Date of Award
8-1976
Document Type
Dissertation - Restricted
Degree Name
Doctor of Philosophy (PhD)
Department
Chemistry
First Advisor
Sheldon E. Cremer
Second Advisor
Steven L. Regan
Third Advisor
Daniel T. Haworth
Fourth Advisor
Michael A. McKinney
Abstract
A general investigation of the aqueous work-up of l-chloro-l-tert.butyl-2,2,3,4,4-pentamethylphosphetanium chloride was carried out. The chloride salt was found to be rather unreactive towards water and underwent slow cis ⇄ trans isomerization by a pseudorotational mechanism. The stereochemical outcome of water treatment was similar to that of other phosphetanium salts studied in this laboratory. Low temperature nmr studies of l-chloro-l-phenyl-2,2,3,4,4-pentamethyl and l-chloro-1.2,2,3,4,4-hexamethylphosphetanlum chlorides supported the concept of isomer interconversion through a pseudorotational process. The hydrogen bromide addition product of both cis- and trans-1,2,2,3,4,4-hexamethylphosphetane l-oxide were made. No isomer interconversion of these adducts was observed when they were heated.
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