{"id":{"repo_id":"cape-town","oai_identifier":"oai:open.uct.ac.za:11427/22138"},"canonical_url":"https://search.dev.ndltd.org/etd/cape-town/oai:open.uct.ac.za:11427/22138","repository":{"repo_id":"cape-town","name":"University of Cape Town","base_url":"https://open.uct.ac.za/oai/request"},"display":{"title":"Intra- and intermolecular reactivity of organic diacyl systems","abstract":"The mechanism or a thermal amino group transfer-fragmentation reaction yielding carboxyamides from mixed phosphoric-carboxylic anhydrides (RO(R¹R²N)P(O)OC(O)R³; R = R¹ = alkyl; R² = H, alkyl, aryl; R³ = alkyl, aryl) was elucidated from structure reactivity studies using a model system, R = R¹ = R² = Me, R³ = Ph. Kinetic data was obtained using ¹H nmr spectroscopy; MNDO molecular orbital and molecular mechanics calculations, and the crystal structure or N-methyl-2-benzoyloxy-2-oxo-1, 3, 2-oxazaphosphorinane (Pna2₁; a = 22.229(6)Å, b = 7.597(2)Å, c = 7.210(2)Å; v = 1217.6(6)ų. Final R = 3. 08% for 1037 reflections with I (rel )> 2αI (rel) and 15 7 parameters) were userul in providing additional in formation about the reaction mechanism .","abstract_html":"The mechanism or a thermal amino group transfer-fragmentation reaction yielding carboxyamides from mixed phosphoric-carboxylic anhydrides (RO(R¹R²N)P(O)OC(O)R³; R = R¹ = alkyl; R² = H, alkyl, aryl; R³ = alkyl, aryl) was elucidated from structure reactivity studies using a model system, R = R¹ = R² = Me, R³ = Ph. Kinetic data was obtained using ¹H nmr spectroscopy; MNDO molecular orbital and molecular mechanics calculations, and the crystal structure or N-methyl-2-benzoyloxy-2-oxo-1, 3, 2-oxazaphosphorinane (Pna2₁; a = 22.229(6)Å, b = 7.597(2)Å, c = 7.210(2)Å; v = 1217.6(6)ų. Final R = 3. 08% for 1037 reflections with I (rel )> 2αI (rel) and 15 7 parameters) were userul in providing additional in formation about the reaction mechanism .","abstract_has_math":false,"creators":["Symes, Jillian Ellis"],"institution":"Department of Chemistry","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Modro, Tomasz A"],"committee_chairs":[],"committee_members":[],"year":1988,"date_issued":"1988","date_published":"1988","updated_at":"2026-07-24T01:34:06Z","subjects":[],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/11427/22138","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Modro, Tomasz A"]},{"key":"dc:creator","label":"Author","values":["Symes, Jillian Ellis"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2016-10-14T06:27:26Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2016-10-14T06:27:26Z"]},{"key":"dc:date.issued","label":"Date","values":["1988"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Department of Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Cape Town"]},{"key":"dc:type","label":"Dc Type","values":["Doctoral Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["Doctoral"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["PhD"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/11427/22138"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The mechanism or a thermal amino group transfer-fragmentation reaction yielding carboxyamides from mixed phosphoric-carboxylic anhydrides (RO(R¹R²N)P(O)OC(O)R³; R = R¹ = alkyl; R² = H, alkyl, aryl; R³ = alkyl, aryl) was elucidated from structure reactivity studies using a model system, R = R¹ = R² = Me, R³ = Ph. Kinetic data was obtained using ¹H nmr spectroscopy; MNDO molecular orbital and molecular mechanics calculations, and the crystal structure or N-methyl-2-benzoyloxy-2-oxo-1, 3, 2-oxazaphosphorinane (Pna2₁; a = 22.229(6)Å, b = 7.597(2)Å, c = 7.210(2)Å; v = 1217.6(6)ų. Final R = 3. 08% for 1037 reflections with I (rel )> 2αI (rel) and 15 7 parameters) were userul in providing additional in formation about the reaction mechanism ."]},{"key":"dc:title","label":"Title","values":["Intra- and intermolecular reactivity of organic diacyl systems"]}]}],"canonical_facts":{"dc:contributor.advisor":["Modro, Tomasz A"],"dc:creator":["Symes, Jillian Ellis"],"dc:date.accessioned":["2016-10-14T06:27:26Z"],"dc:date.available":["2016-10-14T06:27:26Z"],"dc:date.issued":["1988"],"dc:description.abstract":["The mechanism or a thermal amino group transfer-fragmentation reaction yielding carboxyamides from mixed phosphoric-carboxylic anhydrides (RO(R¹R²N)P(O)OC(O)R³; R = R¹ = alkyl; R² = H, alkyl, aryl; R³ = alkyl, aryl) was elucidated from structure reactivity studies using a model system, R = R¹ = R² = Me, R³ = Ph. Kinetic data was obtained using ¹H nmr spectroscopy; MNDO molecular orbital and molecular mechanics calculations, and the crystal structure or N-methyl-2-benzoyloxy-2-oxo-1, 3, 2-oxazaphosphorinane (Pna2₁; a = 22.229(6)Å, b = 7.597(2)Å, c = 7.210(2)Å; v = 1217.6(6)ų. Final R = 3. 08% for 1037 reflections with I (rel )> 2αI (rel) and 15 7 parameters) were userul in providing additional in formation about the reaction mechanism ."],"dc:identifier.uri":["http://hdl.handle.net/11427/22138"],"dc:language.iso":["eng"],"dc:publisher.department":["Department of Chemistry"],"dc:publisher.institution":["University of Cape Town"],"dc:title":["Intra- and intermolecular reactivity of organic diacyl systems"],"dc:type":["Doctoral Thesis"],"dc:type.qualificationlevel":["Doctoral"],"dc:type.qualificationname":["PhD"]},"updated_at":"2026-07-24T01:34:06Z"}