CC BY
14
УДК 547.514.72:544.183.25
V. A. Babkin, L. M. Lisina, A. V. Ignatov, R. G. Fedunov, A. I. Rakhimov, E. S. Titova, O. V. Stoyanov, G. E. Zaikov
THE ANIONS GENERATED FROM 2-MERCAPTO-4-HYDROXY-6-METHYLPYRIMIDINE
Keywords: 2-mercapto-4-hydroxy-6-methylpyrimidine, method AB INITIO.
The geometric and electronic structure of S- and O-anions generated from 2-mercapto-4-hydroxy-6-methylpyrimidine hasbeenstudied by the ab initio method.
Ключевые слова: 2-меркапто-4-гидрокси-5-метилпиримедин, метод AB INITIO.
Методом AB INITIO изучена геометрическая и электронная структура S- и О-анионов, генерируемых из 2-меркапто-4-гидрокси-6-метилпиримидина.
Aim and methodological part
The derivatives of 2-mercapto-4-hydroxy-6-methylpyrimidine are widely used as the medical compounds with the biological activity. The development of the methods of the synthesis of such compounds is an important task [2-6; 9, 10, 12]. To study the reactivity of 2-mercapto-4-hydroxy-6-methylpyrimidine by the AB INITIO method(the restricted Hartree-Fock basis 6-31G **) we have studied the geometric and electronic structure ofS- and O-anions, which can be formed from it (Figure 1) [1,7-9; 11,12].
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Fig. 1 - The geometric and electronicstructure of theanions: Thioanion
Fig. 2 - The geometric and electronic structure of theanions: Oxyanion
Results of the research
The oxy anion is55.9 kJ / mol higher in total energy than the thioanion. That is why the formation of
it in the other equal conditions is improbable. This is confirmed experimentally by the kinetic studies and the synthesis of S-monoderivatives, exclusively in generating the thioanion in the water and dioxane medium atthe temperature of 30—50 °C [2-6; 9,10,12].
References
1. Babkin, V.A. The Quantum-chemical Study of the Mechanism of the Synthesis of 2-methyl(benzyl)thio-4-methyl(benzyl)hydroxypyrimidine / V.A. Babkin , A.I. Rakhimov, E.S. Titova, R.G. Fedunov, R.A. Reshetnikov, V.S. Belousova, G.E. Zaikov // The Chemical Physics and Mesoscopy.- 2007. - V. 9. -№ 3. -Pp. 263-275.
2. Rakhimov, A. I. The Features of the Synthesis of 2-alkyl (aryl-alkyl) thio-6-methylpyrimidin-4 (3H)-ons and 2-alkyl (arylalkyl) thio-4-alkyl (arylalkyl) oxy-6-methylpyrimidine/ A. I. Rakhimov, E.S Titova // The Journal of General Chemistry.- 2007.- V. 43. - № 1.- Pp. 92-98.
3. Rakhimov, A.I.The Generation of S-and O-anion from 6-methyl-2-thio-2-alkyl(arylalkyl)thiouracil in the synthesis S-mono- and S-, O-diderivatives / A.I. Rakhimov, E.S. Titova, R.G. Fedunov, V.A. Babkin, O.V. Stoyanov, G.E. Zaikov / / The Vestnik of the Kazan State Technological University. -2013. - V. 16. - № 5. - Pp. 23-29.
4. Rakhimov, A. I. The Nucleophilic Substitution on the Benzyl 1 - (Chloromethyl)-3-phenoxy-benzyl Chloride with the 4-methyl-6-oxo-1,6-dihydro-2-pirimidintiolat of Anion / A. I. Rakhimov, V. Popov, E.S. Titova // The Izvestia of the Volgograd State Technical University.- 2005. - № 1. - Pp. 61 - 64.
5. Rakhimov, A. I. The Process of Preparing 2 1,3-di[4-(6-methyl-4-pyrimidinone-2-thio)methylphenyl]adamantine : the patent RUS 231141211.07.2006 / A. I. Rakhimov, E.S. Titova.
6. Rakhimov, A.I. The Properties of the Nucleophilic Substitution in Alkyl and Benzyl Halides with Anions Generated from 4-hydroxy-2-mercapto-6-methylpyrimidine / A.I. Rakhimov, E.S. Titova, R.G. Fedunov, V.A. Babkin // The Chemistry of Heterocyclic Compounds. -2008. -№ 6. -. Pp.874-883.
7. Rakhimov,A.I. The Quantum Chemical Analysis of the Reactivity of S-and O-anions Generated from 6-methyl-2-thio-2-alkyl(aralkyl)thiouracils. A.I. Rakhimov, E.S. Titova, R.G. Fedunov, V.A. Babkin / The Izvestia of the Volgograd State Technical University. - 2008. -V. 1. - № 5. - Pp. 70 -75.
