{"id":{"repo_id":"greenwich","oai_identifier":"oai:gala.gre.ac.uk:14969"},"canonical_url":"https://search.dev.ndltd.org/etd/greenwich/oai:gala.gre.ac.uk:14969","repository":{"repo_id":"greenwich","name":"University of Greenwich","base_url":"https://gala.gre.ac.uk/cgi/oai2"},"display":{"title":"The Beckmann and Schmidt rearrangements as an approach to the synthesis of diazabiphenylenes","abstract":"The Schmidt reaction of cis, trans, cis-tri cyclop, [5,3,0,0 2,6] deca-3,8-dione, a photodimer of cyclopent-2-en-l-one was found to give a mixture of two dilactams. The structure of the major dilactam was established as cis, trans, cis-3, 9-diazatricyclol [6,4,0,0 2,7] dodecane-4, 10-dione on the basis of its spectroscopic properties and those of its N,,N' –dimethyl and N,N'-dibenzyl derivatives. Single ring expansion of the diketone gave mainly cis, trans, cis 3-azatricyclo [6,3,0,0 2,7] undecane-4,9-dione, and a number of its transformation products are described. The Beckmann rearrangement of the mixture of dioximes derived from the diketone, also gave a mixture of two dilactams; the major component was established as cis, trans, cis-4,10-diazatricyclo [6,4,0,0 2,7] dodecane-3,9-dione on the basis of its spectroscopic data and those of its N,N'-dimethyl and N,N ! -dibenzyl derivatives. The minor component was found to be identical with that of the other dilactam obtained from the Schinidt reaction and was tentatively assigned as cis, trans, cis-3,10-diazatricyclo-[6,4,0,0 2,7] dodecane-4, 9-dione. Attempted reduction of the dilactams to the corresponding diamines was not successful but reduction of N,N'-dibenzyl-cis, trans, cis-3, 9-diazatricyclo [6,4,0,0 2,7] dodecane-4, 10-dione gave the corresponding diamine. Attempted dehydrogenation of the above diamine did not give any diazabiphenylene.","abstract_html":"The Schmidt reaction of cis, trans, cis-tri cyclop, [5,3,0,0 2,6] deca-3,8-dione, a photodimer of cyclopent-2-en-l-one was found to give a mixture of two dilactams. The structure of the major dilactam was established as cis, trans, cis-3, 9-diazatricyclol [6,4,0,0 2,7] dodecane-4, 10-dione on the basis of its spectroscopic properties and those of its N,,N' –dimethyl and N,N'-dibenzyl derivatives. Single ring expansion of the diketone gave mainly cis, trans, cis 3-azatricyclo [6,3,0,0 2,7] undecane-4,9-dione, and a number of its transformation products are described. The Beckmann rearrangement of the mixture of dioximes derived from the diketone, also gave a mixture of two dilactams; the major component was established as cis, trans, cis-4,10-diazatricyclo [6,4,0,0 2,7] dodecane-3,9-dione on the basis of its spectroscopic data and those of its N,N'-dimethyl and N,N ! -dibenzyl derivatives. The minor component was found to be identical with that of the other dilactam obtained from the Schinidt reaction and was tentatively assigned as cis, trans, cis-3,10-diazatricyclo-[6,4,0,0 2,7] dodecane-4, 9-dione. Attempted reduction of the dilactams to the corresponding diamines was not successful but reduction of N,N'-dibenzyl-cis, trans, cis-3, 9-diazatricyclo [6,4,0,0 2,7] dodecane-4, 10-dione gave the corresponding diamine. Attempted dehydrogenation of the above diamine did not give any diazabiphenylene.","abstract_has_math":false,"creators":["Mendonca, S."],"institution":"Thanes Polytechnic","degree_name":null,"degree_level":"mphil","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Rogers, V."],"committee_chairs":[],"committee_members":[],"year":1974,"date_issued":"1974-06","date_published":"1974-06","updated_at":"2026-07-24T02:25:50Z","subjects":["QD Chemistry"],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Rogers, V."]},{"key":"dc:contributor.sponsor","label":"Sponsor","values":["Thomas Morson and Son Limited, Enfield, Middlesex","Chemical Society Research Fund"]},{"key":"dc:creator","label":"Author","values":["Mendonca, S."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["1974-06"]},{"key":"dc:date.issued","label":"Date","values":["1974-06"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["School of Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["Thanes Polytechnic"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://gala.gre.ac.uk/id/eprint/14969/"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["mphil"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["QD Chemistry"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://gala.gre.ac.uk/id/eprint/14969/7/S.