Date of Award

Spring 1981

Degree Type

Thesis - Restricted

Degree Name

Master of Arts (MA)

Department

Chemistry

First Advisor

Cremer, Sheldon E.

Second Advisor

Hoffman, Norman

Third Advisor

Pollard, Bruce D.

Abstract

A synthetic sequence for the preparation of exo-3- methoxy-endo-3-phenyl- 3-phosphoniabicyclo [3. 2.1] oct-6-ene tetrafluoroborate (9) and (+)methoxyethylmethylphenylphosphonium hexafluorophosphate (18) is described. Alkaline decomposition of (9) affords the corresponding phosphine oxide with complete inversion of configuration at phosphorus. An oxygen-18 labeling experiment indicates that exclusive P-O bond cleavage occurs rather than C-O bond cleavage. On the other hand, aqueous decomposition of (9) in the presence of various organic bases, namely pyridine, urea, triethylamine, or aniline, gives varying results from nearly complete retention to complete inversion. It appears, from another oxygen-18 labeling experiment, that aqueous decomposition of (9) in the presence of aniline gives C-O cleavage with retention of configuration at phosphorus. In addition, the hydrolysis of (18) was studied. Alkaline decomposition of (18) affords 75% inversion of configuration at phosphorus (determined by optical rotation). Aqueous decomposition of (18) affords 58-63 % retention of configuration.

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