{"id":{"repo_id":"cape-town","oai_identifier":"oai:open.uct.ac.za:11427/17035"},"canonical_url":"https://search.dev.ndltd.org/etd/cape-town/oai:open.uct.ac.za:11427/17035","repository":{"repo_id":"cape-town","name":"University of Cape Town","base_url":"https://open.uct.ac.za/oai/request"},"display":{"title":"Tertiary N-acyl phosphoramidates : a mechanistic study of their formation and collapse in reactions with nucleophiles","abstract":"Different synthetic approaches to tertiary mixed phosphoric-carboxylic imides(III) are discussed. The preparation of (III) via the N-acylation of phosphoramidates was investigated. The reaction of PhC(O)X (X = Br, Cl, F) with the conjugate base of (EtO)₂P(O)NHMe (IX) yields three products: PhCO₂Et (4), PhC(O)NHMe (5) and (PhCO)₂NMe (6). (5) and (6) are formed via the initial rapid formation of (EtO)₂P(O)-NMe-C(O)Ph (IIIe), while (4) results from the E1cB related reaction of (EtO)₂P(O)NMe involving electrophilic assistance by PhC(O)X. The attack of various nucleophilic species at the mixed-imide (IIIe) was studied, and the possible mechanisms of the P-N bond cleavage, followed by the N-methyl transfer from the phosphoryl to the carbonyl centre are discussed.","abstract_html":"Different synthetic approaches to tertiary mixed phosphoric-carboxylic imides(III) are discussed. The preparation of (III) via the N-acylation of phosphoramidates was investigated. The reaction of PhC(O)X (X = Br, Cl, F) with the conjugate base of (EtO)₂P(O)NHMe (IX) yields three products: PhCO₂Et (4), PhC(O)NHMe (5) and (PhCO)₂NMe (6). (5) and (6) are formed via the initial rapid formation of (EtO)₂P(O)-NMe-C(O)Ph (IIIe), while (4) results from the E1cB related reaction of (EtO)₂P(O)NMe involving electrophilic assistance by PhC(O)X. The attack of various nucleophilic species at the mixed-imide (IIIe) was studied, and the possible mechanisms of the P-N bond cleavage, followed by the N-methyl transfer from the phosphoryl to the carbonyl centre are discussed.","abstract_has_math":false,"creators":["Hendrickse, Theodore Franklin"],"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":1983,"date_issued":"1983","date_published":"1983","updated_at":"2026-07-22T22:23:46Z","subjects":[],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/11427/17035","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":["Hendrickse, Theodore Franklin"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2016-02-15T07:15:33Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2016-02-15T07:15:33Z"]},{"key":"dc:date.issued","label":"Date","values":["1983"]},{"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":["Master Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["Masters"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["MSc"]}]},{"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/11427/17035"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Bibliography: pages 91-96."]},{"key":"dc:description.abstract","label":"Abstract","values":["Different synthetic approaches to tertiary mixed phosphoric-carboxylic imides(III) are discussed. The preparation of (III) via the N-acylation of phosphoramidates was investigated. The reaction of PhC(O)X (X = Br, Cl, F) with the conjugate base of (EtO)₂P(O)NHMe (IX) yields three products: PhCO₂Et (4), PhC(O)NHMe (5) and (PhCO)₂NMe (6). (5) and (6) are formed via the initial rapid formation of (EtO)₂P(O)-NMe-C(O)Ph (IIIe), while (4) results from the E1cB related reaction of (EtO)₂P(O)NMe involving electrophilic assistance by PhC(O)X. The attack of various nucleophilic species at the mixed-imide (IIIe) was studied, and the possible mechanisms of the P-N bond cleavage, followed by the N-methyl transfer from the phosphoryl to the carbonyl centre are discussed."]},{"key":"dc:title","label":"Title","values":["Tertiary N-acyl phosphoramidates : a mechanistic study of their formation and collapse in reactions with nucleophiles"]}]}],"canonical_facts":{"dc:contributor.advisor":["Modro, Tomasz A"],"dc:creator":["Hendrickse, Theodore Franklin"],"dc:date.accessioned":["2016-02-15T07:15:33Z"],"dc:date.available":["2016-02-15T07:15:33Z"],"dc:date.issued":["1983"],"dc:description":["Bibliography: pages 91-96."],"dc:description.abstract":["Different synthetic approaches to tertiary mixed phosphoric-carboxylic imides(III) are discussed. The preparation of (III) via the N-acylation of phosphoramidates was investigated. The reaction of PhC(O)X (X = Br, Cl, F) with the conjugate base of (EtO)₂P(O)NHMe (IX) yields three products: PhCO₂Et (4), PhC(O)NHMe (5) and (PhCO)₂NMe (6). (5) and (6) are formed via the initial rapid formation of (EtO)₂P(O)-NMe-C(O)Ph (IIIe), while (4) results from the E1cB related reaction of (EtO)₂P(O)NMe involving electrophilic assistance by PhC(O)X. The attack of various nucleophilic species at the mixed-imide (IIIe) was studied, and the possible mechanisms of the P-N bond cleavage, followed by the N-methyl transfer from the phosphoryl to the carbonyl centre are discussed."],"dc:identifier.uri":["http://hdl.handle.net/11427/17035"],"dc:language.iso":["eng"],"dc:publisher.department":["Department of Chemistry"],"dc:publisher.institution":["University of Cape Town"],"dc:title":["Tertiary N-acyl phosphoramidates : a mechanistic study of their formation and collapse in reactions with nucleophiles"],"dc:type":["Master Thesis"],"dc:type.qualificationlevel":["Masters"],"dc:type.qualificationname":["MSc"]},"updated_at":"2026-07-22T22:23:46Z"}