{"id":{"repo_id":"rgu","oai_identifier":"oai:rgu-repository.worktribe.com:1993226"},"canonical_url":"https://search.dev.ndltd.org/etd/rgu/oai:rgu-repository.worktribe.com:1993226","repository":{"repo_id":"rgu","name":"Robert Gordon University","base_url":"https://rgu-repository.worktribe.com/oaiprovider"},"display":{"title":"The synthesis and reactivity of 7-azaindolizines.","abstract":"Synthetic routes leading to 7-azaindolizines and the reactivity of this system together with other azaindolizines have been briefly reviewed. A number of simple alkyl, aryl, carboethoxy, methoxy, chloro and amino substituted 7-azaindolizines have been synthesised via the Chichibabin reaction between suitably substituted methylpyrazines and a-bromoketones. The structures of the products obtained have been confirmed spectroscopically (mainly by pmr spectroscopy) and elemental analysis. Examination of the pmr spectra of 7-azaindolizines in trifluoroacetic acid showed solely protonation at the non-bridgehead nitrogen. Similarly quaternisation was found to occur at the non-bridgehead nitrogen. Lithiation of 8-methyl-7-azaindolizine showed the 8-methyl group of 2,8-dimethy1-7-azaindoilzine to be acidic. Reaction between 2,3,8-trimethyl-7-azaindolizine and ethoxalyl chloride gave a diketodipyrrolo[1 ,2-a:2,1-c]pyrazine system. A number of electrophilic substitution reactions occurred at C-3 position. Nucleophilic replacement of chlorine by methoxide and amino from 8-chloro-2-methyl-7-azaindolizine occurred readily. A number of simple alkyl, aryl, and carboethoxy substituted dipyrrolo[1 ,2-a;2,1-c]pyrazines have been obtained by the Chichibabin reaction between appropriate substituted 8-methyl-7-azaindolizines and a-bromoketones. The structures of these products have been established spectroscopically. An examination of the pmr spectra of dipyrrolo-[1,2-a:2,1-c]pyrazines in trifluoroacetic acid showed this system preferentially protonates at C-3 and C-8 postions. When positions 3 and 8 are substituted the C-3 conjugate acid cation predominates together with minor amounts of the C-1 cation. Dipyrrolo[1,2-a:2,1-c]pyrazines undergo electrophilic substitution preferentially at C-3(C-8) and when 3,8-disubstituted, substitution then occurs at C-1(C-10). A brief survey of reaction between relevant nitrogen heteroaromatics and DMAD has been reviewed. The reaction between 7-azaindolizines and DMAD gave products involving bonding at the non-bridgehead nitrogen and the adjacent C-8 position or 8-substituent.","abstract_html":"Synthetic routes leading to 7-azaindolizines and the reactivity of this system together with other azaindolizines have been briefly reviewed. A number of simple alkyl, aryl, carboethoxy, methoxy, chloro and amino substituted 7-azaindolizines have been synthesised via the Chichibabin reaction between suitably substituted methylpyrazines and a-bromoketones. The structures of the products obtained have been confirmed spectroscopically (mainly by pmr spectroscopy) and elemental analysis. Examination of the pmr spectra of 7-azaindolizines in trifluoroacetic acid showed solely protonation at the non-bridgehead nitrogen. Similarly quaternisation was found to occur at the non-bridgehead nitrogen. Lithiation of 8-methyl-7-azaindolizine showed the 8-methyl group of 2,8-dimethy1-7-azaindoilzine to be acidic. Reaction between 2,3,8-trimethyl-7-azaindolizine and ethoxalyl chloride gave a diketodipyrrolo[1 ,2-a:2,1-c]pyrazine system. A number of electrophilic substitution reactions occurred at C-3 position. Nucleophilic replacement of chlorine by methoxide and amino from 8-chloro-2-methyl-7-azaindolizine occurred readily. A number of