THE QUANTUM-CHEMICAL ASPECTS OF STRUCTURING IN THERMAL CURTIUS REARRANGEMENT MECHANISM FOR SOME ARYL- AS WELL AS HETARYLACYL AZIDES: INFLUENCE OF ACID-CATALYTIC AND SOLVATION EFFECTS OF MEDIUM
DOI:
https://doi.org/10.15421/jchemtech.v34i1.336743Keywords:
ab initio calculations, thermal Curtius rearrangement, activation barrier, «ortho-effect» of а substituent, acid catalysis, solvation effectAbstract
Using ab initio density functional method at the PBE1PBE/6-31G(d,p) level of theory, the features of the tautomeric equilibrium of open syn-forms for some aryl- as well as hetarylacyl azides have been investigated, which turned out to be more stable than the corresponding cyclic forms containing an oxatriazole fragment. Further analysis of individual sections for the thermal Curtius rearrangement potential energy surfaces using the model compound 2,6-dimethylpyridine-3,5-diacyl diazide as an example demonstrated the presence of a reaction pathway corresponding to the stepwise transformation of the syn,syn-form for the starting compound into the corresponding diisocyanate as the final reaction product. In this case, the sequential transformation of both acyl azide groups has been accompanied by intramolecular migration of the hetaryl fragment with simultaneous cleavage of the nitrogen molecule at each of the reaction stages. The results of calculations are in good agreement with data of this type obtained earlier and indicate a low sensitivity of the reaction to structural modifications of the substrate, among which the greatest contribution is made by the manifestations of the "ortho-effect" of methyl substituents in the aromatic fragment of the molecules. The overall increase in the reactivity of the studied systems is also shown under the acid catalysis conditions with simultaneous consideration of nonspecific solvation effects of the benzene solution. This approach allows for the detailed conditions of the target transformation and can be actively used to predict the behavior of related systems within the selected computational approximation.
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