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Cyanoethylation of cyclopentadiene: Isolation of penta- and hexa(β-cyanoethyl)cyclopentadiene and an unexpected acrylonitrile polymer

Summary

The cyanoethylation of cyclopentadiene was examined under a variety of reaction conditions. Approximately 9% of cyclopentadiene was converted to the desired hexa(β-cyanoethyl)cyclopentadiene when the amount of acrylonitrile to cyclopentadiene was increased from 2 to 7 equivalents under phase transfer conditions. The low conversion is due to competitive formation of various unreactive side-products. For example, termination leading to less-highly substituted products was confirmed by isolation of crystalline 1,1,2,3,4-penta(β-cyanoethyl)cyclopentadiene. Another side product isolated and characterized by 13C NMR was an oligomer of acrylonitrile attached to hexa(β-cyanoethyl)cyclopentadiene; the anion (at a β-alkyl position) of the latter apparently acted as anionic initiator. Attempts to induce thermal polymerization and cyclotrimerization of the pendent cyano groups of hexa(β-cyanoethyl)cyclopentadiene were unsuccessful even with added Lewis acid catalysts. Reduction to the hexaamine was only partially successful.

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Mathias, L.J., Roberts, C.C. & Muthiah, J. Cyanoethylation of cyclopentadiene: Isolation of penta- and hexa(β-cyanoethyl)cyclopentadiene and an unexpected acrylonitrile polymer. Polymer Bulletin 27, 389–394 (1992). https://doi.org/10.1007/BF00309694

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Keywords

  • Hexa
  • Oligomer
  • Penta
  • Lewis Acid
  • Acrylonitrile