Polyfluorinated organic

Polyfluorinated organic compounds often have much lower boiling points than might be expected. 

A specific challenge remains for the metal-induced cleavage of the strongest bond that carbon can form, the C-F bond [57 f). The functionalization of polyfluorinated organic compounds - important building blocks of chemical, pharmaceutical, and advanced materials industries - would promise a diverse market for such a process. First success in this area is based on the stoichiometric reaction of eq. (9),... 

Furin, G.G., Phosphorus-containing nucleophiles in reactions with polyfluorinated organic compounds, Usp. Khim., 62, 201, 1993 Russ. Chem. Rev., 62, 243, 1993. 

Cathodic Reduction of Other Polyfluorinated Organic Compounds. 57... 

CATHODIC REDUCTION OF PERFLUORINATED AND POLYFLUORINATED ORGANIC HALIDES... 

CATHODIC REDUCTION OF OTHER POLYFLUORINATED ORGANIC COMPOUNDS... 

The radiation chemistry of polyfluorinated organic compounds has been reviewed and publications have appeared that deal with the following (i) free-radical yields in the radiolysis of gaseous hexafluoroethane (ii) radiolysis free-ion yields and electron ranges in liquid fluoromethanes (CH4- Fn, n = I—4) (iii) ring-opening products of the radiolysis of perfluoro(methylcyclohexane) ... 

Contents of Vol. 6 The Radiation Chemistry of Polyfluorinated Organic Compounds (H. Sutcliffe and I. McAlpine) Fluoro-jS-diketones and Metal Fluoro- S-diketonates (P. Mushak, M. Glenn, and J. Savory) N.M.R. Spectra and Characteristic Frequencies of Compounds containing N—S—F Bonds (M. Horn). 

Fluorinated diacids offer a convenient method for introducing a perfluoro moiety into organic molecules. They are of potential interest in the preparation of polyamides and other fluorinated polymers. A detailed description of the perfluorocarboxyUc acids and their derivatives has been pubflshed (1), and a review article on polyfluorinated linear biflmctional compounds has appeared (35). 

Abramovitch et al. " and Banks et al. discovered that unlike most aryMtrenes, polyfluorinated arylnitrenes have a bountiful bimolecular chemistry. Perfluorophen-ylnitrene reacts with diethylamine to form a hydrazine, with tetramethylethylene to form an aziridine and forms robust adducts with benzene and even cyclohexane. Polyfluorinated arylnitrenes are useful reagents in synthetic organic chemistry, photoaffinity labeling, and for the covalent modification of polymer surfaces. ... 

Perfluoroalkyl acids (PFAs) are synthetic, perfluorinated, straight- or bran-ched-chain organic acids characterized by a carboxylate or sulfonate moiety [1]. PFAs are manufactured directly but can also be formed through transformation of many precursor molecules containing a perfluoroalkyl moiety [2], These include fluorotelomer alcohols (FTOHs) and perfluoroalkyl-sulfonamides (Table 1, Fig. 1), however, others likely exist. Collectively, this family of chemicals including PFAs and their polyfluorinated precursors will be referred to in this document as perfluoroalkyl substances (PFSs). 

Generation of electrophilic species from organic polyfluorinated materials usually requires direct interaction of a strong Lewis acid with a substrate, which can result in formation of a cation either by abstraction of a halogen anion (usually F ) from a substrate (Eq. 8) or by formation of a zwitterionic intermediate as a result of coordination of the Lewis acid with an unshared electron pair on a multiply bonded heteroatom (Eq. 9) [12] ... 

Simons process — Electrochemical polyfluorination reactions of organic compounds are the only efficient way to industrial production of perfluorinated compounds. The reaction proceeds in the solution of KF in liquid HF (b.p. 19.5 °C), where the starting substances as alcohols, amines, ethers, esters, aliphatic hydrocarbons and halo-hydrocarbons, aromatic and heterocyclic compounds, sulfo- or carboxylic acids are dissolved. During anodic oxidation, splitting of the C-H bonds and saturation of the C=C bonds occur and fluorine atoms are introduced. 

In an alternative approach, volatile organic substrates were fluorinated in the gas phase on contact with a copper mesh. This work was pioneered by Fredenhagen and Cadenbach in the early 1930s [5] and then continued by Bigelow and Fukuhara [6] as a part of the Manhattan Project (Figure 2.1). Vapor phase fluorination finally enabled the preparation of (relatively) defined polyfluorination products from aliphatic hydrocarbons, benzene, or acetone. 

Moldavski, D.D. Furin, G.G. Polyfluorination of organic compounds. Zhurn. Obsch. Khimii. 1996, 66, 1995-2002. 

---