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Title:Synthesis and Chemistry of an Unusual Bridgehead Olefin
Author(s):Suits, Joan Zitzmann
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(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.
Issue Date:1982
Description:170 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1982.
Other Identifier(s):(UMI)AAI8302996
Date Available in IDEALS:2014-12-15
Date Deposited:1982

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