{"id":{"repo_id":"arizona-thes","oai_identifier":"oai:repository.arizona.edu:10150/183991"},"canonical_url":"https://search.dev.ndltd.org/etd/arizona-thes/oai:repository.arizona.edu:10150/183991","repository":{"repo_id":"arizona-thes","name":"University of Arizona","base_url":"https://repository.arizona.edu/oai/request"},"display":{"title":"ALKYLATION AND OXIDATIONS OF SYMMETRICAL DIMETHYLENEBIPHENYL AND RELATED DIANIONS (CYCLOPHANE, BIPHENYLOPHANE, NMR, CONFORMATION).","abstract":"Bis-benzyl dianions were prepared from the three symmetrical dimethylbiphenyls in yields of 79-86%, and shown to react with a variety of electrophiles on the benzylic carbons. Electrophiles included dimethyl and diethyl sulfate, isopropyl bromide, t-butyl iodide, allyl chloride, trimethylsilyl chloride, trimethylgermyl bromide, and trimethyltin chloride. Reaction of the dianions with (alpha),(omega)-dihalides provides an excellent route to n.0 - and n.0.n.0 cyclophanes. An X-ray study on 14.0 paracyclophane showed it to have a conformation different from that observed in solution by NMR; MM2 calculations were used in determining what the solution conformation is likely to be. Oxidation of the dianions produced the monomer dihydrophenanthrene from the ortho isomer, dimer 2.0.2.0 metacyclophane from the meta isomer, and polymer from the para isomer. An X-ray study on 2.0.2.0 metacyclophane showed it to have the same conformation in the crystal as is observed in solution by NMR. An NMR method for determining the angle of twist in a biphenyl based on the chemical shift of the ortho hydrogens was developed. Many oxidizing agents were evaluated for the oxidation of the dianion from 2,3-dimethyl-1,3-butadiene to 1,2,5,6-tetramethylenecyclooctane; cupric bromide was found to be the best.","abstract_html":"Bis-benzyl dianions were prepared from the three symmetrical dimethylbiphenyls in yields of 79-86%, and shown to react with a variety of electrophiles on the benzylic carbons. Electrophiles included dimethyl and diethyl sulfate, isopropyl bromide, t-butyl iodide, allyl chloride, trimethylsilyl chloride, trimethylgermyl bromide, and trimethyltin chloride. Reaction of the dianions with (alpha),(omega)-dihalides provides an excellent route to n.0 - and n.0.n.0 cyclophanes. An X-ray study on 14.0 paracyclophane showed it to have a conformation different from that observed in solution by NMR; MM2 calculations were used in determining what the solution conformation is likely to be. Oxidation of the dianions produced the monomer dihydrophenanthrene from the ortho isomer, dimer 2.0.2.0 metacyclophane from the meta isomer, and polymer from the para isomer. An X-ray study on 2.0.2.0 metacyclophane showed it to have the same conformation in the crystal as is observed in solution by NMR. An NMR method for determining the angle of twist in a biphenyl based on the chemical shift of the ortho hydrogens was developed. Many oxidizing agents were evaluated for the oxidation of the dianion from 2,3-dimethyl-1,3-butadiene to 1,2,5,6-tetramethylenecyclooctane; cupric bromide was found to be the best.","abstract_has_math":false,"creators":["WHITE, JAMES JEFFREY."],"institution":"The University of Arizona.","degree_name":"Ph.D.","degree_level":"doctoral","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":["Bates, Robert B."],"committee_chairs":[],"committee_members":[],"year":1986,"date_issued":"1986","date_published":"1986","updated_at":"2026-07-24T00:56:22Z","subjects":["Anions.","Organic compounds -- Synthesis."],"languages":["en"],"rights":["Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10150/183991","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Bates, Robert B."]},{"key":"dc:creator","label":"Author","values":["WHITE, JAMES JEFFREY."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2011-10-31T16:55:43Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2011-10-31T16:55:43Z"]},{"key":"dc:date.issued","label":"Date","values":["1986"]},{"key":"dc:publisher","label":"Institution","values":["The University of Arizona."]