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N-alkylation of 2,3-dihydroimidazo[2,1-b]quinazolin-1(10)H-5-one. On the cryptoanionic mechanism of N-substitution

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Abstract

Quantum chemical methods involving studies of transition states of the reaction showed that the main products of N-alkylation of prototropic 2,3-dihydroimidazo[2,1-b]quinazolin-1(10)H-5-one (1) in the gas phase and under neutral conditions in solution occurring via the SN2 mechanism should be N(10)-alkyl-substituted derivatives formed from the 1H-tautomer. Minor N(1)-substituted derivatives in solution can be produced from both tautomers. For the alkylation of the free N-anion of compound 1, position 1 is attacked first. Validity of conclusions concerning the overall regioselectivity of the reaction was confirmed experimentally. In the absence of solvent, the alkylation proceeds abnormally with a sharp increase in the content of the 1-substituted isomers up to inversion of the regioselectivity of the reaction, which is explained by the participation in the process of the H-bonded dimer of the substrate (1a)2, which undergoes alkylation via the cryptoanionic mechanism.

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Authors and Affiliations

  1. Research Institute of Physical and Organic Chemistry, Rostov-on-Don State University, 194/2 prosp. Stachki, 344090, Rostov-on-Don, Russian Federation

    A. S. Morkovnik, L. N. Divaeva & T. A. Kuz’menko

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  1. A. S. Morkovnik
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  2. L. N. Divaeva
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  3. T. A. Kuz’menko
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 876–887, May, 2006.

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Morkovnik, A.S., Divaeva, L.N. & Kuz’menko, T.A. N-alkylation of 2,3-dihydroimidazo[2,1-b]quinazolin-1(10)H-5-one. On the cryptoanionic mechanism of N-substitution. Russ Chem Bull 55, 907–919 (2006). https://doi.org/10.1007/s11172-006-0351-7

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  • DOI: https://doi.org/10.1007/s11172-006-0351-7

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