title: Chiroptical properties of 2-chloropropionitrile.
abstract: (S)-(-)-2-chloropropionitrile has been prepared from (S)-(+)-alanine, and the ORD curves have been obtained in several solvents and in the gas phase. A reaction field extrapolation of the solution data to the gas phase led to an estimated value of [alpha]D = -21 degrees, whereas the interpolated gas phase value is -8 degrees. The specific rotation was found to be temperature dependent in ethylcyclohexane solution over the range 0-100 degrees C. Although rotation of the methyl group leads to large calculated effects on the specific rotation, it does not lead to the temperature dependence. Rather, a low frequency mode at 224 cm(-1) was found to be responsible. This is a mixed mode involving methyl torsion and C-C[triple bond]N bending. The specific rotations calculated at the B3LYP/aug-cc-pVDZ level including electric field dependent functions are in very good agreement with the measured gas phase values.
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, USA.
authors.forename: Kenneth B
authors.initials: KB
authors.lastname: Wiberg
authors.forename: Yi-gui
authors.initials: YG
authors.lastname: Wang
authors.forename: Shaun M
authors.initials: SM
authors.lastname: Wilson
authors.forename: Patrick H
authors.initials: PH
authors.lastname: Vaccaro
authors.forename: James R
authors.initials: JR
authors.lastname: Cheeseman