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Kinetic and quantum chemical studies of the mechanism of formation of 1,2-dialkyldiaziridines Full article

Journal Russian Chemical Bulletin
ISSN: 1573-9171 , E-ISSN: 1066-5285
Output data Year: 2012, Volume: 61, Number: 6, Pages: 1121-1127 Pages count : 7 DOI: 10.1007/s11172-012-0152-0
Authors Kuznetsov V.V. 1 , Seregin V.V. 2 , Laptev A.A. 2 , Khakimov D.V. 1 , Pivina T.S. 1 , Simakova A.P. 1 , Vedenyapina M.D. 1 , Vedenyapin A.A. 1 , Makhova N.N. 1
Affiliations
1 N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation
2 Russian D. I. Mendeleev Chemical Technology University, 9 Miusskaya pl., 125047, Moscow, Russian Federation

Abstract: The regularities of AlkNHBr consumption in the reaction of formation of 1,2-dialkyldiaziridines in aqueous media were studied for the first time by UV spectrometry. The rate constants of particular steps of the reaction were estimated starting from the possibility of formation of the precursor of 1,2-dialkyldiaziridine, N-halogenaminal, due to the amination of the intermediate iminium cation along with the parallel halogenation of the intermediate gem-diamine. The quantum chemical calculations (DFT, B3LYP, 6–31++G(d,p) and 3–21G basis sets) were performed for the spatial and electronic structures of the compounds and indices of the local reactivity and global electrophilicity of the key intermediates of the reactions. The results of the calculations allowed us to explain the retardation of the reaction when using EtNHBr instead of MeNHBr.
Cite: Kuznetsov V.V. , Seregin V.V. , Laptev A.A. , Khakimov D.V. , Pivina T.S. , Simakova A.P. , Vedenyapina M.D. , Vedenyapin A.A. , Makhova N.N.
Kinetic and quantum chemical studies of the mechanism of formation of 1,2-dialkyldiaziridines
Russian Chemical Bulletin. 2012. V.61. N6. P.1121-1127. DOI: 10.1007/s11172-012-0152-0 WOS Scopus OpenAlex
Identifiers:
Web of science: WOS:000316288800011
Scopus: 2-s2.0-84879629659
OpenAlex: W2065215427
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