[{"key":"dc.contributor.author","value":"Millward, Stewart","language":null},{"key":"dc.date.accessioned","value":"2011-10-27T16:06:38Z","language":null},{"key":"dc.date.available","value":"2011-10-27T16:06:38Z","language":null},{"key":"dc.date.issued","value":"1963","language":null},{"key":"dc.identifier.uri","value":"http:\/\/hdl.handle.net\/2429\/38346","language":null},{"key":"dc.description.abstract","value":"Benzophenone semicarbazone reacted with carbon monoxide at about 300 atmospheres and at 235-245\u00b0 in the presence of preformed dicobalt octacarbonyl as catalyst to yield 3-phenylphthalimidine (XXXVII), 3-phenyl-2-(N-benzhydrylcarboxamido)phthalimidine (XXXIV), N,N\u2019-dibenzhydrylurea (XXXV), and N-benzhydrylurea (XXXVI). At 200-220\u00b0 benzophenone semicarbazone gave N-benzhydrylurea (XXXVI), benzophenone azine (XXXVIIl), and benzophenone 4benzhydrylsemicarbazone (XXXJX). When the reaction temperature was further reduced to 175-180\u00b0, benzophenone semicarbazone did not produce the carbonylation product obtained in the second experiment but only the degradation and reduction products, XXXVIIl and XXXIX respectively. Carbonylation of benzophenone azine (XXXVIIl) at 235-245\u00b0 produced 3-phenylphthalimidine (XXXVIl), whereas carbonylation of benzophenone 4-benzhydrylsemicarbazone at the same temperature yielded 3-phenylphthalimidine and 3-phenyl-2-(N-benzhydryl-carboxaraido)phthalimidine (XXXIV).\r\nAn independent synthesis of the latter compound and of benzophenone 4-benzhydrylsemicarbazone, both in good yield, has been carried out.\r\nWhen benzaldehyde semicarbazone was carbonylated at 200-220\u00b0 only the degradation product, benzaldehyde azine (XLIl) was formed. Increasing the temperature to 235-245\u00b0 did not alter the course of the reaction. Carbonylation of benzaldehyde azine at 235-245\u00b0 yielded 2-benzylphthalimidine (XLVIIl), phthalimidine (L), and 2-(N-benzyl-carboxamido)phthalimidine (XLVI). The significance of the presence of phthalimidine and 2-(N-benzylcarboxaraido)phthalimidine in the carbonylation products of benzaldehyde azine is discussed in regard to the mechanism of the cyclization reaction. A mechanism is proposed for the cyclization reaction and evidence is presented in support of the proposal.\r\nThe ureido group (-NHCONH\u2082) or its degradation products has been shown to have an inhibitory effect on the catalytic activity of dicobalt octacarbonyl.\r\nAn independent synthesis of 2-(N-benzyIcarboxamido)phthalimidine is also reported.","language":"en"},{"key":"dc.language.iso","value":"eng","language":"en"},{"key":"dc.publisher","value":"University of British Columbia","language":"en"},{"key":"dc.rights","value":"For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https:\/\/open.library.ubc.ca\/terms_of_use.","language":null},{"key":"dc.title","value":"Direct carbonylation of aromatic semi-carbazones and azines","language":"en"},{"key":"dc.type","value":"Text","language":"en"},{"key":"dc.degree.name","value":"Master of Science - MSc","language":"en"},{"key":"dc.degree.discipline","value":"Chemistry","language":"en"},{"key":"dc.degree.grantor","value":"University of British Columbia","language":"en"},{"key":"dc.type.text","value":"Thesis\/Dissertation","language":"en"},{"key":"dc.description.affiliation","value":"Science, Faculty of","language":"en"},{"key":"dc.description.affiliation","value":"Chemistry, Department of","language":null},{"key":"dc.degree.campus","value":"UBCV","language":"en"},{"key":"dc.description.scholarlevel","value":"Graduate","language":"en"}]