Fluorination review

Volume II of Organic Reac tions an annual series that reviews reactions of interest to organic chemists contains the statement Most organic compounds burn or explode when brought in contact with fluorine... 

The halogen fluorides are binary compounds of bromine, chlorine, and iodine with fluorine. Of the eight known compounds, only bromine trifluoride, chlorine trifluoride, and iodine pentafluoride have been of commercial importance. Properties and appHcations have been reviewed (1 7) as have the reactions with organic compounds (8). Reviews covering the methods of preparation, properties, and analytical chemistry of the halogen fluorides are also available (9). 

P. Tarrant, ed.. Fluorine Chemisty Reviews, Vols. 1—8, Marcel Dekker, Inc., New York, 1967—1977. 

Electrochemical Fluorination. In the Simons electrochemical fluorination (ECF) process the organic reactant is dissolved in anhydrous hydrogen fluoride and fluorinated at the anode, usually nickel, of an electrochemical ceU. This process has been reviewed (6). Essentially all hydrogen atoms are substituted by fluorine atoms carbon—carbon multiple bonds are saturated. The product phase is heavier than the HF phase and insoluble in it and is recovered by phase separation. 

Perfluoroepoxid.es were first prepared ia the late 1950s by Du Pont Co. Subsequent work on these compounds has taken place throughout the world and is the subject of a number of reviews (1 5). The main use of these epoxides is as intermediates in the preparation of other fluorinated monomers. Although the polymerisation of the epoxides has been described (6—12), the resulting homopolymers and their derivatives are not significant commercial products. Almost all the work on perfluoroepoxides has been with three compounds tetrafluoroethylene oxide (TFEO), hexafluoropropylene oxide (HFPO), and perfluoroisobutylene oxide (PIBO). Most of this work has dealt with HFPO, the most versatile and by far the most valuable of this class of materials (4). 

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). 

MISCELLANEOUS FLUORINATED NITROGEN HETEROGYGLIGS Two reviews (1981, 1990) include nitrogen heterocychcs not covered in the present survey (482,483). The 1990 review dealing with four-, five-, and six-membered ring heterocycHc compounds emphasizes biological properties (482). 

Synthesis and Properties. Several polymers containing HFIP-O groups have been investigated, the most common beeing epoxies and polyurethanes. The development of fluorinated epoxy resins and the basic understanding of their chemistry has been reviewed (127). 

This article focuses on the commercial, ethylene-based ionomers and includes information on industrial uses and manufacture. The fluorinated polymers used as membranes are frequently included in ionomer reviews. Owing to the high concentration of polar groups, these polymers are generally not melt processible and are specially designed for specific membrane uses (see Fluorine compounds, organic—perfluoroalkane sulfonic acids Membrane technology). 

J. Y. Godard, ki R. E. Banks and K. C. Lowe, eds.. Fluorine Medicines of the 21st Century, Paper 10, University of Manchester, Institute of Science and Technology, Manchester, U.K., 1994, for a review kitroduckig fluorine kito corticosteroids. 

Fluorinated and Ghlorfluorinated Sulfonic Acids. The synthesis of chlorinated and fluorinated sulfonic acids has been extensively reviewed (91,92). The Hterature discusses the reaction of dialkyl sulfides and disulfides, sulfoxides and sulfones, alkanesulfonyl haHdes, alkanesulfonic acids and alkanethiols with oxygen, hydrogen chloride, hydrogen fluoride, and oxygen—chloride—hydrogen fluoride mixtures over metal haHde catalysts, such as... 

In dimers composed of equal molecules the dimer components can replace each other through tunneling. This effect has been discovered by Dyke et al. [1972] as interconversion splitting of rotational levels of (HF)2 in molecular beam electric resonance spectra. This dimer has been studied in many papers by microwave and far infrared tunable difference-frequency laser spectroscopy (see review papers by Truhlar [1990] and by Quack and Suhm [1991]). The dimer consists of two inequivalent HE molecules, the H atom of one of them participating in the hydrogen bond between the fluorine atoms (fig. 60). PES is a function of six variables indicated in this figure. 

