{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70261"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70261","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Reaction of Nucleophiles With Perfluoroalkyl, Perfluoroacyl and Perfluoroalkanesulfonyl Groups","abstract":"Trifluoroacetyl triflate is readily prepared in 82% yield by the dehydration (phosphorus pentoxide) of a 2:1 mixture of trifluoroacetic acid and trifluoromethanesulfonic (triflic) acid. Reactions of this highly electrophilic trifluoroacetylating reagent with alcohols, ketones, ethers, amines, pyridines, and with ionic and covalent halides are reported. Trifluoroacetyl triflate is used in the synthesis of the first member of a new class of pyrylium salts, 2,6-dimethoxypyrylium triflate.","abstract_html":"Trifluoroacetyl triflate is readily prepared in 82% yield by the dehydration (phosphorus pentoxide) of a 2:1 mixture of trifluoroacetic acid and trifluoromethanesulfonic (triflic) acid. Reactions of this highly electrophilic trifluoroacetylating reagent with alcohols, ketones, ethers, amines, pyridines, and with ionic and covalent halides are reported. Trifluoroacetyl triflate is used in the synthesis of the first member of a new class of pyrylium salts, 2,6-dimethoxypyrylium triflate.","abstract_has_math":false,"creators":["Taylor, Stephen Lee"],"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":"2014-12-15T23:18:13Z","date_published":"2014-12-15T23:18:13Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8422166"],"render_values":[{"text":"(UMI)AAI8422166","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70261","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Taylor, Stephen Lee"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:13Z","10000-01-01","1984"]},{"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/2142/70261","(UMI)AAI8422166"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Trifluoroacetyl triflate is readily prepared in 82% yield by the dehydration (phosphorus pentoxide) of a 2:1 mixture of trifluoroacetic acid and trifluoromethanesulfonic (triflic) acid. Reactions of this highly electrophilic trifluoroacetylating reagent with alcohols, ketones, ethers, amines, pyridines, and with ionic and covalent halides are reported. Trifluoroacetyl triflate is used in the synthesis of the first member of a new class of pyrylium salts, 2,6-dimethoxypyrylium triflate.","A new and convenient synthesis of trifluoromethyl triflate (TFMT) has been devised. The addition of triflic anhydride to a catalytic amount of antimony pentafluoride produces TFMT in 94% yield utilizing a new and stronger Lewis acid catalyst produced in the reaction, F(,4)SbOSO(,2)CF(,3). A mechanism is presented which accounts for the substitution of fluorine ligand with a triflate ligand. Trifluoromethyl triflate does not trifluoromethylate nucleophiles (pyridine, triethylamine, iodide, phenyllithium, phenylmagnesium bromide, lithium thiophenolate, or sodium naphthalenide) but gives products which result from an initial attack of the nucleophile at sulfur. Fluoride ion, which is formed from the displacement of trifluoromethoxide ion from sulfur, is a chain carrier in the rapid decomposition of TFMT to give trifluoromethanesulfonyl fluoride and fluorophosgene.","Efficient synthetic routes to 2-substituted pyridines and 2,6-disubstituted pyridines and pyridine 1-oxides involving direction lithiation with the sterically hindered bases, lithium 2,2,6,6-tetramethylpiperidide (LiTMP) and lithium diisopropylamide (LDA), in the presence of electrophiles that are compatible with the base, e.g., trimethylsilylchloride (Me(,3)SiCl) and hexafluoroacetone (HFA), are described.","Made available in DSpace on 2014-12-15T23:18:13Z (GMT). No. of bitstreams: 1 8422166.pdf: 2881400 bytes, checksum: cc6c4923e6b481610572c9a388dace7f (MD5) Previous issue date: 1984","Embargo set by: Seth Robbins for item 70427 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","98 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1984."]},{"key":"dc:title","label":"Title","values":["Reaction of Nucleophiles With Perfluoroalkyl, Perfluoroacyl and Perfluoroalkanesulfonyl Groups"]}]}],"canonical_facts":{"dc:creator":["Taylor, Stephen Lee"],"dc:date":["2014-12-15T23:18:13Z","10000-01-01","1984"],"dc:description":["Trifluoroacetyl triflate is readily prepared in 82% yield by the dehydration (phosphorus pentoxide) of a 2:1 mixture of trifluoroacetic acid and trifluoromethanesulfonic (triflic) acid. Reactions of this highly electrophilic trifluoroacetylating reagent with alcohols, ketones, ethers, amines, pyridines, and with ionic and covalent halides are reported. Trifluoroacetyl triflate is used in the synthesis of the first member of a new class of pyrylium salts, 2,6-dimethoxypyrylium triflate.","A new and convenient synthesis of trifluoromethyl triflate (TFMT) has been devised. The addition of triflic anhydride to a catalytic amount of antimony pentafluoride produces TFMT in 94% yield utilizing a new and stronger Lewis acid catalyst produced in the reaction, F(,4)SbOSO(,2)CF(,3). A mechanism is presented which accounts for the substitution of fluorine ligand with a triflate ligand. Trifluoromethyl triflate does not trifluoromethylate nucleophiles (pyridine, triethylamine, iodide, phenyllithium, phenylmagnesium bromide, lithium thiophenolate, or sodium naphthalenide) but gives products which result from an initial attack of the nucleophile at sulfur. Fluoride ion, which is formed from the displacement of trifluoromethoxide ion from sulfur, is a chain carrier in the rapid decomposition of TFMT to give trifluoromethanesulfonyl fluoride and fluorophosgene.","Efficient synthetic routes to 2-substituted pyridines and 2,6-disubstituted pyridines and pyridine 1-oxides involving direction lithiation with the sterically hindered bases, lithium 2,2,6,6-tetramethylpiperidide (LiTMP) and lithium diisopropylamide (LDA), in the presence of electrophiles that are compatible with the base, e.g., trimethylsilylchloride (Me(,3)SiCl) and hexafluoroacetone (HFA), are described.","Made available in DSpace on 2014-12-15T23:18:13Z (GMT). No. of bitstreams: 1 8422166.pdf: 2881400 bytes, checksum: cc6c4923e6b481610572c9a388dace7f (MD5) Previous issue date: 1984","Embargo set by: Seth Robbins for item 70427 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","98 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1984."],"dc:identifier":["http://hdl.handle.net/2142/70261","(UMI)AAI8422166"],"dc:subject":["Chemistry, Organic"],"dc:title":["Reaction of Nucleophiles With Perfluoroalkyl, Perfluoroacyl and Perfluoroalkanesulfonyl Groups"],"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"}