Record Details
Conformation and reactivity studies of some bicyclo(3.3.1) nonane derivatives
ScholarsArchive at Oregon State University
| Field | Value |
|---|---|
| Title | Conformation and reactivity studies of some bicyclo(3.3.1) nonane derivatives |
| Names |
Sturmer, David Michael
(creator) Bond, F. Thomas (advisor) |
| Date Issued | 1966-07-26 (iso8601) |
| Note | Graduation date: 1967 |
| Abstract | 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. |
| Genre | Thesis/Dissertation |
| Topic | Bicyclic compounds |
| Identifier | http://hdl.handle.net/1957/47194 |