Alkyl fluorides have been prepared by reaction between elementary fluorine and the paraffins, by the addition of hydrogen fluoride to olefins, by the reaction of alkyl halides with mercurous fluoride, with mercuric fluoride, with silver fluoride, or with potassium fluoride under pressure. The procedure used is based on that of Hoffmann involving interaction at atmospheric pressure of anhydrous potassium fluoride with an alkyl halide in the presence of ethylene glycol as a solvent for the inorganic fluoride a small amount of olefin accompanies the alkyl fluoride produced and is readily removed by treatment with bromine-potassium bromide solution. Methods for the preparation of alkyl monofluorides have been reviewed. ... 

As a result, the intervening 15 years have witnessed the development of procedures for the introduction of fluorine in practically every available position of the steroid nucleus. Moreover, fluorine-containing groups such as CF2 and CF3 have been substituted at various positions. A number of recent books and reviews deal extensively with this subject. ... 

The survey of the organic fluorine literature is subdivided into a section on monographs that is practically exhaustive and a section of review papers published in various [ournals The review papers mentioned were selected on the basis of the... 

Following are the contents of the most recent volume of P Tarrant s Fluorine Chemistry Reviews... 

Tarrant P Fluorine Chemistry Reviews, Vol 8 Marcel Dekker New York 206... 

Fluorinatton of graphite with fluorine gives graphite fluorides that have interesting properties, as recently reviewed [63]. Pyridine and its derivatives add elemental fluorine to form unstable N-fluoro adducts [14, 26, 64, 65]. These may decompose to 2-fluoropyndines [65] or be stabilized by treatment with inflate salts to form useful electrophilic fluonnating agents [64]... 

Many mtrogen-contammg functional groups react with fluorine to give a variety of products Several reagents add fluorine to nitro anions, as shown in equations 7 and 8 66, 67, 68] A detailed review of these reactions was recently published [69]... 

Electropositive fluorinating agents are categorized in distinct classes as (1) fluoroxy reagents, in which the fluorine is bound to an oxygen atom (for reviews, see references 1,2,3, 4, 5, and 6) (2) fluoraza reagents, in which the fluorine atom IS bound to the nitrogen atom of either an amide or ammonium ion structure (for a partial review, see reference 6), (3) xenon difluoride, in which the fluorine atoms are bound to xenon (for reviews, see references 5, 7, 8, and 114) and (4) perchloryl Iluoride, in which the fluorine atom is bound to the chlorine atom of the perchloryl function (for a review, see reference 9). 

Many fluorinations by electropositive fluorine reagents produce a-fluoro carbonyl compounds as the final result An extensive review exists on the preparation of a-fiuorocarbonyl compounds [101 Also, electropositive reagents are used widely in the preparation of F-labeled radioactive materials required in positron etmssion tomography for biomedical research Excellent reviews are available on fluonne-18 labeling [//, 72]. 

The vapor-phase catalytic replacement of chlorine by fluorine with hydrogen fluoride as the fluorine source has been the subject of a number of patents for the synthesis of Freons or Genetrons This topic has been carefully reviewed in the literature [2, p 97ff] One advantage of using a catalyst with hydrogen fluoride is to allow some degree of selectivity in the displacement of a specific chlorine from... 

This topic has been reviewed [2, pp 94, 100-111, 130-134] All of the standard approaches to the synthesis of a compound like methyl 2-fluorostearate from methyl 2-bromostearate result mall yield of the 2-fluoro ester and the unsaturated esters. Although silver fluoride is not a new reagent, its use moist in wet acetonitrile to convert methyl 2-bromostearate to its fluoro ester is a departure from the traditional set of anhydrous conditions (Procedure 6, p 194) [71] In contrast, silver tetrafluoroborate converts a-chloroketones to their respective fluoroketones under anhydrous conditions. The displacement of less activated halogen groups by silver tetrafluoroborate to form their respective fluorides is novel Although silver tetrafluoroborate could not be used to convert an aliphatic terminal dichloromethyl or trichloromethyl group to its corresponding fluoro derivative, it is an effective fluorine source in other situations [72] (Table 8)... 

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