PERTURBATION EFFECTS BETWEEN MULTIPLE BONDS.
Abstract
The interaction between sites of unsaturation in organic molecules spatially oriented to produce anomalies in their ultraviolet spectra were studied. The products, intermediates and mechanisms involved in reduction by sodium in liquid ammonia were considered. After preparation, 1-t-butyl-3, 3-dimethylcyclopropene and bicyclo(4.2.0)oct-7-ene were treated with sodium in liquid ammonia to evaluate strain effects. The former was completely reduced but the latter was unaffected. The unstrained cyclodec-5-en-1-one was readily reduced by this reagent to bicyclo(5.3.0)decane-1-ol. An attempted synthesis of cyclodec-5-en-1-one starting with 1, 6-cyclodecadiene led to a series of interesting transannular rearrangements. Bicyclo(2.2.1)hept-5-ene-2-one with one equivalent of sodium in ammonia afforded a high yield of a dimeric material, while a large excess of sodium gave reduction of the ketone group to the unsaturated alcohol. Tricyclo(1.1.1.0)hept-2-one on reduction gave bicyclo(2.2.1)hept-2-one. cis-Bicyclo(3.3.0)oct-7-ene-2-one was reduced to a mixture of the endo and exo-cis-bicyclo 3.3.0 oct-7-ene-2-ols. Reduction of (2.2)paracyclophane with sodium in liquid ammonia gave both 1, 4-dihydro and tetrahydro products. When ethanol as a proton donor was added the reaction proceeded by a different course to give 4,4'-di-p-tolylethane. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Feb 01, 1969
- Accession Number
- AD0685185
Entities
People
- Ben Arthur Loving
Organizations
- Air Force Research Laboratory