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Reactivity of 2-amino[1,2,4]triazolo[1,5-а]-pyrimidines with various saturation of the pyrimidine ring towards electrophiles

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Chemistry of Heterocyclic Compounds Aims and scope

The effect of pyrimidine ring saturation in 2-amino[1,2,4]triazolo[1,5-а]pyrimidines on their reactivity as polyfunctional N-nucleophiles was studied by computational methods (reactivity indices and transition state energy values for the model reaction of S N2 alkylation with chloromethane, DFT B3LYP/6-311++G(2d,2p)), as well as experimentally (alkylation with benzyl bromide). The global nucleophilicity of partially hydrogenated aminotriazolopyrimidines was shown to be substantially higher than for aromatic analogs. The most likely sites for electrophilic attack in partially hydrogenated aminotriazolopyrimidines were the N-1 and N-3 atoms, as well as the amino group, and the probability of attack at the N-3 atom increased with harder electrophiles. The nucleophilicity of amino group and the N-1 atom was substantially decreased in aromatic aminotriazolopyrimidines, where the most likely sites of attack by hard electrophiles were the N-3 and N-4 atoms.

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This work received financial support from the Russian Science Foundation (project 14-23-00078). The authors would also like to acknowledge the assistance with GC-MS analysis received at the Collective Use Center „Nanotechnologies” of the Platov South-Russian State Polytechnic University.

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Authors and Affiliations

  1. Platov South-Russian State Polytechnic University (NPI), 132 Prosveschenya St., Novocherkassk, 346428, Russia

    Alexander V. Astakhov, Andrey N. Sokolov, Dmitry A. Pyatakov & Victor M. Chernyshev

  2. State Scientific Institution “Institute of Single Crystals” of National Academy of Sciences of Ukraine, 60 Lenin Ave., 61001, Kharkiv, Ukraine

    Svetlana V. Shishkina & Oleg V. Shishkin

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  1. Alexander V. Astakhov
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  2. Andrey N. Sokolov
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Correspondence to Victor M. Chernyshev.

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Translated from Khimiya Geterotsiklicheskikh Soedinenii, 2015, 51(11/12), 1039–1047

(Oleg V. Shishkin) Deceased.

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Astakhov, A.V., Sokolov, A.N., Pyatakov, D.A. et al. Reactivity of 2-amino[1,2,4]triazolo[1,5-а]-pyrimidines with various saturation of the pyrimidine ring towards electrophiles. Chem Heterocycl Comp 51, 1039–1047 (2015). https://doi.org/10.1007/s10593-016-1816-8

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