Part I. The structure of lyconnotine. Part II. Studies of some derivatives of cyclohexane. Part III. Studies of some derivatives of bicyclo[2.2.1]heptane.

Abstract

Part I. Lyconnotine, an alkaloid of Lycopodium annotinum L. has been isolated by an improved method. Isolation of a derivative of lyconnotine has also been accomplished. The structure and stereochemistry of these alkaloids have been established on the basis of chemical and spectral evidence. Attempts to interrelate acrifoline and dihydro-acrifoline to lyconnotine by photochemical cleavage of the former two alkaloids have been unsuccessful. On photolysis, a complicated mixture of a number of components is obtained. It has been shown that the major photoproducts cannot be readily converted to lyconnotine. Part II. The preparation of (i) cyclohexane- cis-3,3,4,5,6,6-d6, (ii) cis-1,2-dicarbomethoxy cyclohexane-cis-3,3,4,5,6,6-d6, and (iii) cyclohexane-3,3,6,6-d 4 has been achieved. The N.M.R. spectra of these compounds at ambient and lower temperatures are discussed and various kinetic parameters for conformational changes in cyclohexene have been obtained. Values of the coupling constants in cyclohexane are furnished. Part III. The syntheses of a number of 7-substituted bicyclo[2.2.1]heptane derivatives are described. Representative compounds include 7-isopropylidene bicyclo[2.2.1]hept-5-ene-exo-2,3-diol carbonate Ia, the corresponding endo isomer Ib, exo-2,3-dihydroxy-7-isopropylidene bicyclo[2.2.1]hept-5-ene IIa, the corresponding endo diol IIb, 7-isopropylidene bicyclo[2.2.1]hept-5-ene- exo-2,3-diol thionocarbonate, IIIa and its endo counterpart IIIb. Products of catalytic reduction of compounds Ia, IIa and IIIa have also been obtained. Configurations of these compounds have been established on the basis of their N.M.R. spectra. Attempts to obtain 7-isopropylidene bicyclo[2.2.1]hepta-2,5-diene have been unsuccessful. The anisotropic effect of the double bond in the above series and in the 7,7-dimethylene bicyclo[2.2.1]heptane derivatives is discussed and compared with the previous results in the literature.