{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70342"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70342","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Development of Fluorine-18 Halofluorination and Fluorine-18 Fluoride Ion Displacement Reactions for the Synthesis of Fluorine-18 Labeled Radiopharmaceuticals (Spiperone, Spiroperidol, N-Alkylation, Radioactivity)","abstract":"Two fluorine-18 labeling methods, ('18)F halofluorination and ('18)F fluoride ion displacement reactions, have been developed to assess their potential for labeling molecules with the positron-emitting radionuclide fluorine-18 at the no-carrier-added level.","abstract_html":"Two fluorine-18 labeling methods, ('18)F halofluorination and ('18)F fluoride ion displacement reactions, have been developed to assess their potential for labeling molecules with the positron-emitting radionuclide fluorine-18 at the no-carrier-added level.","abstract_has_math":false,"creators":["Chi, Dae Yoon"],"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":"2014-12-15T23:18:49Z","date_published":"2014-12-15T23:18:49Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8701459"],"render_values":[{"text":"(UMI)AAI8701459","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70342","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Chi, Dae Yoon"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:49Z","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/2142/70342","(UMI)AAI8701459"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Two fluorine-18 labeling methods, ('18)F halofluorination and ('18)F fluoride ion displacement reactions, have been developed to assess their potential for labeling molecules with the positron-emitting radionuclide fluorine-18 at the no-carrier-added level.","Olefin halofluorination involves the in situ generation of a halogen-fluoride reagent and subsequent addition to an olefin. The characteristics of this reaction were investigated with three model olefins (allylbenzene, 1-hexene, and propene). The most favorable conditions for halofluorination utilized 1,3-dibromo-5,5-dimethylhydantoin with dichloromethane as solvent. By this reaction, allylbenzene was labeled with fluorine-18 in 32% yield, under either carrier-added or no-carrier-added conditions. Transformations of halofluorination products, by either dehalogenation or N-alkylation, provide fluoroalkyl compounds or N-fluoroalkylated nitrogen compounds, respectively.","A two-step method for the preparation of fluoroalkyl substituted amines and amides has been achieved. The sequence involves fluoride ion displacement of trifluoromethanesulfonates (triflates) from short-chain haloalkyl triflates, followed by fluoroalkylation of the amine or amide. Alternatively, short-chain fluoroalkyl halides can be prepared by halofluorination of a terminal olefin. These reactions have been used to prepare various fluoroalkyl derivatives of 1-phenylpiperazine and N-fluoroalkyl derivatives of the neuroleptic agent spiperone. The sequence is rapid, convenient, and efficient, even when fluoride ion is the limiting reagent.","A series of fluorine-18 labeled N-fluoroalkylated spiperone derivatives were synthesized by N-alkylation of spiperone with fluoroalkyl halides. The fluoroalkylating species 2- ('18)F fluoroethyl bromide and 3- ('18)F fluoropropyl bromide were prepared by ('18)F fluoride ion displacement of the corresponding triflates. By this method, 2- ('18)F fluoroethyl and 3- ('18)F fluoropropyl spiperone derivatives can be both prepared and purified rapidly and conveniently (within 40 min) in yields of 30-40%. An alternative approach, suitable for the preparation of 2- ('18)F fluoroalkyl (ethyl, propyl, butyl, pentyl and hexyl) spiperone derivatives, involves iodo ('18)F fluorination of terminal olefins, followed by N-alkylation of spiperone (overall yields, <5%). N-(3- ('18)F Fluoropropyl)spiperone shows excellent selectivity for target tissue uptake in vivo.","Olefin halofluorination and fluoride ion displacement of haloalkyl triflate are readily adaptable to the preparation of a variety of compounds labeled with the short half-life (t(, 1/2) = 110 min) positron-emitting radionuclide fluorine-18.","Made available in DSpace on 2014-12-15T23:18:49Z (GMT). No. of bitstreams: 1 8701459.pdf: 4152320 bytes, checksum: 4bbb7319804a2c8fd22461bfe5bdb14f (MD5) Previous issue date: 1986","Embargo set by: Seth Robbins for item 70508 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","132 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986."]