THEORETICAL STUDY OF THERMAL CURTIUS REARRANGEMENT MECHANISM FOR SOME ARYL- AS WELL AS HETARYLACYL AZIDES WITH PREDICTION OF THE FOLLOWING CYCLOTRIMERIZATION PROGRESS
DOI:
https://doi.org/10.15421/jchemtech.v32i4.310213Keywords:
ab initio розрахунки; термічне перегрупування Курціуса; енергія активації; метод поляризуючого континууму; механізм циклотримеризації.Abstract
With the aid of ab initio density functional method in the non-empirical generalized gradient approximation on the example of syn-conformers of aryl- as well as hetarylacyl azides, which turned out to be thermodynamically more stable than the corresponding anti-analogues, some areas of the potential energy surfaces have been investigated for the thermal Curtius rearrangement, which occures according to a concerted mechanism and includes the cleavage of a nitrogen molecule under the simultaneous migration of an aromatic fragment with the corresponding isocyanate formation in vacuo as well as in bulk of benzene solution. The analysis of the calculated values of activation barriers showed that the introduction of a pyridine-type Nitrogen atom into the meta- and para-positions of the benzene ring practically does not affect on the EACT absolute values, while in the ortho-position such a modification of the substrate leads to only a slight decrease of it, especially in comparison with unsubstituted prototype. As for the non-catalytic cyclotrimerization processes, that can take place with the participation of obtained in the previous stage isocyanates, the only transition state corresponding to the concerted mechanism of this transformation has not been localized at all on the potential energy surface. Instead of the process takes place as stepwise and includes the sequential addition of an aryl isocyanate molecule to the dimer formed at the previous stage with the expansion of a four-membered ring to a six-membered one. The results of calculations are in good agreement with theoretical data, which have been obtained for such type modeling previously and indicating the low sensitivity of the reaction to the solvation effects of medium.
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