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

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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.

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作者简介

E. Chirkina

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

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Email: chirkina_ea@mail.ru
ORCID iD: 0000-0002-1733-0685
俄罗斯联邦, Favorskogo, 1, Irkutsk, 664033; ul. Chaikovskogo, 60, Angarsk, 665835

V. 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. 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 作者 ID: 0000-0001-5729-9080
Favorskogo, 1, Irkutsk, 664033; ul. Chaikovskogo, 60, Angarsk, 665835

L. 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
俄罗斯联邦, Favorskogo, 1, Irkutsk, 664033; ul. Chaikovskogo, 60, Angarsk, 665835

I. 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
俄罗斯联邦, , ul. Favorskogo, 1, Irkutsk, 664033

参考

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  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
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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.

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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.

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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]

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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.

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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.

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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].

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8. Scheme 1

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9. Scheme 2

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10. Scheme 3

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11. Scheme 4

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12. Scheme 5

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13. Scheme 6

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14. Scheme 7

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15. Scheme 8

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16. Scheme 9

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17. Figure from Contents

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