%20Mendonca%201974%20-%20secured.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The Schmidt reaction of cis, trans, cis-tri cyclop, [5,3,0,0 2,6] deca-3,8-dione, a photodimer of cyclopent-2-en-l-one was found to give a mixture of two dilactams. The structure of the major dilactam was established as cis, trans, cis-3, 9-diazatricyclol [6,4,0,0 2,7] dodecane-4, 10-dione on the basis of its spectroscopic properties and those of its N,,N' –dimethyl and N,N'-dibenzyl derivatives. Single ring expansion of the diketone gave mainly cis, trans, cis 3-azatricyclo [6,3,0,0 2,7] undecane-4,9-dione, and a number of its transformation products are described. The Beckmann rearrangement of the mixture of dioximes derived from the diketone, also gave a mixture of two dilactams; the major component was established as cis, trans, cis-4,10-diazatricyclo [6,4,0,0 2,7] dodecane-3,9-dione on the basis of its spectroscopic data and those of its N,N'-dimethyl and N,N ! -dibenzyl derivatives. The minor component was found to be identical with that of the other dilactam obtained from the Schinidt reaction and was tentatively assigned as cis, trans, cis-3,10-diazatricyclo-[6,4,0,0 2,7] dodecane-4, 9-dione. Attempted reduction of the dilactams to the corresponding diamines was not successful but reduction of N,N'-dibenzyl-cis, trans, cis-3, 9-diazatricyclo [6,4,0,0 2,7] dodecane-4, 10-dione gave the corresponding diamine. Attempted dehydrogenation of the above diamine did not give any diazabiphenylene."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["The Beckmann and Schmidt rearrangements as an approach to the synthesis of diazabiphenylenes"]}]}],"canonical_facts":{"dc:contributor.advisor":["Rogers, V."],"dc:contributor.sponsor":["Thomas Morson and Son Limited, Enfield, Middlesex","Chemical Society Research Fund"],"dc:creator":["Mendonca, S."],"dc:date":["1974-06"],"dc:date.issued":["1974-06"],"dc:description.abstract":["The Schmidt reaction of cis, trans, cis-tri cyclop, [5,3,0,0 2,6] deca-3,8-dione, a photodimer of cyclopent-2-en-l-one was found to give a mixture of two dilactams. The structure of the major dilactam was established as cis, trans, cis-3, 9-diazatricyclol [6,4,0,0 2,7] dodecane-4, 10-dione on the basis of its spectroscopic properties and those of its N,,N' –dimethyl and N,N'-dibenzyl derivatives. Single ring expansion of the diketone gave mainly cis, trans, cis 3-azatricyclo [6,3,0,0 2,7] undecane-4,9-dione, and a number of its transformation products are described. The Beckmann rearrangement of the mixture of dioximes derived from the diketone, also gave a mixture of two dilactams; the major component was established as cis, trans, cis-4,10-diazatricyclo [6,4,0,0 2,7] dodecane-3,9-dione on the basis of its spectroscopic data and those of its N,N'-dimethyl and N,N ! -dibenzyl derivatives. The minor component was found to be identical with that of the other dilactam obtained from the Schinidt reaction and was tentatively assigned as cis, trans, cis-3,10-diazatricyclo-[6,4,0,0 2,7] dodecane-4, 9-dione. Attempted reduction of the dilactams to the corresponding diamines was not successful but reduction of N,N'-dibenzyl-cis, trans, cis-3, 9-diazatricyclo [6,4,0,0 2,7] dodecane-4, 10-dione gave the corresponding diamine. Attempted dehydrogenation of the above diamine did not give any diazabiphenylene."],"dc:format":["application/pdf"],"dc:identifier.uri":["https://gala.gre.ac.uk/id/eprint/14969/7/S.%20Mendonca%201974%20-%20secured.pdf"],"dc:language":["en"],"dc:publisher.department":["School of Chemistry"],"dc:publisher.institution":["Thanes Polytechnic"],"dc:relation.isreferencedby":["https://gala.gre.ac.uk/id/eprint/14969/"],"dc:subject":["QD Chemistry"],"dc:title":["The Beckmann and Schmidt rearrangements as an approach to the synthesis of diazabiphenylenes"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["mphil"]},"updated_at":"2026-07-24T02:25:50Z"}