{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/67290"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/67290","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Synthesis and Structure Assignments of Novel Azolinone Ribonucleosides","abstract":"Ribosidation of a series of azolinones was achieved via silylation and SnCl(,4) catalysis. Ribosidation of 4-imidazolin-2-one gave 1-(beta)-D-ribofuranosyl-4-imidazolin-2-one; of 1,2,4-triazolin-3-one gave 1-, 2-, and 4-(beta)-D-ribofuranosyl-1,2,4-triazolin-3-one, and 2,4-bis-(beta)-D-ribofuranosyl-1,2,4-triazolin-3-one; and of 2-tetrazolin-5-one gave 1-(beta)-D-ribofuranosyl-2-tetrazolin-5-one and 1,4-bis-(beta)-D-ribofuranosyl-2-tetrazolin-5-one. Structure assignments were based on microanalyses and ('1)H and ('13)C NMR spectra. The triazolinone mono-riboside isomer structures are differentiated by ('13)C NMR long-range coupling patterns, and two of the assignments were confirmed by X-ray crystallography. Improved syntheses were developed for two of the ribosides by fashioning the azolinone rings onto 2,3,5-tri-O-benzoylribofuranosyl isocyanate. Reaction of 2,3,5-tri-O-benzoylribofuranosyl isocyanate with (alpha)-aminoacetaldehyde diethyl acetal gave N-(2,2-diethoxyethyl)-N'-(beta)-D-(2,3,5-tri-O-benzoylribofuranosyl)-4-imidazolin-2-one in the presence of acid. Addition of formic acid hydrazide to 2,3,5-tri-O-benzoylribofuranosyl isocyanate gave 1-formyl-4-(beta)-D-(2,3,5-tri-O-benzoyl-ribofuranosyl)semicarbazide, which gave 4-(beta)-D-(2,3,5-tri-O-benzoylribofuranosyl)-1,2,4-triazolin-3-one upon dehydrative silylation. Methyl N-carbomethoxyformimidate was synthesized as a possible reagent for the synthesis of the other 1,2,4-triazolin-3-one products.","abstract_html":"Ribosidation of a series of azolinones was achieved via silylation and SnCl(,4) catalysis. Ribosidation of 4-imidazolin-2-one gave 1-(beta)-D-ribofuranosyl-4-imidazolin-2-one; of 1,2,4-triazolin-3-one gave 1-, 2-, and 4-(beta)-D-ribofuranosyl-1,2,4-triazolin-3-one, and 2,4-bis-(beta)-D-ribofuranosyl-1,2,4-triazolin-3-one; and of 2-tetrazolin-5-one gave 1-(beta)-D-ribofuranosyl-2-tetrazolin-5-one and 1,4-bis-(beta)-D-ribofuranosyl-2-tetrazolin-5-one. Structure assignments were based on microanalyses and ('1)H and ('13)C NMR spectra. The triazolinone mono-riboside isomer structures are differentiated by ('13)C NMR long-range coupling patterns, and two of the assignments were confirmed by X-ray crystallography. Improved syntheses were developed for two of the ribosides by fashioning the azolinone rings onto 2,3,5-tri-O-benzoylribofuranosyl isocyanate. Reaction of 2,3,5-tri-O-benzoylribofuranosyl isocyanate with (alpha)-aminoacetaldehyde diethyl acetal gave N-(2,2-diethoxyethyl)-N'-(beta)-D-(2,3,5-tri-O-benzoylribofuranosyl)-4-imidazolin-2-one in the presence of acid. Addition of formic acid hydrazide to 2,3,5-tri-O-benzoylribofuranosyl isocyanate gave 1-formyl-4-(beta)-D-(2,3,5-tri-O-benzoyl-ribofuranosyl)semicarbazide, which gave 4-(beta)-D-(2,3,5-tri-O-benzoylribofuranosyl)-1,2,4-triazolin-3-one upon dehydrative silylation. Methyl N-carbomethoxyformimidate was synthesized as a possible reagent for the synthesis of the other 1,2,4-triazolin-3-one products.","abstract_has_math":false,"creators":["Haines, David Richard"],"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":"2014-12-13T20:11:23Z","date_published":"2014-12-13T20:11:23Z","updated_at":"2026-07-22T22:25:57Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8203477"],"render_values":[{"text":"(UMI)AAI8203477","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/67290","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Haines, David Richard"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-13T20:11:23Z","10000-01-01","1981"]},{"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":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/67290","(UMI)AAI8203477"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Ribosidation of a series of azolinones was achieved via silylation and SnCl(,4) catalysis. Ribosidation of 4-imidazolin-2-one gave 1-(beta)-D-ribofuranosyl-4-imidazolin-2-one; of 1,2,4-triazolin-3-one gave 1-, 2-, and 4-(beta)-D-ribofuranosyl-1,2,4-triazolin-3-one, and 2,4-bis-(beta)-D-ribofuranosyl-1,2,4-triazolin-3-one; and of 2-tetrazolin-5-one gave 1-(beta)-D-ribofuranosyl-2-tetrazolin-5-one and 1,4-bis-(beta)-D-ribofuranosyl-2-tetrazolin-5-one. Structure assignments were based on microanalyses and ('1)H and ('13)C NMR spectra. The triazolinone mono-riboside isomer structures are differentiated by ('13)C NMR long-range coupling patterns, and two of the assignments were confirmed by X-ray