Investigation of the reaction mechanism of [4 + 2] cyclization of 2,3 dimethylbuta-1,3-diene to methylacrylate using the Michaelis-Menten equation

Authors

  • Irina Svitozarivna Kostiv Department of Chemical Engineering, National University “Lviv Polytechnic”

DOI:

https://doi.org/10.17721/fujcV6I1P74-81

Keywords:

2, 3 dimethylbuta-1, 3-diene, methylacrylate, methyl-3, 4-dimethylcyclohex-3-ene-1-carboxylate, Michaelis–Menten equation, intermediate complex

Abstract

The cycloaddition reaction between 2,3‑dimethylbuta-1,3-diene and methylacrylate proceeds by the second order kinetics. The rate constants increase with the increase in the excess of one of the reactants. The change in the effective rate constants is described by the Michaelis–Menten equation indicating that the reaction proceeds through the initial equilibrium stage of formation of a molecular complex stabilized by van der Waals interaction which then transforms into the product. The limiting stage of the reaction is established and its mechanism is suggested.

Author Biography

Irina Svitozarivna Kostiv, Department of Chemical Engineering, National University “Lviv Polytechnic”

Department of Chemical Engineering,

PhD, lecturer assistant

References

Anisimova N, Kuzhaeva A, Berkova G, Berestovitskaya V. Synthesis and structure of nitrocyclohexenylcarboxylates. Russian Journal of General Chemistry 2011;81(9):1845-1852. https://doi.org/10.1134/s1070363211090180

Monnier-Benoit P, Jabin I, Jaubert J, Netchitaïlo P, Goyau B. Synthesis of 2,4-dimethyl-cyclohex-3-ene carboxaldehyde derivatives with olfactory properties. Comptes Rendus Chimie 2007;10(3):259-267. https://doi.org/10.1016/j.crci.2006.10.006

Farina V, Reeves J, Senanayake C, Song J. Asymmetric Synthesis of Active Pharmaceutical Ingredients. Chemical Reviews 2006;106(7):2734-2793. https://doi.org/10.1021/cr040700c

Polyova I, Marshalok G, Yatchyshyn J, Polyuzhin I. Кinetics of allyl-1,3,4-trimethylcyclo-hex-3-encarboxylate obtaining. Сhemistry & Сhemical Тechnology 2012;6(2):119-122

Polevaya I, Fedevich M, Polyuzhin I, Marshalok O. Optimization of synthesis conditions of 2,3-dimethylbutadiene. Russian Journal of Applied Chemistry 2011;84(2):261-265. https://doi.org/10.1134/s1070427211020169

Marshaloka H. Optimization of the production of methyl 1,3,4-trimethylcyclohex-3-ene-1-carboxylate Optymalizacja procesu otrzymywania 1,3,4-trimetylocykloheks-3-eno-1-karboksylanu metylu. PRZEMYSŁ CHEMICZNY 2016;1(4):67-72. https://doi.org/10.15199/62.2016.4.6

Jasiński R. A reexamination of the molecular mechanism of the Diels–Alder reaction between tetrafluoroethene and cyclopentadiene. Reaction Kinetics, Mechanisms and Catalysis 2016;119(1):49-57. https://doi.org/10.1007/s11144-016-1038-1

Firestone R. Volume of concert and heavy atom effects in Diels-Alder reaction mechanisms. Tetrahedron 1996;52(46):14459-14468. https://doi.org/10.1016/0040-4020(96)00891-5

Ormachea C, Mancini P, Kneeteman M, Domingo L. Understanding the participation of 3-nitropyridine in polar Diels–Alder reactions. A DFT study. Computational and Theoretical Chemistry 2015;1072:37-42. https://doi.org/10.1016/j.comptc.2015.08.024

Lakhdar S, Terrier F, Vichard D, Berionni G, El Guesmi N, Goumont R, Boubaker T. The Diels-Alder Reaction of 4,6-Dinitrobenzofuroxan with 1-Trimethylsilyloxybuta-1,3-diene: A Case Example of a Stepwise Cycloaddition. Chemistry - A European Journal 2010;16(19):5681-5690. https://doi.org/10.1002/chem.200903008

Kessler S, Neuburger M, Wegner H. Domino Inverse Electron-Demand Diels–Alder/Cyclopropanation Reaction of Diazines Catalyzed by a Bidentate Lewis Acid. Journal of the American Chemical Society 2012;134(43):17885-17888. https://doi.org/10.1021/ja308858y

Korotaev V, Barkov A, Slepukhin P, Kodess M, Sosnovskikh V. Diastereoselective reactions of 1,1,1-trichloro(trifluoro)-3-nitrobut-2-enes with 2-morpholinoalk-1-enes. Mendeleev Communications 2011;21(2):112-114. https://doi.org/10.1016/j.mencom.2011.03.020

Polevaya I, Makitra G, Marshalok G, Kovalskyi Y. Effect of the reactants molar ratio on the kinetics of cycloaddition of 2,3-dimethylbuta-1,3-diene to allyl methacrylate. Russian Journal of General Chemistry 2012;82(12):1970-1974. https://doi.org/10.1134/s1070363212120109

Kostiv I, , Marshalok O, Marshalok G, Pyrig I, , , . Effect of the Reactants Molar Ratio on the Kinetics of the Reaction to Obtain 2-hydroxyethyl-1,3,4 trimethyl-cyclohex-3-encarboxylate. Chemistry & Chemical Technology 2015;9(3):277-280. https://doi.org/10.23939/chcht09.03.277

Corsico Coda A, Desimoni G, Ferrari E, Righetti P, Tacconi G. Solvent effect as the result of frontier molecular orbital interaction-1. Tetrahedron 1984;40(9):1611-1615. https://doi.org/10.1016/s0040-4020(01)91813-7

Desimoni G, Faita G, Righetti P, Tacconi G. Diels Alder Reactions in Micellar Media. J. Chem. Soc. 1989;2(3):437-441

Blankenburg B, Fiedler H, Hampel M, Hauthal H, Just G, Kahlert K, Korn J, Müller K, Pritzkow W, Reinhold Y, Röllig M, Sauer E, Schnurpfeil D, Zimmermann G. DIELS-ALDER-Reaktionen. II. Über die Anwendung linearer Freier-Energie-Beziehungen auf DIELS-ALDER-Reaktionen. Journal für Praktische Chemie 1974;316(5):804-816. https://doi.org/10.1002/prac.19743160513

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Published

2018-07-24