Acetalization and thioacetalization of cabonyl compounds: A case study based on global and local electrophilicity descriptors

Abstract

Acetalization of benzaldehyde and substituted benzaldehydes (containing both electron-donating and electron-withdrawing groups) is explained qualitatively on the basis of global electrophilicity descriptor, w, as proposed by Parr and coworkers (11). The generated values of w can explain qualitatively the preferential electrophilic addition, and hence, the yield of acetalization obtained in an earlier experimental study carried by Patel and coworkers (17). The present study also reveals that although both steric and electronic factors affect the yield, only later can be taken care of by w. In the case of a competitive formation of cyclic acetals and cyclic thioacetals from a reaction mixture containing p-hydroxybenzaldehyde, p-nitrobenzaldehyde, 1,2-ethanediol (i.e., glycol), and 1,2-ethanedithiol, the relative experimental yields (18) could be explained from the difference of the global electrophilicity values between aldehydes and acetalizing agents in the same line of arguments of Maynard et al.