Cyanothaylation of Cyclopentadiene: Isolation of Penta(beta-cyanoethyl)cyclopentadiene and Hexa(beta-cyanoethyl)cyclopentadiene and an Unexpected Acrylonitrile Polymer

Document Type

Article

Publication Date

1-1-1992

Department

Polymers and High Performance Materials

Abstract

The cyanoethylation of cyclopentadiene was examined under a variety of reaction conditions. Approximately 9% of cyclopentadiene was converted to the desired hexa(beta-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(beta-cyanoethyl)cyclopentadiene. Another side product isolated and characterized by C-13 NMR was an oligomer of acrylonitrile attached to hexa(beta-cyanoethyl)cyclopentadiene; the anion (at a beta-alkyl position) of the latter apparently acted as anionic initiator. Attempts to induce thermal polymerization and cyclotrimerization of the pendent cyano groups of hexa(beta-cyanoethyl)cyclopentadiene were unsuccessful even with added Lewis acid catalysts. Reduction to the hexaamine was only partially successful.

Publication Title

Polymer Bulletin

Volume

27

Issue

4

First Page

389

Last Page

394

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