Iminium salt dimethyliminium hexafluorophosphate (5), a precursor of the target compound BPDO-TTF, was synthesized in five steps with significant modifications in the previously worked out scheme. 2,3-Dihydrobenzo-1, 4-dioxin(1) was synthesized from catechol in a strongly alkaline medium. Compound (1) was dichlorinated with SO2Cl2 to give 2,3-dichloro-2,3-dihydrobenzo-1,4-dioxin (2). Subsequent reaction of compound (2) with sodium dimethyldithiocarbamate followed by dehydrochlorination in triethyl amine gave 1,4-Benzodioxin-2-N,N-dimethyldithiocarbamate (3). Bromination of compound (3) followed by treatment with hexafluorophosphoric acid yielded bromo-dimethyliminium hexafluorophosphate (4). Dehydrobromination of compound (4) by solid phase thermolysis reaction resulted in dimethyliminium hexafluorophosphate (5). In an effort to prepare BPDO-TTF from a coupling reaction of dithioselenone (7), the dimethyl iminium salt (5) was reacted with NaHSe; however, no pure dithioselenone was isolable from the reaction mixture. A photochemical coupling reaction was also attempted using dimethyl iminium salt (5) and trimethyl phosphite but the desired product did not form in a detectable amount.
","abstract_html":"<p>Iminium salt dimethyliminium hexafluorophosphate <em><strong>(5)</strong></em>, a precursor of the target compound BPDO-TTF, was synthesized in five steps with significant modifications in the previously worked out scheme. 2,3-Dihydrobenzo-1, 4-dioxin<em><strong>(1)</strong></em> was synthesized from catechol in a strongly alkaline medium. Compound <em><strong>(1)</strong></em> was dichlorinated with SO<sub>2</sub>Cl<sub>2</sub> to give 2,3-dichloro-2,3-dihydrobenzo-1,4-dioxin <em><strong>(2)</strong></em>. Subsequent reaction of compound <em><strong>(2)</strong></em> with sodium dimethyldithiocarbamate followed by dehydrochlorination in triethyl amine gave 1,4-Benzodioxin-2-N,N-dimethyldithiocarbamate <em><strong>(3)</strong></em>. Bromination of compound <em><strong>(3)</strong></em> followed by treatment with hexafluorophosphoric acid yielded bromo-dimethyliminium hexafluorophosphate (4). Dehydrobromination of compound <em><strong>(4)</strong></em> by solid phase thermolysis reaction resulted in dimethyliminium hexafluorophosphate <em><strong>(5)</strong></em>. In an effort to prepare BPDO-TTF from a coupling reaction of dithioselenone <em><strong>(7)</strong></em>, the dimethyl iminium salt <em><strong>(5)</strong></em> was reacted with NaHSe; however, no pure dithioselenone was isolable from the reaction mixture. A photochemical coupling reaction was also attempted using dimethyl iminium salt <em><strong>(5)</strong></em> and trimethyl phosphite but the desired product did not form in a detectable amount.</p>","abstract_has_math":false,"creators":["Biswas, Debanjan"],"institution":null,"degree_name":"MS (Master of Science)","degree_level":"Thesis - restricted","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2002,"date_issued":"2002-08-01T07:00:00Z","date_published":"2002-08-01T07:00:00Z","updated_at":"2026-07-24T02:19:21Z","subjects":["reduction","oxidation","Chemistry","Physical Sciences and Mathematics"],"languages":[],"rights":["Copyright by the authors."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://dc.etsu.edu/etd/689","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Biswas, Debanjan"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.available","label":"Dc Date Available","values":["1990-01-01T08:00:00Z"]},{"key":"dc:date.issued","label":"Date","values":["2002-08-01T07:00:00Z"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Thesis - restricted"]},{"key":"thesis:degree_name","label":"Degree Name","values":["MS (Master of Science)"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["reduction","oxidation","Chemistry","Physical Sciences and Mathematics"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["Copyright by the authors."