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The study of the formation mechanism of 1,2,3-trialkyldiaziridines by kinetic and quantum chemistry methods Full article

Journal Russian Chemical Bulletin
ISSN: 1573-9171 , E-ISSN: 1066-5285
Output data Year: 2014, Volume: 63, Number: 9, Pages: 2000-2006 Pages count : 7 DOI: 10.1007/s11172-014-0691-7
Authors Kuznetsov V.V. 1 , Seregin V.V. 2 , Khakimov D.V. 1 , Pivina T.S. 1 , Vedenyapina M.D. 3,1 , Vedenyapin A.A. 3,1 , Makhova N.N. 1
Affiliations
1 N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russian Federation
2 D. I. Mendeleev University of Chemical Technology of Russia, Moscow, Russian Federation
3 Moscow Technological Institute ”VTU”, Moscow, Russian Federation

Abstract: Using UV spectrometry, we studied for the first time the regularities of AlkNHBr consumption in two variations of the formation of 1,2,3-trialkyldiaziridines in aqueous media: by mixing acetaldehyde and AlkNHBr in excess of AlkNH2 (method 1) and by the reaction of MeCH=NEt with EtNHBr in excess of EtNH2 (method 2). We determined the rate constants of the individual stages of the reaction. Using quantum chemistry methods (DFT/B3LYP/3-21G), we performed calculations of spatial and electronic structures of the reacting compounds, indices of local reactivity, and global electrophilicity of atoms of the individual reaction intermediates, based on which we explained the decrease in the reaction rate when using EtNHBr instead of MeNHBr in method 1. In method 2, the formation of 1,2-diethyl-3-methyldiaziridine occurs exclusively through the intermediate iminium cation.
Cite: Kuznetsov V.V. , Seregin V.V. , Khakimov D.V. , Pivina T.S. , Vedenyapina M.D. , Vedenyapin A.A. , Makhova N.N.
The study of the formation mechanism of 1,2,3-trialkyldiaziridines by kinetic and quantum chemistry methods
Russian Chemical Bulletin. 2014. V.63. N9. P.2000-2006. DOI: 10.1007/s11172-014-0691-7 WOS Scopus OpenAlex
Identifiers:
Web of science: WOS:000355183300011
Scopus: 2-s2.0-84930225637
OpenAlex: W368107223
Citing:
DB Citing
OpenAlex 4
Scopus 3
Web of science 2
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