New routes to novel oeganofluorine compounds

Abstract

Use of the carbon hydrogen bond as a functional group in free radical addition reactions to fluorinated olefins has been studied. Using cyclic ethers a detailed investigation of the products obtained revealed that not only carbon hydrogen bonds a to oxygen but also the β and γ carbon hydrogen bonds reacted. Employing hydrocarbons, clean free radical addition reactions initiated by either γ rays or peroxides were observed. Whereas aliphatic hydrocarbons gave reasonable yields, cyclic hydrocarbons gave nearly complete conversions. Some modifications of polyethylene using fluorinated olefins and fluorinated ketones proved successful. Free radical reactions of tributyltin hydride with fluoro-olefins gave quantitative yields of new tributyl fluoroalkyltin compounds. Employing partly fluorinated ethers, amines and hydrocarbons exhaustive fluorinations using two different techniques were carried out. Photofluorination gave good yields of the corresponding perfluorinated compounds and a new apparatus, making this technique more generally applicable was designed. Electrochemical fluorination also gave remarkably good yields of perfluorinated products. This demonstrated the suitability of partly fluorinated compounds for further fluorination to perfluorinated derivatives by these techniques.