Ab initio and density functional evaluations of the molecular conformations of β-caryophyllene and 6-hydroxycaryophyllene

The four conformations of beta -caryophyllene (alpha alpha, alpha beta, beta alpha, and beta beta) were investigated ab initio at the 6-31G*/HF and MP2 levels and additionally hth density functional methods (B3LYP/6-31G*), as it concerns their relative thermodynamic stabilities. The alpha alpha is predicted to be the most stable geometry, in agreement with low-temperature NMR measurements. In the case of 6-hydroxycaryophyllene, the alpha alpha is still the most stable conformation when the configuration at C-6 is S, but when the configuration is reversed to R the beta beta geometry becomes the most stable one. This is again in agreement with NMR data. On the other hand, for both molecules the AM1 semiempirical model Hamiltonian fails to predict the alpha alpha as a low-energy geometry, mainly due to an incorrect description of the cyclobutane ring puckering. The interconversion paths among the different minima are also analyzed and discussed. The solvent effect (either chloroform or water) on the stability of the different conformers of beta -caryophyllene and 6-hydroxycaryophyllene was studied in the polarizable continuum model framework.