Ярославль, Ярославская область, Россия
Ярославль, Ярославская область, Россия
Ярославль, Ярославская область, Россия
Ярославль, Ярославская область, Россия
We performed quantum-chemical AM1 modelling of the Diels-Alder heteroreaction of 1-phenylbut-2-ene-3-thione and 2-(N-pyrrolidinyl)pent-2-ene-4-thione with symmetrical dienophiles. We calculated the HOMO/LUMO energies of dienes and dienophiles as well as the activation energies of the corresponding reactions. The reaction has direct electron requirements. The principal possibility of the reaction of 2-(N-pyrrolidinyl)pent-2-ene-4-thione with electron-excessive dienophiles was outlined. Also we proved the significant difference in the reactivity of norbornene and cyclohexene dienophiles with α,β-unsaturated thiocarbonyl compounds.
unsaturated thiocarbonyl compounds, the Diels-Alder heteroreaction, thiopyranes synthesis, quantum-chemical modelling, AM1 method
1. Merkulova E.A., Kolobov A.V., Ovchinnikov K.L. A convenient synthesis of 3,4-dihydro-2H-thiopyran-2,3-dicarboxylic acid derivatives. Rus. Chem. Bull. 2019. V. 68. N 3. P. 606–609. DOI:https://doi.org/10.1007/s11172-019-2462-y.
2. Merkulova E.A., Kolobov A.V, Ovchinnikov K.L., Khrustalev V.N., Nenajdenko V.G. Unsaturated carboxylic acids in the one-pot synthesis of novel derivatives of 3,4-dihydro-2H-thiopyran. Chemistry of Heterocyclic Compounds. 2021. V. 57. N 3. P. 245–252. DOI:https://doi.org/10.1007/s10593-021-02900-y.
3. Rasmussen J.B, Shabana R., Lawesson S. Enamine chemistry-XXIII: The [4+2] cycloaddition reactions between enaminothiones and electrophilic olefins and acetylenes. Tetrahedron. 1981. V. 37. N 21. P. 3693–3698. DOI:https://doi.org/10.1016/S0040-4020(01)98900-8.
4. Takehiko Nishio, Naoko Nakajima, Yoshimori Omote. Photochemical reactions of β-aminovinyl aryl thioketones. Journal of Heterocyclic Chemistry. 1980. V. 17. N 2. P. 405-406. DOI:https://doi.org/10.1002/jhet.5570170242.
5. Bogdanowicz-Szwed K., Budzowski A. Hetero-Diels-Alder Reactions of Enaminothione with Electrophilic Olefins. Synthesis of 2-Furyl Substituted 2H-Thiopyrans. Zeitschrift für Naturforschung B. 2002. V. 57. N 6. P. 637–644. DOI:https://doi.org/10.1515/znb-2002-0608.
6. Takayuki Karakasa, Shinichi Motoki. Chemistry of α,β-Unsaturated Thione Dimers. 1. Preparation of α,β Unsaturated Thione Dimers and Thermolysis of These Dimers in the Presence of Acrylonitrile or Acrylamide. J. Org. Chem. 1978. V. 43. N 21. P. 4147–4150. DOI:https://doi.org/10.1021/jo00415a036.
7. Greif D., Pulst M., Weißenfels M. Die Synthese von 2H-Thiopyranen aus β-Thioxoaldehyden. Synthesis. 1987. N 5. P. 456–460. DOI:https://doi.org/10.1055/s-1987-33432.
8. Dewar M.J.S., Zoebisch E.G., Healy E.F., Stewart J.J.P. Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model. J. Am. Chem. Soc. 1985. V. 107. N 13. P. 3902–3909. DOI:https://doi.org/10.1021/ja00299a024.
9. Dewar M.J.S., Yuan Y.C. AM1 parameters for sulfur. Inorg. Chem. 1990. V. 29. N 19. P. 3881–3890. DOI:https://doi.org/10.1021/ic00344a045.
10. Solovyov M.E., Solovyov M.M. Computer Chemistry. M.: SOLON-Press. 2005. 536 p. (in Russian).
11. Soloviev M.E., Dmitriev K.E. Computer modelling in chemistry. Yaroslavl: Izd-vo YAGTU, 2021. 256 p. (in Russian).
12. Ovchinnikov K.L., Starostin M.V., Larionov N.N. Quantum-chemical study of regioselectivity of Diels-Alder heteroreaction of α,β-unsaturated thiocarbonyl compounds with unsymmetrical dienophiles. From chemistry to technology step by step. 2021. V. 2. N 3. P. 56-60. DOI:https://doi.org/10.52957/27821900_2021_03_56 (in Russian).
