Date of Award
Summer 1973
Document 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.
Recommended Citation
Hwang, Hai Ok, "The Chemistry of Selected Phosphetanes" (1973). Master's Theses (1922-2009) Access restricted to Marquette Campus. 2487.
https://epublications.marquette.edu/theses/2487