Synthesis, Proton Magnetic Resonance, and Stereochemistry of Certain o-Tolylcyclohexanediols¹

Abstract

The three new o-tolylcyclohexanediols, irans-2-o-toIyI-as-4-hydroxycycIohexanol, trans-2-o-tolyl-trans-5hydroxycyclohexanol, and irans-2-o-tolyl-as-6-hydroxycyclohexanol, have been synthesized and their configurations and conformations have been established by n.m.r.Chemical proof of configurations is also given. The n.m.r. spectra, measured in deuteriochloroform, are consistent with chair conformations with the tolyl group in an equatorial orientation. Evidence is given for the deshielding effect of an axial hydroxyl group on an axial proton when in 1-3 diaxial spatial proximity. Complications resulting from virtual long-range coupling are observed and discussed.the n.m.r. spectra.Retenes. III.

NMR Study on 1,2,4,5-Tetrasubstituted 3,3,6,6-Tetradeuterated Cyclohexanes: Conformational Contributions and 1,3-Diaxial and Vicinal Deshielding Effects of Amino and Alkylated Amino Groups and Their Protonated Forms

“…The corresponding hydrogencontaining comRound was reported previously (6). The corresponding hydrogencontaining comRound was reported previously (6).…”

“…Compounds 111, IV, V, and XI-These compounds were prepared by the methods previously described for the Corresponding hydrogen-containing compounds (6,21), except that m-chloroperbenzoic acid was used instead of perbenzoic acid for the epoxidation. The selective incorporation of deuterium on carbons 3 and 6 was accomplished by using buta$ene-1,l,4,4-d4 (1,22) instead of butadiene in the Diels-Alder condensation step of the synthetic scheme (6).…”