SpringerLink
Log in

Quantum-chemical study of organic reactions mechanisms

XII.1 The reaction of propargyl chloride with potassium 1,3-propandithiolate in the system hydrazine hydrate–KOH: calculations and experiment

  • Research
  • Published:
Structural Chemistry Aims and scope Submit manuscript

Abstract

The interaction of 1,3-propanedithiolate with propargyl chloride leads to the formation of a mixture of products. After completion of the reaction (40–42 °C, 6.5 h), two main compounds were isolated: 2-methyl-6,7-dihydro-5H-1,4-dithiepin (62%) and 4,8-dithioundecadiin-2.9 (12%). Quantum chemical modeling of the mechanism of interaction between propargyl chloride and potassium 1,3-propanedithiolate in the hydrazine hydrate–KOH system was carried out using the combined approach CCSD(T)/6–31 + G*//B3LYP/6–311 +  + G**. It was shown that the interaction of potassium propane dithiolate with propargyl chloride, leading to the formation of 2-methyl-6,7-dihydro-5H-1,4-dithiepine, proceeds sequentially via several stages. They include the nucleophilic substitution of the chlorine atom of propargyl chloride by one of the sulfide anions 1,3-propanedithiolate leading to the formation of a monosubstitution product. Under the influence of the medium, the latter undergoes an acetylene-allene rearrangement and turns into a more stable cumulated diene. The resulting diene derivative transforms into a dithiepine cycle due to the nucleophilic attack of the second sulfide anion of propane dithiolate on the sp-hybridized carbon atom. The formation of 4,8-dithioundecadiin-2,9 occurs when potassium propane dithiolate replaces chlorine atoms in two molecules of propargyl chloride, which is followed by the isomerization of the triple bond.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Scheme 2
Scheme 3
Scheme 4
Fig. 1
Scheme 5
Scheme 6
Scheme 7
Fig. 2
Fig. 3
Scheme 8
Fig. 4
Scheme 9
Fig. 5
Fig. 6

Similar content being viewed by others

Data availability

The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

References

  1. Chirkina EA, Larina LI (2022) Quantum‑chemical study of organic reaction mechanisms. XI. Biologically active 4‑substituted 1,2,4‑triazoles from diformylhydrazine and aminophenols. Struct Chem 33:2023–2032. https://doi.org/10.1007/s11224-022-01969-1

  2. Smith VA, Dil’man AD (2003) Foundations of modern organic synthesis. M.: Binom 750

  3. Schmid GN (1978) The chemistry of carbon-carbon triple bond. Ed. S. Patai, John Wiley & Sons, Chichester. 275. https://doi.org/10.1002/9780470771563.ch8

  4. Levanova EP, Grabelnykh VA, Vahrina VS et al (2014) Domino reactions of alkane dithiolates with 2,3-dichloro-1-propene in hydrazine hydrate – KOH medium. J Sulphur Chem 35:179–187. https://doi.org/10.1080/17415993.2013.849704

  5. Deryagina EN, Russavskaya NV, Papernaya LK et al (2005) Synthesis of organochalcogen compounds in basic reducing systems. Izv. Ross. Akad. Nauk, Ser. Khim 11:2395

  6. Deryagina EN, Korchevin NA, Russavskaya NV et al (1998) A mechanism of the hydrogenation of the double bond in the synthesis of allyl chalcogenides in the hydrazine hydrate-potassium hydroxide system. Izv. Ross. Akad. Nauk. Ser Khim 9:1874–1875

    Google Scholar 

  7. Barton D, Ollis WD (1981) Comprehensive organic chemistry. M.: Khimiya. 1:736

  8. Gaussian 09, Revision C.01 (2009) Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ, Gaussian, Inc., Wallingford CT

  9. Khusainov ZK, Oimatova KhKh, Safarov MM et al (2019) Dielectric capacity of hydrazine aqueous solutions at various temperatures and atmospheric pressures. Bulletin of the Tajik National University. Nat Sci Ser 2:196–203

    Google Scholar 

  10. Mandelshtam TV, Ioffe BV, Artsybasheva YuP (1980) Modern methods of organic synthesis. Leningrad 232

  11. Berne BJ, Tuckerman M, Martyna G (1991) Molecular dynamics algorithm for multiple time scales: systems with long range forces. J Chemical Phys 94:6811. https://doi.org/10.1063/1.460259

    Article  Google Scholar 

  12. Hratchian HP, Schlegel HB (2005) Finding minima, transition state, and following reaction pathways on ab initio potential energy surfaces: theory and applications of computational chemistry: the first 40 years, Edited by Dykstra CE, Frenking G, Kim KS, Scuseria G 195−249. https://doi.org/10.1016/B978-044451719-7/50053-6

Download references

Acknowledgements

The work was carried out using the material and technical base of the Baikal Analytical Center for Collective Use of the Siberian Branch of the Russian Academy of Sciences.

Author information

Authors and Affiliations

  1. A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1, Favorsky Str., 664033, Irkutsk, Russia

    Elena A. Chirkina, Valentina A. Grabelnykh, Nikolay A. Korchevin, Leonid B. Krivdin, Igor A. Ushakov & Igor B. Rozentsveig

  2. Angarsk State Technical University, 60 Chaikovsky Str., 665835, Angarsk, Irkutsk region, Russia

    Elena A. Chirkina, Nikolay A. Korchevin & Leonid B. Krivdin

  3. Irkutsk State University, Karl Marx Str., 1, 664003, Irkutsk, Russia

    Igor B. Rozentsveig

Authors
  1. Elena A. Chirkina
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Valentina A. Grabelnykh
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Nikolay A. Korchevin
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Leonid B. Krivdin
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Igor A. Ushakov
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Igor B. Rozentsveig
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

All authors contributed to the study conception and design. Valentina Grabelnykh and Nikolay Korchevin conducted experimental studies of the reaction. Igor Ushakov established the structure of the obtained compounds. Elena Chirkina performed quantum-chemical calculations of the reaction under reseach. The first version of the manuscript was written by Elena Chirkina and Nikolay Korchevin, and the correction of the manuscript was carried out by Leonid Krivdin and Igor Rozentsveig. All authors read and approved the final manuscript.

Corresponding author

Correspondence to Elena A. Chirkina.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

1Previous publication: XI see [1]

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 27216 KB)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chirkina, E.A., Grabelnykh, V.A., Korchevin, N.A. et al. Quantum-chemical study of organic reactions mechanisms. Struct Chem 34, 2263–2272 (2023). https://doi.org/10.1007/s11224-023-02199-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11224-023-02199-9

Keywords

Search

Navigation