Abstract
The values of the energy barriers to intramolecular 1,3-H shift reactions, in whichaci-forms of N- and C-nitro-compounds:\(\begin{array}{*{20}c} {} & {} & O & {} & {} & {} & {Me} \\ {} & {} & {} & {} & {} & {} & {} \\ {} & {} & {} & {} & {N = N} & {} & {} \\ {} & {} & {} & {} & {} & {} & {} \\ H & - & O & {} & {} & {} & {} \\ \end{array}\) 1 and\(\begin{array}{*{20}c} {} & {} & O & {} & {} & {} & {Me} \\ {} & {} & {} & {} & {} & {} & {} \\ {} & {} & {} & {} & {N = C} & {} & {} \\ {} & {} & {} & {} & {} & {} & {} \\ H & - & O & {} & {} & {} & H \\ \end{array}\) are capable of transforming into\(\begin{array}{*{20}c} {} & {} & O & {} & {} & {} & {Me} \\ {} & {} & {} & {} & {} & {} & {} \\ {} & {} & {} & {} & {N = N} & {} & {} \\ {} & {} & {} & {} & {} & {} & {} \\ {} & {} & O & {} & {} & {} & H \\ \end{array}\) 2 and\(\begin{array}{*{20}c} {} & {} & O & {} & {} & {} & {Me} \\ {} & {} & {} & {} & {} & {} & {} \\ {} & {} & {} & {} & {N = C} & - & H \\ {} & {} & {} & {} & {} & {} & {} \\ {} & {} & O & {} & {} & {} & H \\ \end{array}\), respectively, have been calculated by the semi-empirical AM1 method. The barrier heights (39 and 59.4 kcal/mol) reflect the kinetic stability of both tautomeric forms of the N- and C-nitro-compounds.Ab initio calculations in the 3–21G basis set of the structure and energies of stationary points on the potential energy surface of the system MeN=NO2 H3O demonstrated that there exists the principal possibility of the formation of only tautomer 2 (which is more stable than1).
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Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No 1, pp. 100–104, January, 1993.
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Avakyan, V.G., Fateyev, O.V. Quantum-chemical study on the tautomerism of primary nitramines: the mechanism of N-nitro-anion protonation excludingaci-form formation. Russ Chem Bull 42, 90–94 (1993). https://doi.org/10.1007/BF00699982
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DOI: https://doi.org/10.1007/BF00699982