Silver® fluoride

Fluorinations with Silver Fluoride. Reaction of AgF with alkyl and aryl halides often results in the formation of the corresponding fluorides usually under mild conditions. With gemi-nal dihalides, this conversion has been shown to involve a carbo-nium ion intermediate (eq 1). Chloro quinones react with AgF under high pressure and temperature conditions to give partial conversion to the fluoro quinone (eq 2). Cis- and trans-2,3-difluoro-2,3-dihydrobenzofuran can be similarly obtained by the reaction of AgF with trans-2,3-dibromo-2,3-dihydrobenzofuran (eq 3). Bromoadamantanes and l-bromobicyclo[3.3.1]nonan-3-one undergo fluorination with AgF to yield bridgehead fluorine derivatives (eq 4). 

A list of General Abbreviations appears on the front Endpapers 

Fluorination of Alkenes by Addition Reactions. /S-Ruoro thioethers can be prepared by the addition of sulfenyl chlorides to alkenes in the presence of AgF. The addition to alkyl-substituted terminal alkenes usually produces anti-Markovnikov adducts with a primary fluorine. Unlike the corresponding chlorides, these materials do not undergo rearrangement to the thermodynamically more stable Markovnikov products (eq 5).  

Silver fluoride adds to electron deficient alkenes. The reaction of l,l-dichloro-2,2-dicyanoethylene with AgF, for example, does not produce the expected 1,1-difluoro derivative. Instead, this reaction yields the silver salt of trifluoromethylmalononitrile, presumably through the 1,1-difluoro derivative by subsequent addition of AgF to the strongly electrophilic double bond. Perfluo-roalkylsilver compounds can be prepared by the addition of AgF to perfluoroalkenes. The fluorination of tetrabromo-2,3-diaza-1,3-butadiene affords the tetrafluoro derivative. 

In work by Evans and co-workers, deprotection of a silyl ether with AgF leads to the formation of an intermediate positioned to undergo a rapid Cope rearrangement. Subsequent loss of methanol results in the formation of the deoxylapachol product in 95% yield (eq 12). Additionally, certain nitrosoalkenes, which can be active dienes in [4 + 2] cycloadditions, can be prepared from a-chlorosilyloximes by 1,4-elimination in the presence of an appropriate fluoride source, such as AgE Successful cycloadditions are also observed with cesium fluoride and potassium fluoride (eq 13). 

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Many ionic halides dissolve in water to give hydrated ions. The solubility of a given halide depends on several factors, and generalisations are difficult. Ionic fluorides, however, often differ from other halides in solubility. For example, calcium fluoride is insoluble but the other halides of calcium are highly soluble silver fluoride. AgF, is very soluble but the other silver halides are insoluble. 

Silicon Alkali carbonates, calcium, chlorine, cobalt(II) fluoride, manganese trifluoride, oxidants, silver fluoride, sodium-potassium alloy... 

Preparation. Silver fluoride can be prepared by dissolving Ag20 or Ag2C02 iu anhydrous hydrogen fluoride or aqueous hydrofluoric acid, evaporating to dryness, and then treating with methanol or ether. 

Silver fluoride forms explosive adducts with ammonia (qv) (5,6), and therefore all of the reactions involving Hquid or gaseous ammonia should be carried out with extreme precautions. 

Uses. Silver fluoride has found many laboratory and special industrial appHcations. It is used as a soft (nHld) fluorinating agent for selective fluorination (7—17), as a cathode material in batteries (qv) (18), and as an antimicrobial agent (19). Silver fluoride is commercially available from Advance Research Chemicals, Inc., Aldrich Chemicals, Cerac Corp., Johnson/Matthey, PCR, Atochem, and other sources in the United States. The U.S. price of silver fluoride in 1993 was 1000— 1400/kg and the total U.S. consumption was less than 200 kg/yr. 

Silver difluoride, commercially available from the same sources as those of AgF, had a 1993 price between 1000— 1400/kg. In spite of the technical success in laboratory experiments, silver fluorides have found limited use on a large scale mainly because of the high cost of the reagents. Demand for silver difluoride is less than 100 kg/yr. 

Silver Fluoride. Silver fluoride, AgF, is prepared by treating a basic silver salt such as silver oxide or silver carbonate, with hydrogen fluoride. Silver fluoride can exist as the anhydrous salt, a dihydrate [72214-21-2] (<42° C), and a tetrahydrate [22424-42-6] (<18° C). The anhydrous salt is colorless, but the dihydrate and tetrahydrate are yellow. Ultraviolet light or electrolysis decomposes silver fluoride to silver subfluoride [1302-01 -8] Ag2p, and fluorine. 

The best known of the hahdes are the trialkyldihalo- and triaryldihaloantimony compounds. The dichloro, dibromo, and diiodo compounds are generally prepared by direct halogenation of the corresponding tertiary stibiaes. The difluoro compounds are obtained by metathasis from the dichloro or dibromo compounds and silver fluoride. The diiodo compounds are the least stable and are difficult to obtain ia a pure state. The tri alkyl- and triaryldichloro- and dibromoantimony compounds are all crystalline soHds which are stable at room temperature that but decompose on heating ... 

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. ... 

Fluoride ion sources include alkali metal, ammonium, tetraalkylammomum, and silver fluorides. With silver fluoride, the polyfluoroalkylsilver intermediates can be isolated [/, 37] (equation 6)... 

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)... 

Preparation of Methyl 2-Fluorostearate by Using Wet Silver Fluoride [71]... 

Rearrangement of fluorine with concomitant ring opening takes place in fluorinated epoxides Hexafluoroacetone can be prepared easily from perfluo-ropropylene oxide by isomerization with a fluorinated catalyst like alumina pre treated with hydrogen fluoride [26, 27, 28] In ring-opening reactions of epoxides, the distribution of products, ketone versus acyl fluoride, depends on the catalyst [29] (equation 7) When cesium, potassium, or silver fluoride are used as catalysts, dimenc products also are formed [29]... 

Alkyl fluorides can be prepared by the Finkelstein reaction. The fluoride anion is a bad leaving group the reverse reaction thus does not take place easily, and the equilibrium lies far to the right. As reagents potassium fluoride, silver fluoride or gaseous hydrogen fluoride may be used. 

Fluor-jod, n. iodine fluoride, -kalium, n. potassium fluoride, -kalzium, n. calcium fluoride, -kiesel, m. silicon fluoride, -kie-selsaure,/. fluosilicic acid, -kohlenstoff, m. carbon fluoride, -lithium, n. lithium fluoride. -metall, n. metallic fluoride, -natrium, n. sodium fluoride, -phosphat, n. fluophosphate. -phosphor, m. phosphorus fluoride, -salz, n. fluoride, -schwefel, m. sulfur fluoride, -selen, n. selenium fluoride, -silber, n. silver fluoride, -silikat, n. fluo-silicate. -silizium, n. silicon fluoride, -sili-ziumverbindung, /. fluosilicate. -tantal-sMure, /. fluotantalic acid, -tellur, n. tellurium fluoride, -titan, n. titanium fluoride, -toluol, n. fluorotoluene, fluotoluene. 

A crystalline 5,5 -diene, or bis (vinyl ether), derivative of sucrose has been prepared from 6,6 -dideoxy- 6,6 -diiodo-sucrose hexa-acetate, derived from the 6,6 -ditosylate, by treatment with silver fluoride in pyridine (26). 

The use of the silver fluoride reaction in the preparation of a nucleoside containing a 4, 5 double bond was recently reported (44). Thus treat-... 

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