Date of Award

Summer 1973

Degree Type

Thesis - Restricted

Degree Name

Master of Science (MS)

Department

Chemistry

First Advisor

Cremer, Sheldon E.

Second Advisor

McKinney, Michael A.

Third Advisor

Haworth, Daniel T.

Abstract

The reaction intermediates, 1-chloro-1-phenyl-2,2,J,4,4- pentamethyl (3b) and 1-chloro-1,2,2,3,4,4-hexamethylphosphetanium tetrachloroalurninate (3c), derived from PhPCl2-A1C13 or CH3PC12-A1C13 and 2,4,4-trimethyl-2-pentene have been isolated and fully characterized. The cis-trans isomer distribution in these salts has been correlated with the isomer ratio of 1-phenyl-2,2,3,4,4-pentamethyl (4b) and 1,2,2,3,4,4-hexamethylphosphetane 1-oxide (4c) when the former are quenched with water. The experimental mode of water addition is critical and determines the isomeric composition. Treatment of CH3PC12 and PhPBr2 with bicyclo[2.2. 1] hepta- 2.5-diene and subsequent quenching with water produced 4-methyl(35) and 4-phenyl-4-phosphatetracyclo[3.3.0.02,8,03,6 octane 4-oxide (45), respectively. Smooth reduction and quarternization of oxide (35) provided an isomeric mixture of 4-benzyl-4- methyl-4-phosphoniatetracyclo 3.3.0.02,8.03,6] octane bromide (55). The base catalyzed hydrolysis of salt 55 produced benzylmethyltricyclo [2.2.1.02,6]hept-3-ylphosphine oxide (58); ring opening takes place in preference to exocyclic cleavage of the benzyl group. The rate of base decomposition was much faster than for similar monocyclic phosphetane salts. The 1H nmr spectra of the tetracyclic phosphetane compounds and their reaction products were used to corroborate or identify their structures; additional structural support comes from 13c nmr data , X-ray, and satisfactory elemental combustion analysis.

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