Effect of solvent and temperature upon the rotationally averaged vicinal coupling constants of some substituted 1,2-dibromoethanes

Abstract

The solvent dependence of vicinal coupling constants has been investigated for (1,2-dibromoethyl)-benzene and three of its 4-substituted derivatives and for threo- and erythro(1,2-dibromopropyl)benzene. The temperature dependence of the vicinal coupling constants of three of the compounds has also been investigated. The difference between the two vicinal coupling constants of (1,2-dibromoethyl)benzene is dependent upon solution dielectric constant (in non-aromatic solvents) while the sum of coupling constants remains constant. The relative stabilities of its three rotamers are deduced from this information. A polar substituent in the 4-position does not affect the rotational equilibrium in any predictable manner. The vicinal coupling constant of threo(1,2-dibromopropyl)benzene is strongly solvent dependent. The relative stabilities of its three rotamers are deduced from the observation that the vicinal coupling constant is temperature independent. The most stable rotamer of erythro(1,2-dibromopropyl)-benzene is deduced from the observation that the vicinal coupling constant is large and independent of solvent. Factors affecting conformational preference are deduced. It is concluded that dipolar interactions are as important as steric interactions.