Accession Number:

AD0685185

Title:

PERTURBATION EFFECTS BETWEEN MULTIPLE BONDS.

Descriptive Note:

Final rept. Jan 66-Jan 68,

Corporate Author:

AIR FORCE MATERIALS LAB WRIGHT-PATTERSON AFB OHIO

Personal Author(s):

Report Date:

1969-02-01

Pagination or Media Count:

211.0

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 bicyclo4.2.0oct-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 bicyclo5.3.0decane-1-ol. An attempted synthesis of cyclodec-5-en-1-one starting with 1, 6-cyclodecadiene led to a series of interesting transannular rearrangements. Bicyclo2.2.1hept-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. Tricyclo1.1.1.0hept-2-one on reduction gave bicyclo2.2.1hept-2-one. cis-Bicyclo3.3.0oct-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 2.2paracyclophane 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

Subject Categories:

  • Organic Chemistry
  • Atomic and Molecular Physics and Spectroscopy

Distribution Statement:

APPROVED FOR PUBLIC RELEASE