Synthesis and Chemistry of an Unusual Bridgehead Olefin
Suits, Joan Zitzmann
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https://hdl.handle.net/2142/70207
Description
Title
Synthesis and Chemistry of an Unusual Bridgehead Olefin
Author(s)
Suits, Joan Zitzmann
Issue Date
1982
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Abstract
The bridgehead olefin I was synthesized and a number of itsreactions studied. The olefin is unique in that it possesses acyclopropyl ring oriented in such a way that one edge of the ringfaces directly into the back side of the double bond.
I was synthesized in three steps from the corresponding hydrobromide and was characterized by NMR, CMR, IR, and UV spectroscopy as well as elemental analyses and an X-ray crystal structure. Attempted isomerisation of I was unsuccessful. However, the olefin is highly reactive towards many reagents. I reacts readily with halogens by what appears to be primarily a radical process, even in the dark. The olefin is easily epoxidized by reaction with m-chloroperoxybenzoic acid and cyclopropanated by the Simmons-Smith reagent and is very reactive towards many radical and nucleophilic reagents. This reactivity appears to be due to the presence of the cyclopropyl ring, since the non-cyclopropanated bridgehead olefin does not react with radical reagents, and is less reactive towards nucleophilic reagents.
Cycloaddition reactions of I were sluggish. I did not react with dienes such as furan and reacted with cyclopentadiene only at elevated temperatures. Although the reaction between I and azide ion was complete within a few days, the reaction between I and phenyl azide took over two months. I did not react with electrophilic reagents such as silver salts or born trifluoride. However, I did react with hydrogen halides, and the reaction between I and water was found to be acid-catalyzed, implying electrophilic addition. This reactivity again appears to be due to the presence of the cyclopropyl ring, since the non-cyclopropenated bridgehead olefin was found to be unreactive towards hydrogen bromide.
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