Conformational interactions between a phenyl ring and a side-chain halide substituent: A 1H NMR and molecular mechanics study of some 2-aryl-1-halopropanes

Abstract

1H NMR data are reported for a series of 2-aryl-1-halopropanes. Vicinal coupling constants in the CH 2CH—fragment show that the rotamer populations about the CC bond are sensitive to para substituents. The ratio of anti:gauche aryl/halide conformers is greatest when the para substituent is the electron-donating ethyl group and least when it is the strongly electron-withdrawing nitro group. This points to a non-steric conformational interaction involving the ring and the sidechain heteroatom. Comparison of the empirical results with conformational preferences predicted from molecular mechanics calculations using the COSMIC force field suggests that the interaction serves to enhance the population of the anti arrangement.