Abstract
Quantum chemical calculations of the energies, electronic structures, and molecular geometries of 5-methyl-, 2,5-dimethyl-, 3,5-dimethyl-, and 2,3,5-trimethyl-4-oxothieno[2,3-d]pyrimidine-6-carboxylic acids; 5-methyland 3,5-dimethyl-2,4-dioxothieno[2,3-d]pyrimidine6-carboxylic acids; 5-methyland 3,5-dimethyl-4-oxo-2-thiothieno[2,3-d]pyrimidine-6-carboxylic acids; and their ethyl esters were performed in terms of the HF and DFT (B3LYP) approximations in the 3-21G basis set. The reactions routes with nitrating agents were examined, and the factors governing the direction of the reactions, the probability of their occurrence were determined. Selective ipso-substitution of the 5-methyl group by the nitro group at the C(5) atom of the thiophene fragment is hindered for all compounds studied. The reasons for the unfavorable ipso-substitution were discussed taking into account effects of solvents and substituents in positions 2, 3, and 6 of 6-carboxyand 6-ethoxycarbonyl-substituted thieno[2,3-d]pyrimidin-4-ones.
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For Part 5, see Ref. 1.
Dedicated to blessed memory of Professor Kh. M. Shakhidoyatov (March 15, 1941—February 13, 2015).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0654—0657, March, 2016.
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Mamarakhmonov, M.K., Belen’kii, L.I., Chuvylkin, N.D. et al. Quantum chemical studies of pyrimidin-4-ones Part 6. On peculiarities of the reactions with nitrating agents of some carboxylic acids of the thieno[2,3-d]pyrimidin-4-one series and their esters. Russ Chem Bull 65, 654–657 (2016). https://doi.org/10.1007/s11172-016-1351-x
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DOI: https://doi.org/10.1007/s11172-016-1351-x