{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70365"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70365","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Direct Liquid Chromatographic Separation of Enantiomers of Phthalides, Phthalimidines and Related Compounds on Chiral Stationary Phases","abstract":"The enantiomers of a diverse series of 3-arylphthalides are separable by high performance liquid chromatography on chiral stationary phases (CSPs) derived from the N-3,5-dinitrobenzamides of (S)-leucine or (R)-phenylglycine covalently bonded to aminopropyl silanized silica. A chiral recognition model for the separation of phthalide enantiomers has been formulated based on the observed chromatographic behavior of these phthalides. Assignment of elution orders based on the a priori model proposed are consistent with those ultimately determined by independent chemical and spectroscopic means. A phthalide structurally optimized to maximize the chromatographic separability of its enantiomers on the aforementioned CSPs is incorporated into a phthalide-based CSP which has proven to be effective for the separation of enantiomers of numerous analytes. The chromatographic behavior of a variety of 3-arylphthalimidines and their corresponding ureide derivatives on the amino acid CSPs, as well as a novel procedure for C-3 alkylation without N-2 alkylation of these phthalimidines via conversion to the ureide derivatives, is described. Alkylation of certain enantiomerically pure ureides affords enantiomerically enriched products owing to the self-immolative transfer of chirality from central to axial, back to central chirality. Factors affecting this process are discussed.","abstract_html":"The enantiomers of a diverse series of 3-arylphthalides are separable by high performance liquid chromatography on chiral stationary phases (CSPs) derived from the N-3,5-dinitrobenzamides of (S)-leucine or (R)-phenylglycine covalently bonded to aminopropyl silanized silica. A chiral recognition model for the separation of phthalide enantiomers has been formulated based on the observed chromatographic behavior of these phthalides. Assignment of elution orders based on the a priori model proposed are consistent with those ultimately determined by independent chemical and spectroscopic means. A phthalide structurally optimized to maximize the chromatographic separability of its enantiomers on the aforementioned CSPs is incorporated into a phthalide-based CSP which has proven to be effective for the separation of enantiomers of numerous analytes. The chromatographic behavior of a variety of 3-arylphthalimidines and their corresponding ureide derivatives on the amino acid CSPs, as well as a novel procedure for C-3 alkylation without N-2 alkylation of these phthalimidines via conversion to the ureide derivatives, is described. Alkylation of certain enantiomerically pure ureides affords enantiomerically enriched products owing to the self-immolative transfer of chirality from central to axial, back to central chirality. Factors affecting this process are discussed.","abstract_has_math":false,"creators":["Sowin, Thomas Joseph"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-15T23:18:57Z","date_published":"2014-12-15T23:18:57Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8711882"],"render_values":[{"text":"(UMI)AAI8711882","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70365","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Sowin, Thomas Joseph"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:57Z","10000-01-01","1987"]},{"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":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/70365","(UMI)AAI8711882"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The enantiomers of a diverse series of 3-arylphthalides are separable by high performance liquid chromatography on chiral stationary phases (CSPs) derived from the N-3,5-dinitrobenzamides of (S)-leucine or (R)-phenylglycine covalently bonded to aminopropyl silanized silica. A chiral recognition model for the separation of phthalide enantiomers has been formulated based on the observed chromatographic behavior of these phthalides. Assignment of elution orders based on the a priori model proposed are consistent with those ultimately determined by independent chemical and spectroscopic means. A phthalide structurally optimized to maximize the chromatographic separability of its enantiomers on the aforementioned CSPs is incorporated into a phthalide-based CSP which has proven to be effective for the separation of enantiomers of numerous analytes. The chromatographic behavior of a variety of 3-arylphthalimidines and their corresponding ureide derivatives on the amino acid CSPs, as well as a novel procedure for C-3 alkylation without N-2 alkylation of these phthalimidines via conversion to the ureide derivatives, is described. Alkylation of certain enantiomerically pure ureides affords enantiomerically enriched products owing to the self-immolative transfer of chirality from central to axial, back to central chirality. Factors affecting this process are discussed.","Made available in DSpace on 2014-12-15T23:18:57Z (GMT). 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A chiral recognition model for the separation of phthalide enantiomers has been formulated based on the observed chromatographic behavior of these phthalides. Assignment of elution orders based on the a priori model proposed are consistent with those ultimately determined by independent chemical and spectroscopic means. A phthalide structurally optimized to maximize the chromatographic separability of its enantiomers on the aforementioned CSPs is incorporated into a phthalide-based CSP which has proven to be effective for the separation of enantiomers of numerous analytes. The chromatographic behavior of a variety of 3-arylphthalimidines and their corresponding ureide derivatives on the amino acid CSPs, as well as a novel procedure for C-3 alkylation without N-2 alkylation of these phthalimidines via conversion to the ureide derivatives, is described. Alkylation of certain enantiomerically pure ureides affords enantiomerically enriched products owing to the self-immolative transfer of chirality from central to axial, back to central chirality. Factors affecting this process are discussed.","Made available in DSpace on 2014-12-15T23:18:57Z (GMT). No. of bitstreams: 1 8711882.pdf: 4475447 bytes, checksum: d4fa1f698653e4784cef262ce5f1229f (MD5) Previous issue date: 1987","Embargo set by: Seth Robbins for item 70531 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","160 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1987."],"dc:identifier":["http://hdl.handle.net/2142/70365","(UMI)AAI8711882"],"dc:subject":["Chemistry, Organic"],"dc:title":["Direct Liquid Chromatographic Separation of Enantiomers of Phthalides, Phthalimidines and Related Compounds on Chiral Stationary Phases"],"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":"2026-07-22T22:26:02Z"}