Comparison of the intramolecular hydrogen bonds and of the internal barrier to rotation the hydroxyl and sulfhydryl groups in 2-methoxyphenol and 2-methoxythiophenol

Abstract

The long-range spin–spin coupling constants involving the hydroxyl proton in 2-methoxyphenol are consistent with a potential function for rotation of the hydroxyl group derived from far infrared torsion data. The internally hydrogen bonded cis conformer is the only one detected by nmr. In contrast, the long-range couplings of the sulfhydryl group in 2-methoxythiophenol indicate that the trans conformer is favored over the cis conformer by a free energy difference of 0.2 + 0.2 kcal/mol. Furthermore, the barrier to internal rotation of the sulfhydryl group is much smaller than that of the hydroxyl group in these two compounds. It is suggested that the barrier in the thiophenol derivative is 2.7 ± 0.6 kcal/mol, to be compared with a twofold component of 6 kcal/mol in the rotational potential function of the phenol analog.