{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/20222"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/20222","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthetic approaches to a hypervalent trigonal bipyramidal carbon species and a versatile reagent for the oxidation of primary and secondary alcohols to aldehydes and ketones","abstract":"The synthesis of a novel ortho-bridged triarylmethanol, 6-(1,1-dimethylethyl)-12c-hydroxy-4,8-dioxa-4H,8H-dibenzo- (cd,mn) pyren-12(12cH)-one, is described in Part I. The key step involves an intramolecular Friedel-Crafts reaction of a triarylmethyl cation. Some reactions of this methanol derivative are presented as part of an attempted synthesis of a hypervalent (10-C-5) trigonal bipyramidal carbon species.","abstract_html":"The synthesis of a novel ortho-bridged triarylmethanol, 6-(1,1-dimethylethyl)-12c-hydroxy-4,8-dioxa-4H,8H-dibenzo- (cd,mn) pyren-12(12cH)-one, is described in Part I. The key step involves an intramolecular Friedel-Crafts reaction of a triarylmethyl cation. Some reactions of this methanol derivative are presented as part of an attempted synthesis of a hypervalent (10-C-5) trigonal bipyramidal carbon species.","abstract_has_math":false,"creators":["Henderson, Craig Conger"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Deuman, Scott E."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T12:32:46Z","date_published":"2011-05-07T12:32:46Z","updated_at":"2026-07-22T22:25:15Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":["Copyright 1991 Henderson, Craig Conger"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9210835","(UMI)AAI9210835"],"render_values":[{"text":"AAI9210835","href":null,"code":true},{"text":"(UMI)AAI9210835","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/20222","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Deuman, Scott E."]},{"key":"dc:creator","label":"Author","values":["Henderson, Craig Conger"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:32:46Z","10000-01-01","1991"]},{"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":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1991 Henderson, Craig Conger"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9210835","(UMI)AAI9210835","http://hdl.handle.net/2142/20222"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The synthesis of a novel ortho-bridged triarylmethanol, 6-(1,1-dimethylethyl)-12c-hydroxy-4,8-dioxa-4H,8H-dibenzo- (cd,mn) pyren-12(12cH)-one, is described in Part I. The key step involves an intramolecular Friedel-Crafts reaction of a triarylmethyl cation. Some reactions of this methanol derivative are presented as part of an attempted synthesis of a hypervalent (10-C-5) trigonal bipyramidal carbon species.","Other approaches to a hypervalent trigonal bipyramidal carbon species from spiro (anthracene-9,1$\\sp\\prime$-phthalan) derivatives are presented in Part II. The electronic and geometric factors of the ligands in the target hypervalent carbon species are discussed in terms of known ligand-induced stabilization of hypervalent species of higher row main group elements. Stabilization of the hypervalent bond by delocalization of the excess electron density in the three-center, four-electron (3c-4e) bond onto a bidentate $\\pi$-acceptor ligand in the equatorial plane of the trigonal bipyramidal 10-C-5 species is emphasized. The synthesis and reactions of the spiro (anthracene-9,1$\\sp\\prime$-phthalan) precursors is given along with a summary of the attempts to convert these precursors to hypervalent 10-C-5 species. The synthetic value of a mercuration/halogenation reaction for the regiospecific addition of an iodine to an arene is illustrated in the synthesis of one of the precursors, a novel ortho-bridged triarylmethyl trifluoromethylsulfonate.","Another example of the mercuration/halogenation reaction of an arene is given in Part III which describes the large scale synthesis of 4-(1,1-dimethylethyl)-2-iodobenzoic acid, the precursor to 1,1,1-tris(acetoxy)-6-(1,1-dimethylethyl)-1,1-dihydro-1,$ 2$-benziodoxol-3(1H)-one. The use of this 12-I-5 triacetoxyperiodinane, which is a derivative of the so-called Dess-Martin Periodinane, as a reagent for the oxidation of primary and secondary alcohols to aldehydes and ketones is also described. The advantages of the tert-butylated triacetoxyperiodinane