Conformation and reactivity studies of some bicyclo(3.3.1) nonane derivatives Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/gq67jw07k

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  • New syntheses for 2-bicyclo(3.3.1)nonanone and 7-bicyclo-(3.3.1)nonen-2-one were developed. The saturated ketone was prepared from phenol and acrylonitrile via a novel intramolecular S[subscript N]2 cyclization process. A Friedel-Crafts cyclization of 3-(3-cyclohexenyl)propanoyl chloride permitted synthesis of the unsaturated ketone from 4-cyclohexene carboxaldehyde. The formation of the bicyclo(3.3.1)nonane rather than a bicyclo(3.2.2)nonane skeleton in the Friedel-Crafts cyclization was proven by comparative mass spectrometry. An attempt to prepare 2-bicyclo(3.3.1)nonyl acetate by solvolysis of 3-(3-cyclohexenyl)propyl tosylate led only to monocyclic products. The influence of the proximity of carbons 3 and 7 on the chemistry of the bicyclo(3.3.1)nonane ring was studied via the transannular reactions from 2-bicyclo(3.3.1)nonene oxide. This epoxide was shown to be the exo-2, 3-epoxide by reduction to the known exo-2-bicyclo(3.3.1)nonanol. Solvolysis of the epoxide in trifluoroacetic acid gave almost exclusively 7-bicyclo(3.3.1)nonenexo-2-ol. Solvolysis in acetic acid-sodium acetate gave 20% 3-bicyclo(3. 3. 1)nonen-exo-2-ol, 54% exo-2-exo-7-bicyclo(3.3.1)nonadiol, and about 14% exo-2-exo-3-bicyclo(3.3.1)nonadiol. Formation of the strained 1-bicyclo(3.3.1)nonene as a transient enolate ion intermediate in the proton exchange at the bridgehead was shown by synthesis and exchange studies of 3, 3-dimethyl-2-bicyclo(3.3.1)nonanone. In deuteriomethanol at 100.8° the rate of exchange equals 0. 67 x 10⁻⁴ 1./mole-sec. A combination of chemical and spectral methods was used to make some conformational assignments for a number of bicyclo-(3.3.1)nonane derivatives.
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