},{"key":"dc:title","label":"Title","values":["Development of Fluorine-18 Halofluorination and Fluorine-18 Fluoride Ion Displacement Reactions for the Synthesis of Fluorine-18 Labeled Radiopharmaceuticals (Spiperone, Spiroperidol, N-Alkylation, Radioactivity)"]}]}],"canonical_facts":{"dc:creator":["Chi, Dae Yoon"],"dc:date":["2014-12-15T23:18:49Z","10000-01-01","1986"],"dc:description":["Two fluorine-18 labeling methods, ('18)F halofluorination and ('18)F fluoride ion displacement reactions, have been developed to assess their potential for labeling molecules with the positron-emitting radionuclide fluorine-18 at the no-carrier-added level.","Olefin halofluorination involves the in situ generation of a halogen-fluoride reagent and subsequent addition to an olefin. The characteristics of this reaction were investigated with three model olefins (allylbenzene, 1-hexene, and propene). The most favorable conditions for halofluorination utilized 1,3-dibromo-5,5-dimethylhydantoin with dichloromethane as solvent. By this reaction, allylbenzene was labeled with fluorine-18 in 32% yield, under either carrier-added or no-carrier-added conditions. Transformations of halofluorination products, by either dehalogenation or N-alkylation, provide fluoroalkyl compounds or N-fluoroalkylated nitrogen compounds, respectively.","A two-step method for the preparation of fluoroalkyl substituted amines and amides has been achieved. The sequence involves fluoride ion displacement of trifluoromethanesulfonates (triflates) from short-chain haloalkyl triflates, followed by fluoroalkylation of the amine or amide. Alternatively, short-chain fluoroalkyl halides can be prepared by halofluorination of a terminal olefin. These reactions have been used to prepare various fluoroalkyl derivatives of 1-phenylpiperazine and N-fluoroalkyl derivatives of the neuroleptic agent spiperone. The sequence is rapid, convenient, and efficient, even when fluoride ion is the limiting reagent.","A series of fluorine-18 labeled N-fluoroalkylated spiperone derivatives were synthesized by N-alkylation of spiperone with fluoroalkyl halides. The fluoroalkylating species 2- ('18)F fluoroethyl bromide and 3- ('18)F fluoropropyl bromide were prepared by ('18)F fluoride ion displacement of the corresponding triflates. By this method, 2- ('18)F fluoroethyl and 3- ('18)F fluoropropyl spiperone derivatives can be both prepared and purified rapidly and conveniently (within 40 min) in yields of 30-40%. An alternative approach, suitable for the preparation of 2- ('18)F fluoroalkyl (ethyl, propyl, butyl, pentyl and hexyl) spiperone derivatives, involves iodo ('18)F fluorination of terminal olefins, followed by N-alkylation of spiperone (overall yields, <5%). N-(3- ('18)F Fluoropropyl)spiperone shows excellent selectivity for target tissue uptake in vivo.","Olefin halofluorination and fluoride ion displacement of haloalkyl triflate are readily adaptable to the preparation of a variety of compounds labeled with the short half-life (t(, 1/2) = 110 min) positron-emitting radionuclide fluorine-18.","Made available in DSpace on 2014-12-15T23:18:49Z (GMT). No. of bitstreams: 1 8701459.pdf: 4152320 bytes, checksum: 4bbb7319804a2c8fd22461bfe5bdb14f (MD5) Previous issue date: 1986","Embargo set by: Seth Robbins for item 70508 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","132 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986."],"dc:identifier":["http://hdl.handle.net/2142/70342","(UMI)AAI8701459"],"dc:subject":["Chemistry, Organic"],"dc:title":["Development of Fluorine-18 Halofluorination and Fluorine-18 Fluoride Ion Displacement Reactions for the Synthesis of Fluorine-18 Labeled Radiopharmaceuticals (Spiperone, Spiroperidol, N-Alkylation, Radioactivity)"],"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"}