Quantum Chemical Study of Organic Reactions Mechanisms. XIII. The Reaction of Propargyl Chloride with Potassium 1,2-Ethandithiolate in the System Hydrazine Hydrate–KOH: Heterocyclization Paths

Cover Page

Cite item

Full Text

Open Access Open Access
Restricted Access Access granted
Restricted Access Subscription or Fee Access

Abstract

Quantum chemical modeling of the mechanism of interaction of propargyl chloride with potassium 1,2-ethanedithiolate in the hydrazine hydrate–KOH system was carried out using the combined approach CCSD(T)/6-31+G*//B3LYP/6-311++G**. The elementary stages of the reaction and possible routes for the heterocyclization of the initial intermediates have been found. Under experimental conditions at a reaction temperature of 40-42°C, 6 hours, 2-methyl-5,6-dihydro-1,4-dithiine was obtained with a yield of 25% and 4,7-dithiadecadiine-2,8 with a yield of 24%. At a temperature of –10 ÷ –15°С, cyclic products are not formed.

Full Text

Restricted Access

About the authors

E. A. Chirkina

A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences; Angarsky State Technical University, ul. Chaikovskogo

Author for correspondence.
Email: chirkina_ea@mail.ru
ORCID iD: 0000-0002-1733-0685
Russian Federation, Favorskogo, 1, Irkutsk, 664033; ul. Chaikovskogo, 60, Angarsk, 665835

V. A. Grabelnykh

A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences

Email: chirkina_ea@mail.ru
ORCID iD: 0000-0003-1067-7755
ul. Favorskogo, 1, Irkutsk, 664033

N. A. Korchevin

A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences; Angarsky State Technical University, ul. Chaikovskogo

Email: chirkina_ea@mail.ru
Scopus Author ID: 0000-0001-5729-9080
Favorskogo, 1, Irkutsk, 664033; ul. Chaikovskogo, 60, Angarsk, 665835

L. B. Krivdin

A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences; Angarsky State Technical University, ul. Chaikovskogo

Email: chirkina_ea@mail.ru
ORCID iD: 0000-0003-2941-1084
Russian Federation, Favorskogo, 1, Irkutsk, 664033; ul. Chaikovskogo, 60, Angarsk, 665835

I. B. Rosenzweig

A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences

Email: chirkina_ea@mail.ru
ORCID iD: 0000-0001-7817-7816
Russian Federation, , ul. Favorskogo, 1, Irkutsk, 664033

References

  1. Chirkina E.A., Grabelnykh B.A., Korchevin H.A., Krivdin L.B., Ushakov I.A., Rozentsveig I.B. Structural Chemistry, 2023, 34, 2263–2272. doi: 10.1007/s11224-023-02199-9
  2. Levanova E.P., Grabelnykh V.A., Vahrina V.S., Albanov A.I., Klyba L.V., Russavskaya N.V., Korchevin N.A., Rozentsveig I.B. J. Sulfur Chem. 2014, 35, 179–187. doi: 10.1080/17415993.2013.849704
  3. Becke A.D. J. Chem. Phys. 1993, 98, 5648-5652. doi: 10.1063/1.464913
  4. Lee C., Yang W., Parr R.G. Phys. Rev. B 1988, 37, 785-789. doi: 10.1103/PhysRevB.37.785
  5. Леванова Е.П., Никонова В.С., Грабельных В.А., Руссавская Н.В., Албанов А.И., Розенцвейг И.Б., Корчевин Н.А. ЖОрХ. 2016, 52, 540–541. [Levanova E.P., Nikonova V.S., Grabelnykh V.A., Russavskaya N.V., Albanov A.I., Rozentsveig I.B., Korchevin N.A. Russ. J. Org. Chem. 2016, 52, 615–623. doi: 10.1134/S1070428016050018
  6. Gaussian 09, Revision C.01, Frisch M.J., Trucks G.W., Schlegel H.B., Scuseria G.E., Robb M.A., Cheeseman J.R., Scalmani G., Barone V., Mennucci B., Petersson G.A., Nakatsuji H., Caricato M., Li X., Hratchian H.P., Izmaylov A.F., Bloino J., Zheng G., Sonnenberg J.L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery J.A., Peralta J.E., Ogliaro F., Bearpark M., Heyd J.J., Brothers E., Kudin K.N., Staroverov V.N., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J.C., Iyengar S.S., Tomasi J., Cossi M., Rega N., Millam J.M., Klene M., Knox J.E., Cross J.B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R.E., Yazyev O., Austin A.J., Cammi R., Pomelli C., Ochterski J.W., Martin R.L., Morokuma K., Zakrzewski V.G., Voth G. A., Salvador P., Dannenberg J.J., Dapprich S., Daniels A.D., Farkas Ö., Foresman J.B., Ortiz J.V., Cioslowski J., and Fox D.J., Gaussian, Inc., Wallingford CT, 2009.
  7. Хусайнов З.К., Ойматова Х.Х., Сафаров М.М., Тургунбоев М.Т. Вестник Таджикского нац. универ. Сер. естеств. наук. 2019, 2, 196–203.
  8. Современные методы органического синтеза. Ред. Т.В. Мандельштам, Б.В. Иоффе, Ю.П. Арцыбашева. Ленинград, 1980.
  9. Berne B.J., Tuckerman M., Martyna G. J. Chem. Phys. 1991, 94, 6811. doi: 10.1063/1.460259
  10. González C., Schlegel H.B. J. Phys. Chem. 1990, 94, 5523–5527. doi: 10.1021/j100377a021
  11. González C., Schlegel H.B. J. Chem. Phys. 1991, 95, 5853. doi: 10.1063/1.461606