8. Rakhimov, A.I. The Reactivity Ability of S-and O-anions Generated from 6-methyl-2-thio, 2-thioalkyl(aralkyl)uracils / A.I. Rakhimov, E.S. Titova, R.G. Fedunov, V.A. Babkin, V.S. Belousova, S.N. Rusanov, G.E. Zaikov / / The Vestnik
of the Kazan State Technological University. - 2013. - V. 16.- № 5. - Pp. 16-20.
9. Rakhimov, A. I. TheSynthesis of 2-alkyl(aralkyl)sulfanyl-6-methylpyrimidin-4(3h)-ons and4-alkyl(aralkyl)oxy-2-alkyl(aralkyl)sulfanyl-6-methylpyrimidines / A. I. Rakhimov, E. S. Titova // The Russian Journal of Organic Chemistry.- 2007.- V. 43. - № 1. - Pp. 96-102.
10. Rakhimov, A.I. The Synthesis of Symmetrical and Unsymmetrical S-, O-diderivatives of 6-methyl-2-thiouracil / A.I. Rakhimov, E.S. Titova //The Izvestia of the Volgograd State Technical University. -2006. -№ 1. -Pp. 66 - 72.
11. Rakhimov, A.I. The Theoretical Analysis of the Reactivity of S-andO- Anions Generated from 6-methyl-2-thio,2-thioalkyl(aralkyl)uracils / A.I. Rakhimov, V.A. Babkin, E.S. Titova , R.G. Fedunov, V.S. Belousova, G.E. Zaikov //
The Theoretical and Applied Aspects of Quantum-chemical Calculations of the Molecular Systems. The Unique Collection Articles: a 59-th Anniversary of the ProfessorV. A. Babkin. The Ministry of Education and Science of the Russian Federation, the Volgograd State University of Architecture and Civil Engineering, the Serebryakovskiy Branch of the Volgograd State University of Architecture and Civil Engineering, the Department of Mathematics and Natural Sciences; edited by Babkin V.A.- Volgograd, 2011.-Pp. 41-50.
12. Titova, E.S. S- and O-anions generated from 6-methyl-2-thio, 2-alkyl (aralkyl)thiouracil in the synthesis of S-mono-and S-, O-dialkyl, benzyl derivatives : the thesis for the degree of the Candidate of the Chemical Sciences / Titova Yevgeniya Stanislavovna. - Volgograd, 2005. - 154 c.
© V. A. Babkin — Doctor of Chemical Sciences, professor, academician of international academy "Contenant", Head of Science department of Volgograd State Architecture Building University, Sebryakov's Branch, [email protected]; L. M. Lisina — Candidate of Pedagogic Sciences of Volgograd State Architecture Building University, Sebryakov's Branch, [email protected]; A. V. Ignatov — 4th year student of class "S41-d" of Volgograd State Architecture Building University, Sebryakov's Branch, [email protected]; R. G. Fedunov — Candidate of Physico-mathematical Sciences, professor of "Theoretical Physics and Wave Processes" department of Volgograd State University, [email protected]; E. S. Titova — Candidate of Chemical Sciences, professor of department "Organic Chemistry" of Volgograd State Technical University. [email protected]; O. V. Stoyanov-Professor, Doctor of technical Science, processing and certification of plastics and composites, Head of Department "Technology of Plastics" at Kazan National Research Technological University, [email protected]; G. E. Zaikov — Doctor of Chemical Sciences, professor, academician of international academyof Science (Munich, Germany), Honored scientist of Russian Federation. Institute of Biochemical Physics, Moscow, [email protected].
© В. А. Бабкин — д-р хим. наук, проф., академик РАЕ, академик Международной академии «Контенант», нач. научн. отдела Себряковского филиала Волгоградского государственного университета, [email protected]; Л. М. Лисина — кандидат педагогических наук Себряковского филиала Волгоградского государственного технического университета, [email protected]; А. В. Игнатов — студент группы С-41д Себряковского филиала Волгоградского государственного архитектурно-строительного университета, [email protected]; Р. Г. Федунов — кандидат физико-математических наук, доцент кафедры «Теоретической физики и волновых процессов», Волгоградский государственный университет, [email protected]; Е. C. Титова — к.х.н. доц. кафедры «Органическая химия» Волгоградского государственного технического университета, [email protected]; О. В. Стоянов — д-р техн. наук, проф., зав. каф. технологии пластических масс КНИТУ, [email protected]; Г. Е. Заиков — д-р хим. наук, проф., академик Международной академии наук (Мюнхен, Германия), заслуженный деятель РФ, Институт биохимической физики, РАН, Москва, [email protected].
