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dc.contributor.authorSvensen, Haraldnb_NO
dc.date.accessioned2014-12-19T13:10:38Z
dc.date.available2014-12-19T13:10:38Z
dc.date.created2001-12-14nb_NO
dc.date.issued2001nb_NO
dc.identifier121699nb_NO
dc.identifier.isbn82-471-5369-6nb_NO
dc.identifier.urihttp://hdl.handle.net/11250/244442
dc.description.abstractThe goals for the project “Synthesis and Functionaliszation of 3-Nitropyridines” were first to further optimize the procedures for nitration of 3-nitropyridines, and then investigate some aspects of the mechanism. Further was the reactivity of 3- nitropyridines investigated, especially the reactivity toward nitrogen nucleophiles. Pyridines can be nitrated by reacting the pyridine with dinitrogen pentoxide in an organic solvent and then pour the slurry formed into an aqueous solution of sodium bisulfite. After some hours of stirring, the 3-nitropyridine can be isolated. After investigation of the effect of changes in sodium bisulfite concentration, reaction medium and temperature a modified procedure for the nitration was developed. In this procedure the pyridine compound was reacted with dinitrogen pentoxide in dichloromethane or nitro methane and the resulting slurry poured into a solution of bisulfite dissolved in methanol/water (3:1). After some hours of stirring at room temperature the 3-nitropyridine was isolated. The mechanism of the nitration of pyridines with dinitrogen pentoxide was studied, and is shown in the next scheme. The author studied the migration of the nitro group from the nitrogen to the -carbon. It has been by others shown that pyridine and dinitrogen pentoxide forms N-nitro pyridinium nitrate. Which is attacked by the bisulfite nucleophile in either 2- or 4- position to give N-nitro-2- dihydropyridine-2-sulfonate and N-nitro-1,4-dihydropyridine-4-sulfonate. The nitro group in N-nitro-2-dihydropyridine-2-sulfonate migrates to the -carbon, to give via addition of one more bisulfite ion a tetrahydro intermediate. From this the 3-nitropyridine is formed by loss of two bisulfite ions. The mechanism for the nitro group migration was previously not known. The results presented in this thesis together with previous results conclude with that the migration takes place as a [1,5] sigmatropic shift.nb_NO
dc.languageengnb_NO
dc.publisherFakultet for naturvitenskap og teknologinb_NO
dc.relation.ispartofseriesDr. ingeniøravhandling, 0809-103X; 2001:100nb_NO
dc.relation.haspartBakke, JM; Ranes, E; Riha, J; Svensen, H. The Synthesis of β-nitropyridine compounds. Acta Chemica Scandinavia. 53(141), 1999.nb_NO
dc.relation.haspartBakke, JM; Svensen, H; Ranes, E. The reaction mechanism of the nitration of pyridine compounds by N2O5 NaHSO3. J. Chem. Soc., Perkin Trans(11): 2477-2482, 1998.nb_NO
dc.relation.haspartBakke, JM; Svensen, H; Trevisan, R. Selective vicarious nucleophilic amination of 3-nitropyridines. Chem. Soc., Perkin Trans. 1: 376-378, 2001.nb_NO
dc.relation.haspartBakke, JM; Svensen, H. The oxidative amination of 3-nitropyridines. Tetrahedron Letters. 42(26): 4393-4395, 2001.nb_NO
dc.subjecten_GB
dc.subjectKemien_GB
dc.subjectNATURAL SCIENCES: Chemistryen_GB
dc.titleSynthesis and Functionalization of 3-Nitropyridinesnb_NO
dc.typeDoctoral thesisnb_NO
dc.source.pagenumber124nb_NO
dc.contributor.departmentNorges teknisk-naturvitenskapelige universitet, Fakultet for naturvitenskap og teknologinb_NO
dc.description.degreedr.ing.nb_NO
dc.description.degreedr.ing.en_GB


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