Supplementary files

Supplementary Files
Action
1. JATS XML
Download
2. Fig. 1. Energy profile of the reaction of propargyl chloride (1) with 1,2-ethanedithiolate (2) in the N2H4⋅H2O-KOH system, leading to the formation of heterocycles 3-6. The total energy of reactants 1 and 2 is taken as 0.0 kcal/mol.

Download (222KB)
Indexing metadata
3. Fig. 2. Spatial structure of the pre-reaction complex PRC-1, transition states TS-1–TS-4, intermediates IC-1, IC-2 and final products 5, 6 optimized by the B3LYP/6-311++G(d,p) method [3, 4]. Here and in Fig. 3, 6: bond lengths and interatomic distances are given in Å, valence angles are in degrees. The value of the imaginary vibrational frequency of the transition state is given in brackets.

Download (386KB)
Indexing metadata
4. Fig. 3. Spatial structure of transition states TS-5–TS-9, intermediate compound IC-3, prereaction complex PRC-2 and reaction products 3, 4, optimized by the B3LYP/6-311++G(d,p) method [3, 4]

Download (384KB)
Indexing metadata
5. Fig. 4. Energy profile of the reaction of propargyl chloride (1) with 1,2-ethanedithiolate (2) in the N2H4⋅H2O-KOH system, leading to the formation of heterocycle 3. The total energy of reactants 1 and 2 is taken as 0.0 kcal/mol.

Download (136KB)
Indexing metadata
6. Fig. 5. Energy profile of the reaction of 1-chloropropadiene-1,2 1a with 1,2-ethanedithiolate 2 in the N2H4⋅H2O-KOH system, leading to the formation of heterocycle 5. The total energy of the reactants 1a and 2 is taken as 0.0 kcal/mol.

Download (113KB)
Indexing metadata
7. Fig. 6. Spatial structure of the initial reagents 1, 1a, pre-reaction complex PRC-3, transition states TS-10–TS-13 and intermediate compounds IC-4, IC-5, optimized by the B3LYP/6-311++G(d,p) method [3, 4].

Download (379KB)
Indexing metadata
8. Scheme 1

Download (58KB)
Indexing metadata
9. Scheme 2

Download (58KB)
Indexing metadata
10. Scheme 3

Download (37KB)
Indexing metadata
11. Scheme 4

Download (72KB)
Indexing metadata
12. Scheme 5

Download (95KB)
Indexing metadata
13. Scheme 6

Download (116KB)
Indexing metadata
14. Scheme 7

Download (86KB)
Indexing metadata
15. Scheme 8

Download (79KB)
Indexing metadata
16. Scheme 9

Download (102KB)
Indexing metadata
17. Figure from Contents

Download (53KB)
Indexing metadata

Copyright (c) 2025 Russian Academy of Sciences