},{"key":"dc:type","label":"Dc Type","values":["text","Dissertation-Reproduction (electronic)"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry","Graduate College"]},{"key":"thesis:degree_level","label":"Degree Level","values":["doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Arizona"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Anions.","Organic compounds -- Synthesis."]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/10150/183991"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Bis-benzyl dianions were prepared from the three symmetrical dimethylbiphenyls in yields of 79-86%, and shown to react with a variety of electrophiles on the benzylic carbons. Electrophiles included dimethyl and diethyl sulfate, isopropyl bromide, t-butyl iodide, allyl chloride, trimethylsilyl chloride, trimethylgermyl bromide, and trimethyltin chloride. Reaction of the dianions with (alpha),(omega)-dihalides provides an excellent route to n.0 - and n.0.n.0 cyclophanes. An X-ray study on 14.0 paracyclophane showed it to have a conformation different from that observed in solution by NMR; MM2 calculations were used in determining what the solution conformation is likely to be. Oxidation of the dianions produced the monomer dihydrophenanthrene from the ortho isomer, dimer 2.0.2.0 metacyclophane from the meta isomer, and polymer from the para isomer. An X-ray study on 2.0.2.0 metacyclophane showed it to have the same conformation in the crystal as is observed in solution by NMR. An NMR method for determining the angle of twist in a biphenyl based on the chemical shift of the ortho hydrogens was developed. Many oxidizing agents were evaluated for the oxidation of the dianion from 2,3-dimethyl-1,3-butadiene to 1,2,5,6-tetramethylenecyclooctane; cupric bromide was found to be the best."]},{"key":"dc:title","label":"Title","values":["ALKYLATION AND OXIDATIONS OF SYMMETRICAL DIMETHYLENEBIPHENYL AND RELATED DIANIONS (CYCLOPHANE, BIPHENYLOPHANE, NMR, CONFORMATION)."]}]}],"canonical_facts":{"dc:contributor.advisor":["Bates, Robert B."],"dc:creator":["WHITE, JAMES JEFFREY."],"dc:date.accessioned":["2011-10-31T16:55:43Z"],"dc:date.available":["2011-10-31T16:55:43Z"],"dc:date.issued":["1986"],"dc:description.abstract":["Bis-benzyl dianions were prepared from the three symmetrical dimethylbiphenyls in yields of 79-86%, and shown to react with a variety of electrophiles on the benzylic carbons. Electrophiles included dimethyl and diethyl sulfate, isopropyl bromide, t-butyl iodide, allyl chloride, trimethylsilyl chloride, trimethylgermyl bromide, and trimethyltin chloride. Reaction of the dianions with (alpha),(omega)-dihalides provides an excellent route to n.0 - and n.0.n.0 cyclophanes. An X-ray study on 14.0 paracyclophane showed it to have a conformation different from that observed in solution by NMR; MM2 calculations were used in determining what the solution conformation is likely to be. Oxidation of the dianions produced the monomer dihydrophenanthrene from the ortho isomer, dimer 2.0.2.0 metacyclophane from the meta isomer, and polymer from the para isomer. An X-ray study on 2.0.2.0 metacyclophane showed it to have the same conformation in the crystal as is observed in solution by NMR. An NMR method for determining the angle of twist in a biphenyl based on the chemical shift of the ortho hydrogens was developed. Many oxidizing agents were evaluated for the oxidation of the dianion from 2,3-dimethyl-1,3-butadiene to 1,2,5,6-tetramethylenecyclooctane; cupric bromide was found to be the best."],"dc:identifier.uri":["http://hdl.handle.net/10150/183991"],"dc:language.iso":["en"],"dc:publisher":["The University of Arizona."],"dc:rights":["Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author."],"dc:subject":["Anions.","Organic compounds -- Synthesis."],"dc:title":["ALKYLATION AND OXIDATIONS OF SYMMETRICAL DIMETHYLENEBIPHENYL AND RELATED DIANIONS (CYCLOPHANE, BIPHENYLOPHANE, NMR, CONFORMATION)."],"dc:type":["text","Dissertation-Reproduction (electronic)"],"thesis:degree_discipline":["Chemistry","Graduate College"],"thesis:degree_level":["doctoral"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Arizona"]},"updated_at":"2026-07-24T00:56:22Z"}