Date of Award
Spring 1981
Document 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.
Recommended Citation
Borsub, Laddawan, "Synthesis and Aqueous Hydrolysis of the Phosphonium Salts: exo-3-Methoxy-endo-3-Phenyl-3-Phosphoniabicyclo-[3.2.1]Oct-6-Ene Tetrafluoroborate and (+)Methoxyethylmethylphenylphosophonium Hexafluorophosphate" (1981). Master's Theses (1922-2009) Access restricted to Marquette Campus. 2398.
https://epublications.marquette.edu/theses/2398