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://dc.etsu.edu/context/etd/article/1846/viewcontent/BixwasD073102.pdf","https://dc.etsu.edu/etd/689"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Iminium salt dimethyliminium hexafluorophosphate (5), a precursor of the target compound BPDO-TTF, was synthesized in five steps with significant modifications in the previously worked out scheme. 2,3-Dihydrobenzo-1, 4-dioxin(1) was synthesized from catechol in a strongly alkaline medium. Compound (1) was dichlorinated with SO2Cl2 to give 2,3-dichloro-2,3-dihydrobenzo-1,4-dioxin (2). Subsequent reaction of compound (2) with sodium dimethyldithiocarbamate followed by dehydrochlorination in triethyl amine gave 1,4-Benzodioxin-2-N,N-dimethyldithiocarbamate (3). Bromination of compound (3) followed by treatment with hexafluorophosphoric acid yielded bromo-dimethyliminium hexafluorophosphate (4). Dehydrobromination of compound (4) by solid phase thermolysis reaction resulted in dimethyliminium hexafluorophosphate (5). In an effort to prepare BPDO-TTF from a coupling reaction of dithioselenone (7), the dimethyl iminium salt (5) was reacted with NaHSe; however, no pure dithioselenone was isolable from the reaction mixture. A photochemical coupling reaction was also attempted using dimethyl iminium salt (5) and trimethyl phosphite but the desired product did not form in a detectable amount.
"]},{"key":"dc:title","label":"Title","values":["A Modified Procedure for the Synthesis of Bis(phenylenedioxy)tetrathiafulvalene (BPDO-TTF): an Electron Donor for Charge Transfer Organic Complexes."]}]}],"canonical_facts":{"dc:creator":["Biswas, Debanjan"],"dc:date.available":["1990-01-01T08:00:00Z"],"dc:date.issued":["2002-08-01T07:00:00Z"],"dc:description.abstract":["Iminium salt dimethyliminium hexafluorophosphate (5), a precursor of the target compound BPDO-TTF, was synthesized in five steps with significant modifications in the previously worked out scheme. 2,3-Dihydrobenzo-1, 4-dioxin(1) was synthesized from catechol in a strongly alkaline medium. Compound (1) was dichlorinated with SO2Cl2 to give 2,3-dichloro-2,3-dihydrobenzo-1,4-dioxin (2). Subsequent reaction of compound (2) with sodium dimethyldithiocarbamate followed by dehydrochlorination in triethyl amine gave 1,4-Benzodioxin-2-N,N-dimethyldithiocarbamate (3). Bromination of compound (3) followed by treatment with hexafluorophosphoric acid yielded bromo-dimethyliminium hexafluorophosphate (4). Dehydrobromination of compound (4) by solid phase thermolysis reaction resulted in dimethyliminium hexafluorophosphate (5). In an effort to prepare BPDO-TTF from a coupling reaction of dithioselenone (7), the dimethyl iminium salt (5) was reacted with NaHSe; however, no pure dithioselenone was isolable from the reaction mixture. A photochemical coupling reaction was also attempted using dimethyl iminium salt (5) and trimethyl phosphite but the desired product did not form in a detectable amount.
"],"dc:identifier":["https://dc.etsu.edu/context/etd/article/1846/viewcontent/BixwasD073102.pdf","https://dc.etsu.edu/etd/689"],"dc:rights":["Copyright by the authors."],"dc:subject":["reduction","oxidation","Chemistry","Physical Sciences and Mathematics"],"dc:title":["A Modified Procedure for the Synthesis of Bis(phenylenedioxy)tetrathiafulvalene (BPDO-TTF): an Electron Donor for Charge Transfer Organic Complexes."],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Thesis - restricted"],"thesis:degree_name":["MS (Master of Science)"]},"updated_at":"2026-07-24T02:19:21Z"}