CYANOETHYLATION OF CYCLOPENTADIENE - ISOLATION OF PENTA(BETA-CYANOETHYL)CYCLOPENTADIENE AND HEXA(BETA-CYANOETHYL)CYCLOPENTADIENE AND AN UNEXPECTED ACRYLONITRILE POLYMER
Polymers and High Performance Materials
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.
Mathias, L. J.,
(1992). CYANOETHYLATION OF CYCLOPENTADIENE - ISOLATION OF PENTA(BETA-CYANOETHYL)CYCLOPENTADIENE AND HEXA(BETA-CYANOETHYL)CYCLOPENTADIENE AND AN UNEXPECTED ACRYLONITRILE POLYMER. POLYMER BULLETIN, 27(4), 389-394.
Available at: http://aquila.usm.edu/fac_pubs/6747