Conformational effects on optical rotation. 3-substituted 1-butenes

A calculation of the optical rotation of (R)-(-)-3-chloro-1-butene found a remarkably large dependence on the C=C-C-C torsional angle. At tau = 0 degrees, alpha](D) = +244 degrees, whereas at tau = 180 degrees, alpha](D) = -526 degrees. The effect of conformation on the optical rotation was confirmed by a study of the temperature dependence of the rotation. An analysis of the data gave the difference in free energy between the low- and high-energy conformers as 1315 cal/mol and gave the optical rotation of the low-energy conformer and the average of the rotations of the higher energy forms. Although a large effect was found, the observed rotations are a factor of 2.6 smaller than the calculated values, independent of both conformation and wavelength from 589 to 365 nm. The effect of replacing Cl with F, CN, and CCH was examined theoretically. The effects of substituents are remarkably small despite large changes in the calculated electronic transition energies.