Skip to main content
SpringerLink
Log in

Palladium-catalyzed three-component coupling

Polymerization of diyne, aryl dihalide, and hydride

  • Published:
Polymer Bulletin Aims and scope Submit manuscript

Summary

The palladium-catalyzed three-component coupling reaction of acetylenes, aryl halides, and hydride and it’s application to polymer synthesis are described. The coupling reaction of 1,2-diphenylacetylene, iodobenzene, and sodium diethyl benzylmalonate was carried out at 80°C for 48 h in 1,4-dioxane with Pd(OAc)2 / tri-o-tolylphosphine, from which triphenylethylene was obtained in 71% isolated yield. The benzylic hydrogen of sodium diethyl benzylmalonate was supposed to be a hydride source in the present reaction by detecting diethyl benzalmalonate in the reaction system. Based on the results, the coupling polymerization of l,2-bis(4-phenylethynylphenyl) ethane, 4,4′-diiodobiphenyl, and sodium diethyl benzylmalonate was carried out at 80°C for 48 h to produce a polymer (Mn= 8500, Mw / Mn = 3.0) in high yield. Using various aryl dihalides, the corresponding polymers having trisubstituted ethylene units were also obtained in high yields.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References and Notes

  1. Luneva LK, Sladlov AM, Korshak VV (1965) Vyskomol Soedin 7: 427

    CAS  Google Scholar 

  2. Chujo Y, Tomita I, Hashiguchi Y, Saegusa T (1990) Macromolecules 23: 687

    Article  CAS  Google Scholar 

  3. Kobayashi E, Metaka N, Aoshima S, Furukawa J (1990) J Polym Sci: Part A: Polym Chem 28: 2461

    Article  Google Scholar 

  4. Kobayashi E, Jiang J, Ohta H, Furukawa J (1992) J Polym Sci: Part A: Polym Chem 30: 227

    Article  CAS  Google Scholar 

  5. Chujo Y, Tomita I, Saegusa T (1992) Polym Bull 27: 375

    Article  CAS  Google Scholar 

  6. Kuroda H, Tomita I, Endo T (1995) Macromolecules 28: 433

    Article  CAS  Google Scholar 

  7. Kuroda H, Tomita I, Endo T (1995) Macromolecules 28: 6020

    Article  CAS  Google Scholar 

  8. Miyaki N, Tomita I, Endo T (1996) Macromolecules 29: 6685

    Article  CAS  Google Scholar 

  9. idem (1997) J Polym Sci: Part A: Polym Chem 35: 1211

    Article  CAS  Google Scholar 

  10. idem (1997) J Polym Sci: Part A: Polym Chem 35: 2097

    Article  CAS  Google Scholar 

  11. Miyaki N, Tomita I, Endo T idem (1997) Chem Lett 685

  12. idem (1997) Macromolecules 30: 4504

    Article  CAS  Google Scholar 

  13. Perlmutter P (1992) Conjugate Addition Reaction in Organic Synthesis. Pergamon: Oxford

    Google Scholar 

  14. Trost BM (1991) Comprehensive Organic Synthesis Vol. 4. Pergamon: Oxford

    Google Scholar 

  15. Cacchi S, Flelici M, Pietroni B (1984) Tetrahedron Lett 25: 3137

    Article  CAS  Google Scholar 

  16. Arcadi A, Cacchi S, Marinelli F (1985) Tetrahedron 41: 5121

    Article  CAS  Google Scholar 

  17. Arcadi A, Cacchi S, Marinelli F (1986) Tetrahedron Lett 27: 6397

    Article  CAS  Google Scholar 

  18. Arcadi A, Bernocchi E, Burini A, Cacchi S, Marinelli F, Pietroni B (1988) Tetrahedron 44: 481

    Article  CAS  Google Scholar 

  19. Arcadi A, Bernocchi E, Burini A, Cacchi S, Marinelli F, Pietroni B (1989) Tetrahedron Lett 30: 3465

    Article  CAS  Google Scholar 

  20. In the case of the reaction with 3b, the starting material (i.e., 1,2-diphenylethylene) was recovered in 61% yield.

  21. Trost BM (1977) Tetrahedron 33: 2615

    Article  CAS  Google Scholar 

  22. For the review related to the mechanisms on the Pd-catalyzed reactions, see: (a) Ram S, Ehrenkaufer RE (1988) Synthesis 91

  23. Tsuji J, Shimizu I (1990) J Synth Org Chem Jpn 48: 1016

    CAS  Google Scholar 

  24. A white powdery polymer could be isolated when the polymer was purified further by HPLC. Thus, the pale yellow color observed for the polymer after precipitation is originated from any contaminants (e.g., the palladium catalyst).

  25. The small peaks appeared at 6.5 ppm in the 1H-NMR spectrum might be attributed to the protons in the diene unit produced by the double insertion of the acetylene moieties. From the detailed analysis of the minor products in the model reaction of 1,2-diphenylacetylene, p- iodotoluene, and sodium diethyl benzylmalonate (3a), as described above, 1-p-tolyl-l,2,3,4-tetraphenyl-l,3-butadiene (i.e., a double insertion product of the acetylene to the arylpalladium species) was isolated in 19% yield (based on 1,2-diphenylacetylene) beside the major product. Although this result indicates the presence of the branched unit in 5a by means of the double insertion of the acetylene moieties, no gelation was observed unless the polymerization was carried out with an excess amount of the diyne.

  26. The double insertion process was detected as a side reaction in the model experiment. See, ref. (8).

Download references

Author information

Authors and Affiliations

  1. Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Nagatsuta, Midori-ku, 226, Yokohama, Japan

    Nobuyuki Miyaki & Takeshi Endo

  2. Department of Electronic Chemistry, Interdisziplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Nagatsuta, Midori-ku, 226, Yokohama, Japan

    Ikuyoshi Tomita

Authors
  1. Nobuyuki Miyaki
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ikuyoshi Tomita
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Takeshi Endo
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Miyaki, N., Tomita, I. & Endo, T. Palladium-catalyzed three-component coupling. Polymer Bulletin 39, 677–684 (1997). https://doi.org/10.1007/s002890050202

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s002890050202

Keywords

Search

Navigation