simple alkyl, aryl, and carboethoxy substituted dipyrrolo[1 ,2-a;2,1-c]pyrazines have been obtained by the Chichibabin reaction between appropriate substituted 8-methyl-7-azaindolizines and a-bromoketones. The structures of these products have been established spectroscopically. An examination of the pmr spectra of dipyrrolo-[1,2-a:2,1-c]pyrazines in trifluoroacetic acid showed this system preferentially protonates at C-3 and C-8 postions. When positions 3 and 8 are substituted the C-3 conjugate acid cation predominates together with minor amounts of the C-1 cation. Dipyrrolo[1,2-a:2,1-c]pyrazines undergo electrophilic substitution preferentially at C-3(C-8) and when 3,8-disubstituted, substitution then occurs at C-1(C-10). A brief survey of reaction between relevant nitrogen heteroaromatics and DMAD has been reviewed. The reaction between 7-azaindolizines and DMAD gave products involving bonding at the non-bridgehead nitrogen and the adjacent C-8 position or 8-substituent.","abstract_has_math":false,"creators":["Kong Thoo Lin, Paul Vee Siew"],"institution":"Robert Gordon's Institute of Technology","degree_name":"PhD","degree_level":"Doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["M. Fraser, R. Buchan and N.F. Elmore"],"committee_chairs":[],"committee_members":[],"year":1986,"date_issued":"1986","date_published":"1986","updated_at":"2026-07-24T04:10:03Z","subjects":["7-azaindolizines","Chichibabin reaction","Spectroscopy","Protonation","Electrophilic substitution","Nucleophilic replacement"],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["oai:rgu-repository.worktribe.com:1993226","https://doi.org/10.48526/rgu-wt-1993226"],"render_values":[{"text":"oai:rgu-repository.worktribe.com:1993226","href":null,"code":true},{"text":"https://doi.org/10.48526/rgu-wt-1993226","href":"https://doi.org/10.48526/rgu-wt-1993226","code":true}]}]},"links":{"outbound_url":"https://rgu-repository.worktribe.com/1993226/1/KONG%20THOO%20LIN%201986%20The%20synthesis%20and%20reactivity","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["M. 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A number of simple alkyl, aryl, carboethoxy, methoxy, chloro and amino substituted 7-azaindolizines have been synthesised via the Chichibabin reaction between suitably substituted methylpyrazines and a-bromoketones. The structures of the products obtained have been confirmed spectroscopically (mainly by pmr spectroscopy) and elemental analysis. Examination of the pmr spectra of 7-azaindolizines in trifluoroacetic acid showed solely protonation at the non-bridgehead nitrogen. Similarly quaternisation was found to occur at the non-bridgehead nitrogen. Lithiation of 8-methyl-7-azaindolizine showed the 8-methyl group of 2,8-dimethy1-7-azaindoilzine to be acidic. Reaction between 2,3,8-trimethyl-7-azaindolizine and ethoxalyl chloride gave a diketodipyrrolo[1 ,2-a:2,1-c]pyrazine system. A number of electrophilic substitution reactions occurred at C-3 position. Nucleophilic replacement of chlorine by methoxide and amino from 8-chloro-2-methyl-7-azaindolizine occurred readily. A number of simple alkyl, aryl, and carboethoxy substituted dipyrrolo[1 ,2-a;2,1-c]pyrazines have been obtained by the Chichibabin reaction between appropriate substituted 8-methyl-7-azaindolizines and a-bromoketones. The structures of these products have been established spectroscopically. An examination of the pmr spectra of dipyrrolo-[1,2-a:2,1-c]pyrazines in trifluoroacetic acid showed this system preferentially protonates at C-3 and C-8 postions. When positions 3 and 8 are substituted the C-3 conjugate acid cation predominates together with minor amounts of the C-1 cation. Dipyrrolo[1,2-a:2,1-c]pyrazines undergo electrophilic substitution preferentially at C-3(C-8) and when 3,8-disubstituted, substitution then occurs at C-1(C-10). A brief survey of reaction between relevant nitrogen heteroaromatics and DMAD has been reviewed. The reaction between 7-azaindolizines and DMAD gave products involving bonding at the non-bridgehead nitrogen and the adjacent C-8 position or 8-substituent."]