The Synthesis of Glycidylferrocenes and Related Compounds

Abstract

Ferrocene derivatives with one or two glycidyl substituents, desired for the formation of polymeric ferrocene compounds, were synthesized by the epoxidation of chlorohydrin compounds obtained from the products of the addition of ferrocenyllithium to epichlorohydrin at −40–−78°C. In the course of this synthesis, mono- and di-chlorohydrin compound and a disubstituted ferrocene with a 3-chloro-2-hydroxypropyl and a glycidyl substituent were isolated. All of them are stable liquid compounds. The investigation of the relationship between the reaction conditions and the yield of glycidylferrocenes revealed that the larger molar ratio of each reactant to ferrocene at each reaction step causes a higher conversion into glycidylferrocenes. In the epoxidation reaction of chlorohydrins with caustic alkali, a small amount of ethers, formed by the reaction of epoxides and the solvent ethanol, was obtained under some reaction conditions. In all cases, a small amount of biferrocenyl was isolated; the formation of this compound was considered to be attributable to the Wurtz-type coupling reaction of ferrocenyl radicals. The structures of all these products were confirmed by their infrared absorption spectra and, in part, by the NMR spectra.