{"id":{"repo_id":"wku-diss","oai_identifier":"oai:digitalcommons.wku.edu:theses-1704"},"canonical_url":"https://search.dev.ndltd.org/etd/wku-diss/oai:digitalcommons.wku.edu:theses-1704","repository":{"repo_id":"wku-diss","name":"Western Kentucky University","base_url":"https://digitalcommons.wku.edu/do/oai/"},"display":{"title":"Metalation of the Di- and Tri-Methoxybenzenes","abstract":"Hydrocarbon solvents are known to be unreactive towards organolithium reagents and also to afford little support for ortho-metalation reactions. In contrast, both m- and odimethoxybenzene afford 80% \"ion-multiple specific\" monometalation in hydrocarbon solvent (n-hexane, cyclohexane, toluene) without the addition of any catalyst (ether or amine). These observations are, in part, attributed to the 1,2- and 1,3- formation of the n-BuLi dimer, the most reactive form of n-BuLi. In other words these substrates are acting in a \"substrate-catalyzed\" manner. Extensions of these concepts to 1,2,3-, 1,2,4- and 1,3,5-trimethoxybenzenes have led to further unusual observations. In particular, the 1,2,3-system affords an interesting nucleophilic aromatic substitution reaction. This autocatalytic mode of ortho-metalation offers additional insight into the controversy regarding the participation of a dimer intermediate in the mechanism of the directed ortho-metalation reaction.","abstract_html":"Hydrocarbon solvents are known to be unreactive towards organolithium reagents and also to afford little support for ortho-metalation reactions. In contrast, both m- and odimethoxybenzene afford 80% "ion-multiple specific" monometalation in hydrocarbon solvent (n-hexane, cyclohexane, toluene) without the addition of any catalyst (ether or amine). These observations are, in part, attributed to the 1,2- and 1,3- formation of the n-BuLi dimer, the most reactive form of n-BuLi. In other words these substrates are acting in a "substrate-catalyzed" manner. Extensions of these concepts to 1,2,3-, 1,2,4- and 1,3,5-trimethoxybenzenes have led to further unusual observations. In particular, the 1,2,3-system affords an interesting nucleophilic aromatic substitution reaction. This autocatalytic mode of ortho-metalation offers additional insight into the controversy regarding the participation of a dimer intermediate in the mechanism of the directed ortho-metalation reaction.","abstract_has_math":false,"creators":["Shelton, Phillip"],"institution":null,"degree_name":"Master of Science","degree_level":null,"degree_discipline":"Department of Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2001,"date_issued":"2001-08-01T07:00:00Z","date_published":"2001-08-01T07:00:00Z","updated_at":"2026-07-24T06:07:42Z","subjects":["Chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://digitalcommons.wku.edu/theses/701","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Shelton, Phillip"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Department of Chemistry"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Master of Science"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://digitalcommons.wku.edu/theses/701"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Hydrocarbon solvents are known to be unreactive towards organolithium reagents and also to afford little support for ortho-metalation reactions. In contrast, both m- and odimethoxybenzene afford 80% \"ion-multiple specific\" monometalation in hydrocarbon solvent (n-hexane, cyclohexane, toluene) without the addition of any catalyst (ether or amine). These observations are, in part, attributed to the 1,2- and 1,3- formation of the n-BuLi dimer, the most reactive form of n-BuLi. In other words these substrates are acting in a \"substrate-catalyzed\" manner. Extensions of these concepts to 1,2,3-, 1,2,4- and 1,3,5-trimethoxybenzenes have led to further unusual observations. In particular, the 1,2,3-system affords an interesting nucleophilic aromatic substitution reaction. This autocatalytic mode of ortho-metalation offers additional insight into the controversy regarding the participation of a dimer intermediate in the mechanism of the directed ortho-metalation reaction."]},{"key":"dc:title","label":"Title","values":["Metalation of the Di- and Tri-Methoxybenzenes"]}]}],"canonical_facts":{"dc:creator":["Shelton, Phillip"],"dc:description.abstract":["Hydrocarbon solvents are known to be unreactive towards organolithium reagents and also to afford little support for ortho-metalation reactions. In contrast, both m- and odimethoxybenzene afford 80% \"ion-multiple specific\" monometalation in hydrocarbon solvent (n-hexane, cyclohexane, toluene) without the addition of any catalyst (ether or amine). These observations are, in part, attributed to the 1,2- and 1,3- formation of the n-BuLi dimer, the most reactive form of n-BuLi. In other words these substrates are acting in a \"substrate-catalyzed\" manner. Extensions of these concepts to 1,2,3-, 1,2,4- and 1,3,5-trimethoxybenzenes have led to further unusual observations. In particular, the 1,2,3-system affords an interesting nucleophilic aromatic substitution reaction. This autocatalytic mode of ortho-metalation offers additional insight into the controversy regarding the participation of a dimer intermediate in the mechanism of the directed ortho-metalation reaction."],"dc:identifier":["https://digitalcommons.wku.edu/theses/701"],"dc:subject":["Chemistry"],"dc:title":["Metalation of the Di- and Tri-Methoxybenzenes"],"dc:type":["Thesis"],"thesis:degree_discipline":["Department of Chemistry"],"thesis:degree_name":["Master of Science"]},"updated_at":"2026-07-24T06:07:42Z"}