Počet záznamů: 1
Solvent-free, catalyst-free aza-Michael addition of cyclohexylamine to diethyl maleate: reaction mechanism and kinetics
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SYSNO ASEP 0482881 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Solvent-free, catalyst-free aza-Michael addition of cyclohexylamine to diethyl maleate: reaction mechanism and kinetics Tvůrce(i) Bláha, Michal (UMCH-V) RID
Trhlíková, Olga (UMCH-V) RID, ORCID
Podešva, Jiří (UMCH-V) RID
Abbrent, Sabina (UMCH-V) RID, ORCID
Steinhart, Miloš (UMCH-V) RID
Dybal, Jiří (UMCH-V) RID, ORCID
Dušková-Smrčková, Miroslava (UMCH-V) RID, ORCIDZdroj.dok. Tetrahedron. - : Elsevier - ISSN 0040-4020
Roč. 74, č. 1 (2018), s. 58-67Poč.str. 10 s. Jazyk dok. eng - angličtina Země vyd. GB - Velká Británie Klíč. slova Aza-Michael addition ; solvent-free ; catalyst-free Vědní obor RIV CD - Makromolekulární chemie Obor OECD Polymer science Institucionální podpora UMCH-V - RVO:61389013 UT WOS 000418728200008 EID SCOPUS 85035193735 DOI https://doi.org/10.1016/j.tet.2017.11.033 Anotace The aza-Michael reaction is the addition of an amine to an electron deficient C=C double bond. This reaction is also used in the synthesis of precursors of polymeric networks. In this study, we paid attention to the kinetics and mechanism of the aza-Michael addition of cyclohexylamine (CHXA) to diethyl maleate (DEM) performed as a solvent-free, catalyst-free reaction and to concurrent reactions. In situ Raman spectroscopy, NMR spectroscopy and gas chromatography/mass spectrometry have shown the occurrence of three simultaneous reactions: (i) the aza-Michael addition of CHXA to DEM leading to diethyl 2-(cyclohexylamino)succinate, (ii) isomerization of DEM to diethyl fumarate (DEF), and (iii) the aza-Michael addition of CHXA to DEF formed by the reaction (ii). All of these reactions proceed with third order kinetics, first order in DEM or DEF and second order in CHXA. We propose a kinetic model that allows kinetic constants to be estimated. Furthermore, a numerical solution of the set of differential equations confirms the expected kinetic equations of reactions (i) and (ii) and gives values of rate constants comparable to the estimated ones. A DFT mechanistic study illustrates the structure of the reaction intermediates and transition states of all reactions and explains the contribution of the second amine molecule in the reaction mechanism. Pracoviště Ústav makromolekulární chemie Kontakt Eva Čechová, cechova@imc.cas.cz ; Tel.: 296 809 358 Rok sběru 2019
Počet záznamů: 1