{"id":{"repo_id":"cape-town","oai_identifier":"oai:open.uct.ac.za:11427/22276"},"canonical_url":"https://search.dev.ndltd.org/etd/cape-town/oai:open.uct.ac.za:11427/22276","repository":{"repo_id":"cape-town","name":"University of Cape Town","base_url":"https://open.uct.ac.za/oai/request"},"display":{"title":"Reactivity studies of phosphoric amides and esters","abstract":"The effect of protonation and Lewis acid-base interaction on the ¹H n.m.r. chemical shifts of the ester and amide bonds in selected phosphoramidates (RO)₂P(O)NR'₂ was investigated. The results are interpreted in terms of the interaction of the phosphoryl oxygen atom with Lewis acids and oxygen/nitrogen diprotonation in trifluoromethanesulphonic acid. Intramolecular nucleophilic displacement of the halide ion from secondary β-chloroethyl-substituted phosphoramidates X₂P(O)NHCH₂CH₂Cl, diamidates (RO) (MeNH)P(O)NHCH₂CH₂Cl and β-chloroethyl phosphates Y(MeO)P(O)OCH₂CH₂Cl, was studied under conditions of electrophilic (Ag+) and basic (NaH) catalysis. 1,3-Substitution by the nitrogen atom of the phosphdramidates, yielding ethylenimine derivatives was found to be the preferred reaction-pathway; the alternative 1,5-reaction involving the amide nittogen or phosphoryl oxygen atoms was not observed. No intramolecular nucleophilic displacement occurred in the β-chloroethyl phosphate esters.","abstract_html":"The effect of protonation and Lewis acid-base interaction on the ¹H n.m.r. chemical shifts of the ester and amide bonds in selected phosphoramidates (RO)₂P(O)NR'₂ was investigated. The results are interpreted in terms of the interaction of the phosphoryl oxygen atom with Lewis acids and oxygen/nitrogen diprotonation in trifluoromethanesulphonic acid. Intramolecular nucleophilic displacement of the halide ion from secondary β-chloroethyl-substituted phosphoramidates X₂P(O)NHCH₂CH₂Cl, diamidates (RO) (MeNH)P(O)NHCH₂CH₂Cl and β-chloroethyl phosphates Y(MeO)P(O)OCH₂CH₂Cl, was studied under conditions of electrophilic (Ag+) and basic (NaH) catalysis. 1,3-Substitution by the nitrogen atom of the phosphdramidates, yielding ethylenimine derivatives was found to be the preferred reaction-pathway; the alternative 1,5-reaction involving the amide nittogen or phosphoryl oxygen atoms was not observed. No intramolecular nucleophilic displacement occurred in the β-chloroethyl phosphate esters.","abstract_has_math":false,"creators":["Davidowitz, Bette"],"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":1984,"date_issued":"1984","date_published":"1984","updated_at":"2026-07-22T22:23:00Z","subjects":[],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/11427/22276","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":["Davidowitz, Bette"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2016-10-24T03:50:36Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2016-10-24T03:50:36Z"]},{"key":"dc:date.issued","label":"Date","values":["1984"]},{"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/11427/22276"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Bibliography: pages 154-161."]},{"key":"dc:description.abstract","label":"Abstract","values":["The effect of protonation and Lewis acid-base interaction on the ¹H n.m.r. chemical shifts of the ester and amide bonds in selected phosphoramidates (RO)₂P(O)NR'₂ was investigated. The results are interpreted in terms of the interaction of the phosphoryl oxygen atom with Lewis acids and oxygen/nitrogen diprotonation in trifluoromethanesulphonic acid. Intramolecular nucleophilic displacement of the halide ion from secondary β-chloroethyl-substituted phosphoramidates X₂P(O)NHCH₂CH₂Cl, diamidates (RO) (MeNH)P(O)NHCH₂CH₂Cl and β-chloroethyl phosphates Y(MeO)P(O)OCH₂CH₂Cl, was studied under conditions of electrophilic (Ag+) and basic (NaH) catalysis. 1,3-Substitution by the nitrogen atom of the phosphdramidates, yielding ethylenimine derivatives was found to be the preferred reaction-pathway; the alternative 1,5-reaction involving the amide nittogen or phosphoryl oxygen atoms was not observed. No intramolecular nucleophilic displacement occurred in the β-chloroethyl phosphate esters."]},{"key":"dc:title","label":"Title","values":["Reactivity studies of phosphoric amides and esters"]}]}],"canonical_facts":{"dc:contributor.advisor":["Modro, Tomasz A"],"dc:creator":["Davidowitz, Bette"],"dc:date.accessioned":["2016-10-24T03:50:36Z"],"dc:date.available":["2016-10-24T03:50:36Z"],"dc:date.issued":["1984"],"dc:description":["Bibliography: pages 154-161."],"dc:description.abstract":["The effect of protonation and Lewis acid-base interaction on the ¹H n.m.r. chemical shifts of the ester and amide bonds in selected phosphoramidates (RO)₂P(O)NR'₂ was investigated. The results are interpreted in terms of the interaction of the phosphoryl oxygen atom with Lewis acids and oxygen/nitrogen diprotonation in trifluoromethanesulphonic acid. Intramolecular nucleophilic displacement of the halide ion from secondary β-chloroethyl-substituted phosphoramidates X₂P(O)NHCH₂CH₂Cl, diamidates (RO) (MeNH)P(O)NHCH₂CH₂Cl and β-chloroethyl phosphates Y(MeO)P(O)OCH₂CH₂Cl, was studied under conditions of electrophilic (Ag+) and basic (NaH) catalysis. 1,3-Substitution by the nitrogen atom of the phosphdramidates, yielding ethylenimine derivatives was found to be the preferred reaction-pathway; the alternative 1,5-reaction involving the amide nittogen or phosphoryl oxygen atoms was not observed. No intramolecular nucleophilic displacement occurred in the β-chloroethyl phosphate esters."],"dc:identifier.uri":["http://hdl.handle.net/11427/22276"],"dc:language.iso":["eng"],"dc:publisher.department":["Department of Chemistry"],"dc:publisher.institution":["University of Cape Town"],"dc:title":["Reactivity studies of phosphoric amides and esters"],"dc:type":["Doctoral Thesis"],"dc:type.qualificationlevel":["Doctoral"],"dc:type.qualificationname":["PhD"]},"updated_at":"2026-07-22T22:23:00Z"}