Molecular structure, experimental and theoretical¹H and¹³C NMR chemical shift assignment of cyclic and acyclic α,β-unsaturated esters

Abstract

The experimental 1H and 13C NMR spectra of 13 phenyl cinnamates and four 4‐methylcoumarins were investigated and their chemical shifts assigned on the basis of the two‐dimensional spectra. For the unsubstituted cinnamic acid phenyl ester, optimized molecular structures were calculated at a B3LYP/6‐311++G(d,p) level of theory. 1H and 13C NMR chemical shifts were also calculated with the GIAO method at the B3LYP/6‐311 + G(2d,p) level of theory. The comparison between experimental and calculated NMR chemical shift suggests that the experimental spectra are formed from the superposition spectra of the two lowest energy conformers of the compound in solution. The most stable s‐cis configuration found in our studies is also the conformation adopted for a related phenyl cinnamate in solid state. The experimental results were analyzed in terms of the substituent effects. Copyright © 2013 John Wiley & Sons, Ltd.

Aryl Naphthoates: A Conformational Analysis Supported by Single-Crystal X-Ray Diffraction

“…In a previous work, phenyl esters of cinnamic acid showed that the Z conformation was 4.91 kcal mol À1 more stable than its E counterpart. [10] The E p curve around torsion C angle shows only one minimum at 08 as the E conformer forces both aromatic rings to get close to each other (repulsive effect). The E p difference between the two conformers, i.e.…”