crystallography. Improved syntheses were developed for two of the ribosides by fashioning the azolinone rings onto 2,3,5-tri-O-benzoylribofuranosyl isocyanate. Reaction of 2,3,5-tri-O-benzoylribofuranosyl isocyanate with (alpha)-aminoacetaldehyde diethyl acetal gave N-(2,2-diethoxyethyl)-N'-(beta)-D-(2,3,5-tri-O-benzoylribofuranosyl)-4-imidazolin-2-one in the presence of acid. Addition of formic acid hydrazide to 2,3,5-tri-O-benzoylribofuranosyl isocyanate gave 1-formyl-4-(beta)-D-(2,3,5-tri-O-benzoyl-ribofuranosyl)semicarbazide, which gave 4-(beta)-D-(2,3,5-tri-O-benzoylribofuranosyl)-1,2,4-triazolin-3-one upon dehydrative silylation. Methyl N-carbomethoxyformimidate was synthesized as a possible reagent for the synthesis of the other 1,2,4-triazolin-3-one products.","Carbamoylation of 4-imidazolin-2-one, 1,2,4-triazolin-3-one, and 2-tetrazolin-5-one was achieved using either trimethylsilyl isocyanate or phosgene and ammonia, giving 1-carbamoyl-4-imidazolin-2-one, 2- and 4-carbamoyl-1,2,4-triazolin-3-one, and 1-carbamoyl-2-tetrazolin-5-one, respectively. Protection of nucleosides with t-butyldimethylsilyl chloride permitted carbamoylation on the heterocyclic base using trimethylsilyl isocyanate. Protection of inosine gave 2',3',5'-tri-O-t-butyldimethylsilylinosine, which was carbamoylated to give 1-carbamoyl-2',3',5'-tri-O-t-butyldimethylsilylinosine.","Made available in DSpace on 2014-12-13T20:11:23Z (GMT). No. of bitstreams: 1 8203477.pdf: 2614017 bytes, checksum: 6ef4245e94c503a6bf3ab56ce9bb2bb1 (MD5) Previous issue date: 1981","Embargo set by: Seth Robbins for item 67468 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","92 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1981."]},{"key":"dc:title","label":"Title","values":["Synthesis and Structure Assignments of Novel Azolinone Ribonucleosides"]}]}],"canonical_facts":{"dc:creator":["Haines, David Richard"],"dc:date":["2014-12-13T20:11:23Z","10000-01-01","1981"],"dc:description":["Ribosidation of a series of azolinones was achieved via silylation and SnCl(,4) catalysis. Ribosidation of 4-imidazolin-2-one gave 1-(beta)-D-ribofuranosyl-4-imidazolin-2-one; of 1,2,4-triazolin-3-one gave 1-, 2-, and 4-(beta)-D-ribofuranosyl-1,2,4-triazolin-3-one, and 2,4-bis-(beta)-D-ribofuranosyl-1,2,4-triazolin-3-one; and of 2-tetrazolin-5-one gave 1-(beta)-D-ribofuranosyl-2-tetrazolin-5-one and 1,4-bis-(beta)-D-ribofuranosyl-2-tetrazolin-5-one. Structure assignments were based on microanalyses and ('1)H and ('13)C NMR spectra. The triazolinone mono-riboside isomer structures are differentiated by ('13)C NMR long-range coupling patterns, and two of the assignments were confirmed by X-ray crystallography. Improved syntheses were developed for two of the ribosides by fashioning the azolinone rings onto 2,3,5-tri-O-benzoylribofuranosyl isocyanate. Reaction of 2,3,5-tri-O-benzoylribofuranosyl isocyanate with (alpha)-aminoacetaldehyde diethyl acetal gave N-(2,2-diethoxyethyl)-N'-(beta)-D-(2,3,5-tri-O-benzoylribofuranosyl)-4-imidazolin-2-one in the presence of acid. Addition of formic acid hydrazide to 2,3,5-tri-O-benzoylribofuranosyl isocyanate gave 1-formyl-4-(beta)-D-(2,3,5-tri-O-benzoyl-ribofuranosyl)semicarbazide, which gave 4-(beta)-D-(2,3,5-tri-O-benzoylribofuranosyl)-1,2,4-triazolin-3-one upon dehydrative silylation. Methyl N-carbomethoxyformimidate was synthesized as a possible reagent for the synthesis of the other 1,2,4-triazolin-3-one products.","Carbamoylation of 4-imidazolin-2-one, 1,2,4-triazolin-3-one, and 2-tetrazolin-5-one was achieved using either trimethylsilyl isocyanate or phosgene and ammonia, giving 1-carbamoyl-4-imidazolin-2-one, 2- and 4-carbamoyl-1,2,4-triazolin-3-one, and 1-carbamoyl-2-tetrazolin-5-one, respectively. Protection of nucleosides with t-butyldimethylsilyl chloride permitted carbamoylation on the heterocyclic base using trimethylsilyl isocyanate. Protection of inosine gave 2',3',5'-tri-O-t-butyldimethylsilylinosine, which was carbamoylated to give 1-carbamoyl-2',3',5'-tri-O-t-butyldimethylsilylinosine.","Made available in DSpace on 2014-12-13T20:11:23Z (GMT). No. of bitstreams: 1 8203477.pdf: 2614017 bytes, checksum: 6ef4245e94c503a6bf3ab56ce9bb2bb1 (MD5) Previous issue date: 1981","Embargo set by: Seth Robbins for item 67468 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","92 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1981."],"dc:identifier":["http://hdl.handle.net/2142/67290","(UMI)AAI8203477"],"dc:language":["eng"],"dc:subject":["Chemistry, Organic"],"dc:title":["Synthesis and Structure Assignments of Novel Azolinone Ribonucleosides"],"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":"2026-07-22T22:25:57Z"}