{"id":{"repo_id":"wku-diss","oai_identifier":"oai:digitalcommons.wku.edu:theses-1644"},"canonical_url":"https://search.dev.ndltd.org/etd/wku-diss/oai:digitalcommons.wku.edu:theses-1644","repository":{"repo_id":"wku-diss","name":"Western Kentucky University","base_url":"https://digitalcommons.wku.edu/do/oai/"},"display":{"title":"Directed Ortho-Metalation of Dimethylarylamines","abstract":"Site-specific product(s) from the reaction of benzene derivatives with various reagents is a need of researchers at numerous laboratories, particularly those in the pharmaceutical industry. Such derivatives can be synthesized directly, i.e., by substitution of a proton, using either of two procedures: electrophilic aromatic substitution (EAS) or directed ortho-metalation (DoM). Directed ortho-metalation (DoM) is an alternative aromatic substitution process initiated by organolithium reagents which provides regiospecific substitution exclusively at the ortho- position (equation). The focus of this study is to find hydrocarbon media that will permit the maximum extent of metalation of several dimethylarylamines. The dimethylamine-containing substituents constitute directing metalation groups (DMG's) for the various aryl systems investigated. Maximization of the extents of ortho-lithiation of dimethylaniline [DMG = - N(CH3)2] and dimethylbenzylamine [DMG = -CH2N(CH3)2] have now been achieved using novel combinations of solvent, temperature and increments of catalyst. Studies of substituted dimethylanilines and dimethylbenzylamines containing a second DMG have yielded mixed results. Both metalation condition parameters as well as certain mechanistic aspects are altered by inclusion of a second DMG into these two parent systems.","abstract_html":"Site-specific product(s) from the reaction of benzene derivatives with various reagents is a need of researchers at numerous laboratories, particularly those in the pharmaceutical industry. Such derivatives can be synthesized directly, i.e., by substitution of a proton, using either of two procedures: electrophilic aromatic substitution (EAS) or directed ortho-metalation (DoM). Directed ortho-metalation (DoM) is an alternative aromatic substitution process initiated by organolithium reagents which provides regiospecific substitution exclusively at the ortho- position (equation). The focus of this study is to find hydrocarbon media that will permit the maximum extent of metalation of several dimethylarylamines. The dimethylamine-containing substituents constitute directing metalation groups (DMG's) for the various aryl systems investigated. Maximization of the extents of ortho-lithiation of dimethylaniline [DMG = - N(CH3)2] and dimethylbenzylamine [DMG = -CH2N(CH3)2] have now been achieved using novel combinations of solvent, temperature and increments of catalyst. Studies of substituted dimethylanilines and dimethylbenzylamines containing a second DMG have yielded mixed results. Both metalation condition parameters as well as certain mechanistic aspects are altered by inclusion of a second DMG into these two parent systems.","abstract_has_math":false,"creators":["Timmons, Michael"],"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":2002,"date_issued":"2002-12-01T08:00:00Z","date_published":"2002-12-01T08:00:00Z","updated_at":"2026-07-24T06:07:42Z","subjects":["Chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://digitalcommons.wku.edu/theses/641","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Timmons, Michael"]}]},{"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/641"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Site-specific product(s) from the reaction of benzene derivatives with various reagents is a need of researchers at numerous laboratories, particularly those in the pharmaceutical industry. Such derivatives can be synthesized directly, i.e., by substitution of a proton, using either of two procedures: electrophilic aromatic substitution (EAS) or directed ortho-metalation (DoM). Directed ortho-metalation (DoM) is an alternative aromatic substitution process initiated by organolithium reagents which provides regiospecific substitution exclusively at the ortho- position (equation). The focus of this study is to find hydrocarbon media that will permit the maximum extent of metalation of several dimethylarylamines. The dimethylamine-containing substituents constitute directing metalation groups (DMG's) for the various aryl systems investigated. Maximization of the extents of ortho-lithiation of dimethylaniline [DMG = - N(CH3)2] and dimethylbenzylamine [DMG = -CH2N(CH3)2] have now been achieved using novel combinations of solvent, temperature and increments of catalyst. Studies of substituted dimethylanilines and dimethylbenzylamines containing a second DMG have yielded mixed results. Both metalation condition parameters as well as certain mechanistic aspects are altered by inclusion of a second DMG into these two parent systems."]},{"key":"dc:title","label":"Title","values":["Directed Ortho-Metalation of Dimethylarylamines"]}]}],"canonical_facts":{"dc:creator":["Timmons, Michael"],"dc:description.abstract":["Site-specific product(s) from the reaction of benzene derivatives with various reagents is a need of researchers at numerous laboratories, particularly those in the pharmaceutical industry. Such derivatives can be synthesized directly, i.e., by substitution of a proton, using either of two procedures: electrophilic aromatic substitution (EAS) or directed ortho-metalation (DoM). Directed ortho-metalation (DoM) is an alternative aromatic substitution process initiated by organolithium reagents which provides regiospecific substitution exclusively at the ortho- position (equation). The focus of this study is to find hydrocarbon media that will permit the maximum extent of metalation of several dimethylarylamines. The dimethylamine-containing substituents constitute directing metalation groups (DMG's) for the various aryl systems investigated. Maximization of the extents of ortho-lithiation of dimethylaniline [DMG = - N(CH3)2] and dimethylbenzylamine [DMG = -CH2N(CH3)2] have now been achieved using novel combinations of solvent, temperature and increments of catalyst. Studies of substituted dimethylanilines and dimethylbenzylamines containing a second DMG have yielded mixed results. Both metalation condition parameters as well as certain mechanistic aspects are altered by inclusion of a second DMG into these two parent systems."],"dc:identifier":["https://digitalcommons.wku.edu/theses/641"],"dc:subject":["Chemistry"],"dc:title":["Directed Ortho-Metalation of Dimethylarylamines"],"dc:type":["Thesis"],"thesis:degree_discipline":["Department of Chemistry"],"thesis:degree_name":["Master of Science"]},"updated_at":"2026-07-24T06:07:42Z"}