Syntheses, Reactions, and Sterochemical Studies of 1,4-Dimethyl-2-Phosphabicyclo(2.2.1)Heptane and 4-tert-Butylphosphorinane Derivatives

Author

Asher Gamliel, Marquette University

Date of Award

11-1983

Document Type

Dissertation - Restricted

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Sheldon E. Cremer

Abstract

1,4-Dimethyl-2-phenyl-2-phosphabicyclo[2.2.1]heptane 2-oxide was prepared by the reaction of 2,5-dimethyl-1,5-hexadiene with PhPCl₂-AlCl₃; the stereochemistry was established by ¹³C NMR spectroscopy [using lanthanide shift reagents (LSR)] and X-ray analysis. The oxide isomers (exo and endo) were independently reduced (phenylsilane) to give the phenylphosphine with retention of configuration; the phosphines were thermally equilibrated at 190°C (exo-phenylphosphine predominated). Quarternization with benzyl bromide or methyl bromide gave the phosphonium salts. Aqueous, alkaline hydrolysis of the benzylphenylphosphonium salt gave the phenylphosphine oxide (retention). The isomeric methyl-phenylphosphonium salts equilibrated under basic conditions prior to oxide formation.

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