},{"key":"dc:title","label":"Title","values":["The synthesis and reactivity of 7-azaindolizines."]}]}],"canonical_facts":{"dc:contributor.advisor":["M. Fraser, R. Buchan and N.F. Elmore"],"dc:contributor.sponsor":["RGU Internal Funding"],"dc:creator":["Kong Thoo Lin, Paul Vee Siew"],"dc:date":["1986-11-30"],"dc:date.issued":["1986"],"dc:description.abstract":["Synthetic routes leading to 7-azaindolizines and the reactivity of this system together with other azaindolizines have been briefly reviewed. A number of simple alkyl, aryl, carboethoxy, methoxy, chloro and amino substituted 7-azaindolizines have been synthesised via the Chichibabin reaction between suitably substituted methylpyrazines and a-bromoketones. The structures of the products obtained have been confirmed spectroscopically (mainly by pmr spectroscopy) and elemental analysis. Examination of the pmr spectra of 7-azaindolizines in trifluoroacetic acid showed solely protonation at the non-bridgehead nitrogen. Similarly quaternisation was found to occur at the non-bridgehead nitrogen. Lithiation of 8-methyl-7-azaindolizine showed the 8-methyl group of 2,8-dimethy1-7-azaindoilzine to be acidic. Reaction between 2,3,8-trimethyl-7-azaindolizine and ethoxalyl chloride gave a diketodipyrrolo[1 ,2-a:2,1-c]pyrazine system. A number of electrophilic substitution reactions occurred at C-3 position. Nucleophilic replacement of chlorine by methoxide and amino from 8-chloro-2-methyl-7-azaindolizine occurred readily. A number of simple alkyl, aryl, and carboethoxy substituted dipyrrolo[1 ,2-a;2,1-c]pyrazines have been obtained by the Chichibabin reaction between appropriate substituted 8-methyl-7-azaindolizines and a-bromoketones. The structures of these products have been established spectroscopically. An examination of the pmr spectra of dipyrrolo-[1,2-a:2,1-c]pyrazines in trifluoroacetic acid showed this system preferentially protonates at C-3 and C-8 postions. When positions 3 and 8 are substituted the C-3 conjugate acid cation predominates together with minor amounts of the C-1 cation. Dipyrrolo[1,2-a:2,1-c]pyrazines undergo electrophilic substitution preferentially at C-3(C-8) and when 3,8-disubstituted, substitution then occurs at C-1(C-10). A brief survey of reaction between relevant nitrogen heteroaromatics and DMAD has been reviewed. The reaction between 7-azaindolizines and DMAD gave products involving bonding at the non-bridgehead nitrogen and the adjacent C-8 position or 8-substituent."],"dc:identifier":["oai:rgu-repository.worktribe.com:1993226","https://doi.org/10.48526/rgu-wt-1993226"],"dc:identifier.uri":["https://rgu-repository.worktribe.com/1993226/1/KONG%20THOO%20LIN%201986%20The%20synthesis%20and%20reactivity"],"dc:language":["en"],"dc:publisher.institution":["Robert Gordon's Institute of Technology"],"dc:relation.isreferencedby":["https://rgu-repository.worktribe.com/output/1993226"],"dc:subject":["7-azaindolizines","Chichibabin reaction","Spectroscopy","Protonation","Electrophilic substitution","Nucleophilic replacement"],"dc:title":["The synthesis and reactivity of 7-azaindolizines."],"dc:type":["Thesis"],"dc:type.qualificationlevel":["Doctoral"],"dc:type.qualificationname":["PhD"]},"updated_at":"2026-07-24T04:10:03Z"}