{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70322"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70322","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Part One: Radical Cation and Triplex Diels-Alder Reactions. Part Two: Photochemistry of Tri-1-Naphthylboron","abstract":"Part One. The Diels-Alder reactions of electron-rich alkenes and alkadienes in a photochemical electron transfer system are presented. In acetonitrile, the Diels-Alder dimerization of 1,3-cyclohexadiene (1) is shown to be the result of the reaction of the radical cation of 1. A chain mechanism and a fast rate constant for addition of the radical cation of 1 to a neutral molecule of 1 are applied to explain a similar reaction using an aminium salt catalyst. In benzene, the Diels-Alder adducts are produced via a triplex intermediate. Product and spectroscopic studies for five triplex reactions are presented. Some preliminary observations about this reaction also are discussed.","abstract_html":"Part One. The Diels-Alder reactions of electron-rich alkenes and alkadienes in a photochemical electron transfer system are presented. In acetonitrile, the Diels-Alder dimerization of 1,3-cyclohexadiene (1) is shown to be the result of the reaction of the radical cation of 1. A chain mechanism and a fast rate constant for addition of the radical cation of 1 to a neutral molecule of 1 are applied to explain a similar reaction using an aminium salt catalyst. In benzene, the Diels-Alder adducts are produced via a triplex intermediate. Product and spectroscopic studies for five triplex reactions are presented. Some preliminary observations about this reaction also are discussed.","abstract_has_math":false,"creators":["Calhoun, Glenn Charles"],"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":"2014-12-15T23:18:39Z","date_published":"2014-12-15T23:18:39Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8623266"],"render_values":[{"text":"(UMI)AAI8623266","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70322","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Calhoun, Glenn Charles"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:39Z","10000-01-01","1986"]},{"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/2142/70322","(UMI)AAI8623266"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Part One. The Diels-Alder reactions of electron-rich alkenes and alkadienes in a photochemical electron transfer system are presented. In acetonitrile, the Diels-Alder dimerization of 1,3-cyclohexadiene (1) is shown to be the result of the reaction of the radical cation of 1. A chain mechanism and a fast rate constant for addition of the radical cation of 1 to a neutral molecule of 1 are applied to explain a similar reaction using an aminium salt catalyst. In benzene, the Diels-Alder adducts are produced via a triplex intermediate. Product and spectroscopic studies for five triplex reactions are presented. Some preliminary observations about this reaction also are discussed.","Part Two. Irradiation of tri-1-naphthylboron in cyclohexene does not give evidence for the formation of 1-naphthylborene. No cis-1,2-cyclohexanediol is detected after oxidative hydrolysis and 1,1'-binaphthyl, a primary photoproduct, is observed only in low yield. These findings are in contrast to the results of Ramsey and Anjo, which were used to support formation of 1-naphthylborene.","Made available in DSpace on 2014-12-15T23:18:39Z (GMT). No. of bitstreams: 1 8623266.pdf: 5169978 bytes, checksum: 357f217a912df51315c4a04daf5986f7 (MD5) Previous issue date: 1986","Embargo set by: Seth Robbins for item 70488 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","167 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986."]},{"key":"dc:title","label":"Title","values":["Part One: Radical Cation and Triplex Diels-Alder Reactions. Part Two: Photochemistry of Tri-1-Naphthylboron"]}]}],"canonical_facts":{"dc:creator":["Calhoun, Glenn Charles"],"dc:date":["2014-12-15T23:18:39Z","10000-01-01","1986"],"dc:description":["Part One. The Diels-Alder reactions of electron-rich alkenes and alkadienes in a photochemical electron transfer system are presented. In acetonitrile, the Diels-Alder dimerization of 1,3-cyclohexadiene (1) is shown to be the result of the reaction of the radical cation of 1. A chain mechanism and a fast rate constant for addition of the radical cation of 1 to a neutral molecule of 1 are applied to explain a similar reaction using an aminium salt catalyst. In benzene, the Diels-Alder adducts are produced via a triplex intermediate. Product and spectroscopic studies for five triplex reactions are presented. Some preliminary observations about this reaction also are discussed.","Part Two. Irradiation of tri-1-naphthylboron in cyclohexene does not give evidence for the formation of 1-naphthylborene. No cis-1,2-cyclohexanediol is detected after oxidative hydrolysis and 1,1'-binaphthyl, a primary photoproduct, is observed only in low yield. These findings are in contrast to the results of Ramsey and Anjo, which were used to support formation of 1-naphthylborene.","Made available in DSpace on 2014-12-15T23:18:39Z (GMT). No. of bitstreams: 1 8623266.pdf: 5169978 bytes, checksum: 357f217a912df51315c4a04daf5986f7 (MD5) Previous issue date: 1986","Embargo set by: Seth Robbins for item 70488 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","167 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986."],"dc:identifier":["http://hdl.handle.net/2142/70322","(UMI)AAI8623266"],"dc:subject":["Chemistry, Organic"],"dc:title":["Part One: Radical Cation and Triplex Diels-Alder Reactions. Part Two: Photochemistry of Tri-1-Naphthylboron"],"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"}