Abstract
By quantum-chemical method in the framework of the density functional theory [B3LYP/6-31G(d)] a mechanism of reaction between 1,2-dialkyldiaziridines and ketenes CH2=C=O, PhCH=C=O, and aroyl isocyanates was investigated. The fragment Ph-CH-C(O) in the intermediate governing the cleavage of the N-N bond of the diaziridine ring is virtually planar leading to a considerable loosening of the bond. In the intermediate governing the cleavage of the C-N bond of the ring the fragment Ph-C(O)-N−C(O) is nonplanar resulting in significantly lesser loosening of the N-N bond and in the C-N-opening of the diaziridine ring. The calculated thermodynamical parameters are well consistent with the experimental data on the reactivity.
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Dedicated to the Full Member of the Russian Academy of Sciences V.A. Tartakovsky on occasion of his 75th birthday
Original Russian Text © A.V. Shevtsov, V.P. Ananikov, N.N. Makhova, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 8, pp. 1113–1117.
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Shevtsov, A.V., Ananikov, V.P. & Makhova, N.N. Quantum-chemical investigation of the mechanism of reaction between 1,2-dialkyldiaziridines and heterocumulenes. Russ J Org Chem 43, 1101–1105 (2007). https://doi.org/10.1134/S1070428007080015
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DOI: https://doi.org/10.1134/S1070428007080015