{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/19026"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/19026","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthetic and chromatographic study of the spiro-lactams and spiro-lactones based on a 9',10'-dihydro-(9,10)-ethanoanthracene Diels-Alder adduct. Application of flash vacuum thermolysis towards synthesis of exo-methylene lactones and lactams","abstract":"Synthesis of a variety of spiro-lactams and spiro-lactones which are based on a 9$\\sp\\prime$,10$\\sp\\prime$-dihydro- (9,10) -ethanoanthracene Diels-Alder adduct has been performed. Control of relative stereochemistry at the C2 and C2, C3 carbons on the lactone ring during synthesis of the spiro-lactones has been observed and is dependent on the reaction temperature and the length of reaction time.","abstract_html":"Synthesis of a variety of spiro-lactams and spiro-lactones which are based on a 9$\\sp\\prime$,10$\\sp\\prime$-dihydro- (9,10) -ethanoanthracene Diels-Alder adduct has been performed. Control of relative stereochemistry at the C2 and C2, C3 carbons on the lactone ring during synthesis of the spiro-lactones has been observed and is dependent on the reaction temperature and the length of reaction time.","abstract_has_math":true,"creators":["Gruber, James Vincent"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Pirkle, William H."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T11:54:44Z","date_published":"2011-05-07T11:54:44Z","updated_at":"2026-07-22T22:25:12Z","subjects":["Organic Chemistry"],"languages":["eng"],"rights":["Copyright 1989 Gruber, James Vincent"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI8916255","(UMI)AAI8916255"],"render_values":[{"text":"AAI8916255","href":null,"code":true},{"text":"(UMI)AAI8916255","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/19026","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Pirkle, William H."]},{"key":"dc:creator","label":"Author","values":["Gruber, James Vincent"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T11:54:44Z","10000-01-01","1989"]},{"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":["Organic Chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1989 Gruber, James Vincent"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI8916255","(UMI)AAI8916255","http://hdl.handle.net/2142/19026"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Synthesis of a variety of spiro-lactams and spiro-lactones which are based on a 9$\\sp\\prime$,10$\\sp\\prime$-dihydro- (9,10) -ethanoanthracene Diels-Alder adduct has been performed. Control of relative stereochemistry at the C2 and C2, C3 carbons on the lactone ring during synthesis of the spiro-lactones has been observed and is dependent on the reaction temperature and the length of reaction time.","The enantiomers of both the spiro-lactones and the spiro-lactams have been shown to separate on a chiral stationary phase derived from (R)-N-(3,5-dinitrobenzoyl)phenylglycine, (R)-CSP 1. Determination of the absolute stereochemistry at the spiro-junction of the most retained enantiomer on CSP 1 for both the spiro-lactams and spiro-lactones has been done using a variety of techniques including NMR, CD, CNDO/S-CI and force field calculations. In addition, NMR concentration studies using a soluble analogue of CSP 1 have been performed and aid in determining the important interactions responsible for enantiomer recognition. Models have been developed which describe the mode of enantiomer separation of these spiro adducts on (R)-CSP 1.","Flash vacuum thermolysis of the spiro-lactam and spiro-lactone Diels-Alder adducts has allowed formation of a variety of exo-methylene lactams and exo-methylene lactones. In several examples, rearrangement of the exo to the more stable endo products is observed. Application of both the ability to resolve the enantiomers of a spiro-lactam precurser on CSP 1 and subsequent flash vacuum thermolysis affords an enantiomerically enriched exo-methylene lactam.","Made available in DSpace on 2011-05-07T11:54:44Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 8916255.pdf: 4259962 bytes, checksum: 7b081c18813de4caff444f8d33833dc4 (MD5) Previous issue date: 1989","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:34:09Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:12:55-05:00 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 and chromatographic study of the spiro-lactams and spiro-lactones based on a 9',10'-dihydro-(9,10)-ethanoanthracene Diels-Alder adduct. Application of flash vacuum thermolysis towards synthesis of exo-methylene lactones and lactams"]}]}],"canonical_facts":{"dc:contributor":["Pirkle, William H."],"dc:creator":["Gruber, James Vincent"],"dc:date":["2011-05-07T11:54:44Z","10000-01-01","1989"],"dc:description":["Synthesis of a variety of spiro-lactams and spiro-lactones which are based on a 9$\\sp\\prime$,10$\\sp\\prime$-dihydro- (9,10) -ethanoanthracene Diels-Alder adduct has been performed. Control of relative stereochemistry at the C2 and C2, C3 carbons on the lactone ring during synthesis of the spiro-lactones has been observed and is dependent on the reaction temperature and the length of reaction time.","The enantiomers of both the spiro-lactones and the spiro-lactams have been shown to separate on a chiral stationary phase derived from (R)-N-(3,5-dinitrobenzoyl)phenylglycine, (R)-CSP 1. Determination of the absolute stereochemistry at the spiro-junction of the most retained enantiomer on CSP 1 for both the spiro-lactams and spiro-lactones has been done using a variety of techniques including NMR, CD, CNDO/S-CI and force field calculations. In addition, NMR concentration studies using a soluble analogue of CSP 1 have been performed and aid in determining the important interactions responsible for enantiomer recognition. Models have been developed which describe the mode of enantiomer separation of these spiro adducts on (R)-CSP 1.","Flash vacuum thermolysis of the spiro-lactam and spiro-lactone Diels-Alder adducts has allowed formation of a variety of exo-methylene lactams and exo-methylene lactones. In several examples, rearrangement of the exo to the more stable endo products is observed. Application of both the ability to resolve the enantiomers of a spiro-lactam precurser on CSP 1 and subsequent flash vacuum thermolysis affords an enantiomerically enriched exo-methylene lactam.","Made available in DSpace on 2011-05-07T11:54:44Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 8916255.pdf: 4259962 bytes, checksum: 7b081c18813de4caff444f8d33833dc4 (MD5) Previous issue date: 1989","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:34:09Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:12:55-05:00 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":["AAI8916255","(UMI)AAI8916255","http://hdl.handle.net/2142/19026"],"dc:language":["eng"],"dc:rights":["Copyright 1989 Gruber, James Vincent"],"dc:subject":["Organic Chemistry"],"dc:title":["Synthetic and chromatographic study of the spiro-lactams and spiro-lactones based on a 9',10'-dihydro-(9,10)-ethanoanthracene Diels-Alder adduct. Application of flash vacuum thermolysis towards synthesis of exo-methylene lactones and lactams"],"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":"2026-07-22T22:25:12Z"}