compared to the unsubstituted Dess-Martin triacetoxyperiodinane are discussed in terms of ease of preparation, increased solubility, and decreased rate of decomposition of the 10-I-4 iodinane oxide precursor at its melting point. Several examples of oxidations of alcohols with 12-I-5 triacetoxyperiodinanes and 10-I-4 iodinane oxides are given, and a possible mechanism for these reactions is discussed.","Made available in DSpace on 2011-05-07T12:32:46Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9210835.pdf: 6816710 bytes, checksum: ba2b14be237d18f7baaf4d81aefe97ec (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:42:27Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:18:27-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Synthetic approaches to a hypervalent trigonal bipyramidal carbon species and a versatile reagent for the oxidation of primary and secondary alcohols to aldehydes and ketones"]}]}],"canonical_facts":{"dc:contributor":["Deuman, Scott E."],"dc:creator":["Henderson, Craig Conger"],"dc:date":["2011-05-07T12:32:46Z","10000-01-01","1991"],"dc:description":["The synthesis of a novel ortho-bridged triarylmethanol, 6-(1,1-dimethylethyl)-12c-hydroxy-4,8-dioxa-4H,8H-dibenzo- (cd,mn) pyren-12(12cH)-one, is described in Part I. The key step involves an intramolecular Friedel-Crafts reaction of a triarylmethyl cation. Some reactions of this methanol derivative are presented as part of an attempted synthesis of a hypervalent (10-C-5) trigonal bipyramidal carbon species.","Other approaches to a hypervalent trigonal bipyramidal carbon species from spiro (anthracene-9,1$\\sp\\prime$-phthalan) derivatives are presented in Part II. The electronic and geometric factors of the ligands in the target hypervalent carbon species are discussed in terms of known ligand-induced stabilization of hypervalent species of higher row main group elements. Stabilization of the hypervalent bond by delocalization of the excess electron density in the three-center, four-electron (3c-4e) bond onto a bidentate $\\pi$-acceptor ligand in the equatorial plane of the trigonal bipyramidal 10-C-5 species is emphasized. The synthesis and reactions of the spiro (anthracene-9,1$\\sp\\prime$-phthalan) precursors is given along with a summary of the attempts to convert these precursors to hypervalent 10-C-5 species. The synthetic value of a mercuration/halogenation reaction for the regiospecific addition of an iodine to an arene is illustrated in the synthesis of one of the precursors, a novel ortho-bridged triarylmethyl trifluoromethylsulfonate.","Another example of the mercuration/halogenation reaction of an arene is given in Part III which describes the large scale synthesis of 4-(1,1-dimethylethyl)-2-iodobenzoic acid, the precursor to 1,1,1-tris(acetoxy)-6-(1,1-dimethylethyl)-1,1-dihydro-1,$ 2$-benziodoxol-3(1H)-one. The use of this 12-I-5 triacetoxyperiodinane, which is a derivative of the so-called Dess-Martin Periodinane, as a reagent for the oxidation of primary and secondary alcohols to aldehydes and ketones is also described. The advantages of the tert-butylated triacetoxyperiodinane compared to the unsubstituted Dess-Martin triacetoxyperiodinane are discussed in terms of ease of preparation, increased solubility, and decreased rate of decomposition of the 10-I-4 iodinane oxide precursor at its melting point. Several examples of oxidations of alcohols with 12-I-5 triacetoxyperiodinanes and 10-I-4 iodinane oxides are given, and a possible mechanism for these reactions is discussed.","Made available in DSpace on 2011-05-07T12:32:46Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9210835.pdf: 6816710 bytes, checksum: ba2b14be237d18f7baaf4d81aefe97ec (MD5) Previous issue date: 1991","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:42:27Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:18:27-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["AAI9210835","(UMI)AAI9210835","http://hdl.handle.net/2142/20222"],"dc:language":["eng"],"dc:rights":["Copyright 1991 Henderson, Craig Conger"],"dc:subject":["Chemistry, Organic"],"dc:title":["Synthetic approaches to a hypervalent trigonal bipyramidal carbon species and a versatile reagent for the oxidation of primary and secondary alcohols to aldehydes and ketones"],"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":"2026-07-22T22:25:15Z"}