Synthesis and Optical Properties of Phthalonitrile Oligomers

Abstract

Phthalonitrile and its derivatives react with Tin(II) reagents to give intensely colored linear oligomers. Structures are proposed for the oligomers based on elemental analysis, infrared, 1H and 13C spectra, and mass spectra. Stannous chloride has two kinds of properties, reducing reagent and Lewis acid. Tin(II) alkoxide initiates phthalonitrile oligomeriaztion when excess alkoxide is present. The mass spectrum indicates a chain length of at least a hexamer. In semi-empirical AM1 calculations, the helical conformation of a pentamer is indicated to be more stable than a linear conformation. The position of the electronic spectral maximum can be controlled by different kinds of reaction conditions and solution absorption and emission spectra were recorded.

Reactions of phthalonitriles with carbohydrates and alkali: phthalocyanine and oligomer formation

“…One report [16] of a polymerization also suggests this type of structure. We have also observed polymerization at one of two cyano groups in the polymer obtained from reaction of 1,2-dicyanoacenaphthylene with dimethylaminoethanol and its sodium salt [17,18]. Reaction involving one of two cyano groups in a phthalonitrile or dicyanoalkene clearly competes with the better known cyclotetramerization leading to Pcs [1][2][3][4][5][6] and cyclopolymerizations [7,19,20] leading to polyiminopyrrolines or polyisoindolines.…”