereo-genic center, the potential autocatalysis of the reaction has been examined and also the possibility of spontaneousgeneration of chirality when the hemiacetal molecules are involved in the transition state structure. High barriers arefound in the reaction between the isolated molecules that are reduced by the assistance of an additional molecule(methanol or hemiacetal product). The reactions catalyzed by the hemiacetal products show higher barriers than theone catalyzed by methanol.