{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70207"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70207","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthesis and Chemistry of an Unusual Bridgehead Olefin","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.","abstract_html":"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.","abstract_has_math":false,"creators":["Suits, Joan Zitzmann"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-15T23:17:50Z","date_published":"2014-12-15T23:17:50Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8302996"],"render_values":[{"text":"(UMI)AAI8302996","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70207","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Suits, Joan Zitzmann"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:17:50Z","10000-01-01","1982"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Organic"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/70207","(UMI)AAI8302996"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["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.","Made available in DSpace on 2014-12-15T23:17:50Z (GMT). No. of bitstreams: 1 8302996.pdf: 4701568 bytes, checksum: 2b49cf544d489e440e74c0acd7f4368b (MD5) Previous issue date: 1982","Embargo set by: Seth Robbins for item 70373 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","170 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1982."]},{"key":"dc:title","label":"Title","values":["Synthesis and Chemistry of an Unusual Bridgehead Olefin"]}]}],"canonical_facts":{"dc:creator":["Suits, Joan Zitzmann"],"dc:date":["2014-12-15T23:17:50Z","10000-01-01","1982"],"dc:description":["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.","Made available in DSpace on 2014-12-15T23:17:50Z (GMT). No. of bitstreams: 1 8302996.pdf: 4701568 bytes, checksum: 2b49cf544d489e440e74c0acd7f4368b (MD5) Previous issue date: 1982","Embargo set by: Seth Robbins for item 70373 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","170 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1982."],"dc:identifier":["http://hdl.handle.net/2142/70207","(UMI)AAI8302996"],"dc:subject":["Chemistry, Organic"],"dc:title":["Synthesis and Chemistry of an Unusual Bridgehead Olefin"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:26:02Z"}