An NMR and solvation study of rotational isomerism in epihalohydrins

The ¹H NMR spectra of epifluoro, chloro- and bromohydrin have been analysed in a number of solvents of varying polarity. Ab initio and molecular mechanism calculations together with solvation theory allowed an analysis of the observed solvent dependence of the proton couplings in terms of the anti and gauche rotamers only, the syn rotamer being of very small population: The Ga che-anti energy difference in the vapour is 0.1, 0.5 and 0.7 kcal mol^-1 for the three compounds respectively, though these relative energies may be reversed in solutions in which the gauche form is relatively more stabilized. The trans-oriented vicinal coupling has values of 7.3, 8.4 and 9.1 Hz for F, Cl, and Br respectively. Only one long-range coupling showed a pronounced orientation dependence, due to an approximately planar zizag orientation in the gauche rotamer.