Rules for generating conformers and their relative energies in n-alkanes with a heteroelement O or S: ethers and alcohols, or sulfides and thiols.
With the aid of density functional theory calculations, all conformers of several single-chain alcohols, thiols, ethers, and sulfides are investigated. Starting from earlier computational works on n-alkanes, we construct an extended set of general rules for predicting the number and occurrence of conformers in these oxygen- or sulfur-containing compounds. In alcohols and thiols, it is found that only the conformers generated by internal rotations in the HXCH(2)CH(2)CH(2) (X = O or S) top are distinctive from those in n-alkanes. In ethers and sulfides, the primary influence of the heteroelement also extends up to three internal rotations, but many more conformers are possible. However, a number of double gauche sequences are forbidden, and therefore, several conformers can be eliminated. These exclusions in particular make up a set of rules for eventually deducing all possible conformers. Furthermore, on the basis of only an exact calculation of these gg conformations in addition to single gauche conformers, it is possible to make an accurate estimate of the relative energy. This two-dimensional approximation scheme constitutes an effective tool for adequately describing the relative energies of all possible conformers at a minimal computational cost.
Vansteenkiste
P
P
Center for Molecular Modeling, Laboratory of Theoretical Physics, Ghent University, Proeftuinstraat 86, B-9000 Gent, Belgium.
Pauwels
E
E
Van Speybroeck
V
V
Waroquier
M
M
D000438:Alcohols / Q000737:chemistry*; D000473:Alkanes / Q000737:chemistry*; D003198:Computer Simulation; D004987:Ethers / Q000737:chemistry*; D008956:Models, Chemical; D008968:Molecular Conformation; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013440:Sulfides / Q000737:chemistry*
D000438:Alcohols; D000473:Alkanes; D004987:Ethers; D013438:Sulfhydryl Compounds; D013440:Sulfides