Quantum-chemical research of the reaction mechanism of [4+2]-cycloaddition of 2,3-dimethylbuta-1,3-dien and allylmethacrylate
DOI:
https://doi.org/10.15587/1729-4061.2014.27665Keywords:
2, 3-Dimethylbuta-1, 3-diene, Allyl methacrylate, allyl-1, 3, 4-trymethylcyclohex-3encarboxylate, MOPAC2009, RM1Abstract
The mechanism of the [4+2]-cycloaddition reaction of 2,3dimethylbuta-1,3-diene and allyl methacrylate was studied by the quantum-chemical modelling using a semi-empirical programme of MOPAC2009 by the RM1 method. The quantum-chemical calculations allowed analyzing the qualitative sides of the reaction.
It was found that the interaction of 2,3dimethylbuta-1,3-diene and allyl methacrylate has a stepwise mechanism with the formation of an intermediate with an open electron shell, not a synchronous mechanism with a closed electron shell. The end product molecule − allyl-1,3,4-trymethylcyclohex-3-encarboxylate has a semi-armchair form in which a carboxylate group is in the endo-position to a cyclohexene ring. The molecule structure also indicates that the interaction of 2,3dimethylbuta-1,3-diene and allyl methacrylate is agreed by the stepwise mechanism with a disrotatory cycle closure in the second step.
The compliance of the experimental data with the activation parameters obtained by means of the quantum-chemical calculations of this reaction confirms the proposed mechanism.
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Copyright (c) 2014 Петрович Ковальский Ярослав, Ирина Светозаровна Костив, Ольга Игоревна Маршалок, Галина Олексеевна Маршалок, Игорь Юрьевич Пыриг
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