{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70346"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70346","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Kinetics and Mechanism of Syn, Alpha' Lithiation of Tertiary Benzamides","abstract":"The reaction of N,N-dialkyl-2,4,6-triisopropylbenzamides with sec-butyllithium in cyclohexane yields a product in which metalation has occurred exclusively at the carbon adjacent to nitrogen and syn to the carbonyl group. Evidence obtained by nuclear magnetic reso- nance, freezing point depression and stopped-flow infrared spectros- copy indicates the reaction proceeds with rapid initial formation of tetrameric complexes followed by rate determining deprotonation. Model studies using N,N,N',N'-tetramethylethylenediamine (TMEDA)","abstract_html":"The reaction of N,N-dialkyl-2,4,6-triisopropylbenzamides with sec-butyllithium in cyclohexane yields a product in which metalation has occurred exclusively at the carbon adjacent to nitrogen and syn to the carbonyl group. Evidence obtained by nuclear magnetic reso- nance, freezing point depression and stopped-flow infrared spectros- copy indicates the reaction proceeds with rapid initial formation of tetrameric complexes followed by rate determining deprotonation. Model studies using N,N,N',N'-tetramethylethylenediamine (TMEDA)","abstract_has_math":false,"creators":["Hay, David Raymond"],"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":"2014-12-15T23:18:50Z","date_published":"2014-12-15T23:18:50Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8701508"],"render_values":[{"text":"(UMI)AAI8701508","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70346","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Hay, David Raymond"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:50Z","10000-01-01","1986"]},{"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/2142/70346","(UMI)AAI8701508"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The reaction of N,N-dialkyl-2,4,6-triisopropylbenzamides with sec-butyllithium in cyclohexane yields a product in which metalation has occurred exclusively at the carbon adjacent to nitrogen and syn to the carbonyl group. Evidence obtained by nuclear magnetic reso- nance, freezing point depression and stopped-flow infrared spectros- copy indicates the reaction proceeds with rapid initial formation of tetrameric complexes followed by rate determining deprotonation. Model studies using N,N,N',N'-tetramethylethylenediamine (TMEDA)","confirmed the tetrameric nature of the complexes. Computer modelling of the kinetic data gave the following mechanism. (UNFORMATTED TABLE FOLLOWS)","K(,1) k(,4)","(sec-BuLi)(,4) + Amide (DBLHARR) (sec-BuLi)(,4)*Amide (--->) Product","K(,2) k(,5)","(sec-BuLi)(,4)*Amide + Amide (DBLHARR) (sec-BuLi)(,4)*Amide(,2) (--->) Product","K(,3) k(,6)","(sec-BuLi)(,4)*Amide(,2) + Amide (DBLHARR) (sec-BuLi)(,4)*Amide(,3) (--->) Product (TABLE ENDS)","Made available in DSpace on 2014-12-15T23:18:50Z (GMT). No. of bitstreams: 1 8701508.pdf: 4053452 bytes, checksum: 35fb9b09f95cd7bcd25b2a42ef9b3d96 (MD5) Previous issue date: 1986","Embargo set by: Seth Robbins for item 70512 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","185 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986."]},{"key":"dc:title","label":"Title","values":["Kinetics and Mechanism of Syn, Alpha' Lithiation of Tertiary Benzamides"]}]}],"canonical_facts":{"dc:creator":["Hay, David Raymond"],"dc:date":["2014-12-15T23:18:50Z","10000-01-01","1986"],"dc:description":["The reaction of N,N-dialkyl-2,4,6-triisopropylbenzamides with sec-butyllithium in cyclohexane yields a product in which metalation has occurred exclusively at the carbon adjacent to nitrogen and syn to the carbonyl group. Evidence obtained by nuclear magnetic reso- nance, freezing point depression and stopped-flow infrared spectros- copy indicates the reaction proceeds with rapid initial formation of tetrameric complexes followed by rate determining deprotonation. Model studies using N,N,N',N'-tetramethylethylenediamine (TMEDA)","confirmed the tetrameric nature of the complexes. Computer modelling of the kinetic data gave the following mechanism. (UNFORMATTED TABLE FOLLOWS)","K(,1) k(,4)","(sec-BuLi)(,4) + Amide (DBLHARR) (sec-BuLi)(,4)*Amide (--->) Product","K(,2) k(,5)","(sec-BuLi)(,4)*Amide + Amide (DBLHARR) (sec-BuLi)(,4)*Amide(,2) (--->) Product","K(,3) k(,6)","(sec-BuLi)(,4)*Amide(,2) + Amide (DBLHARR) (sec-BuLi)(,4)*Amide(,3) (--->) Product (TABLE ENDS)","Made available in DSpace on 2014-12-15T23:18:50Z (GMT). No. of bitstreams: 1 8701508.pdf: 4053452 bytes, checksum: 35fb9b09f95cd7bcd25b2a42ef9b3d96 (MD5) Previous issue date: 1986","Embargo set by: Seth Robbins for item 70512 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","185 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986."],"dc:identifier":["http://hdl.handle.net/2142/70346","(UMI)AAI8701508"],"dc:subject":["Chemistry, Organic"],"dc:title":["Kinetics and Mechanism of Syn, Alpha' Lithiation of Tertiary Benzamides"],"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"}