Raby, Bruce F.2009-04-172009-04-1719701970Source: Masters Abstracts International, Volume: 45-06, page: 3166.http://hdl.handle.net/10393/10647http://dx.doi.org/10.20381/ruor-8393A series-of substituted methyl 1-methylcyclohex-3-ene-1-carboxylates of the general formula have been synthesized and the proton magnetic resonance spectra measured. The ring protons were extensively coupled to each other and gave complex spectra. The 3, 5, 5'-trideutero analogues have also been synthesized. The geminal coupling constant JAB, was obtained from the AB pattern produced by the magnetically non-equivalent protons in the allylic methylene group. JAB has been found to depend on the nature of the substituent R. A Hammett correlation between JAB and sigma P, the Hammett substituent constant, had a slope or rho value of -2.9. Resonance effects were shown to be much more predominant than field effects.* Long-range coupling over four bonds has been measured between the allylic proton at C2 and the homoallylic proton at C6. The low field proton of each AB group has been tentatively assigned as being cis to the carbomethoxy group. The low field proton of the allylic methylene group showed a larger S. C. S. than the high field proton. Since the low field proton is predominantly in the pseudoequatorial position, this result is opposite to that predicted by a hyperconjugative type of interaction. The chemical shift of the olefinic proton of each compound has been found to obey the additivity scheme of Sternhell and co-workers. *Please refer to dissertation for diagram.64 p.Chemistry, Organic.Thesis