Eclipsed Acetaldehyde as a Precursor for Producing Vinyl Alcohol

Abstract

The MP2 and DFT/B3LYP methods at 6-311++G(d,p) and aug-cc-pdz basis sets have been used to probe the origin of relative stability preference for eclipsed acetaldehyde over its bisected counterpart. A relative energy stability range of 1.02 to 1.20 kcal/mol, in favor of the eclipsed conformer, was found and discussed. An NBO study at these chemistry levels complemented these findings and assigned the eclipsed acetaldehyde preference mainly to the vicinal antiperiplanar hyperconjugative interactions. The tautomeric interconversion between the more stable eclipsed acetaldehyde and vinyl alcohol has been achieved through a four-membered ring transition state (TS). The obtained barrier heights and relative stabilities of eclipsed acetaldehyde and the two conformers of vinyl alchol at these model chemistries have been estimated and discussed.

Characterization of non-covalent contacts in mono- and di-halo substituted acetaldehydes: probing the substitution effects of electron donating and withdrawing groups

“…20 Moorthy, Venugopalan and co-workers have explored the role of formyl C–H⋯O interactions in defining crystal packing through their work on the formyl C–H⋯O interactions in the crystal structures of coumarins and aromatic aldehydes. 21 Osman et al 22 reported the relative stability of the eclipsed and bisected acetaldehydes at the Møller–Plesset second order perturbation level of theory (MP2) employing aug-cc-pVDZ basis sets. The eclipsed conformer of acetaldehyde with a relative energy stability in the range of 4.26 to 5.01 kJ mol −1 was obtained.…”