Fluorine isolation

Fluorine cannot be prepared directly by chemical methods. It is prepared in the laboratory and on an industrial scale by electrolysis. Two methods are employed (a) using fused potassium hydrogen-fluoride, KHFj, ill a cell heated electrically to 520-570 K or (b) using fused electrolyte, of composition KF HF = 1 2, in a cell at 340-370 K which can be electrically or steam heated. Moissan, who first isolated fluorine in 1886, used a method very similar to (b) and it is this process which is commonly used in the laboratory and on an industrial scale today. There have been many cell designs but the cell is usually made from steel, or a copper-nickel alloy ( Monel metal). Steel or copper cathodes and specially made amorphous carbon anodes (to minimise attack by fluorine) are used. Hydrogen is formed at the cathode and fluorine at the anode, and the hydrogen fluoride content of the fused electrolyte is maintained by passing in... 

The F H- H — H —> F—H + H reaction is a common example of a reaction easily studied by classical trajectory analysis. The potential surface we are interested in is that for FH2. This potential surface may have many extrema. One of them corresponds to an isolated Fluorine atom and a stable H2 molecule these are the reactants. Another extremum of the surface corresponds to an isolated hydrogen atom and the stable H-Fmolecule these are the products. Depending on how the potential surface was obtained there may or may not be an extremum corresponding to stable H2F, but at the least you would expect an extremum corresponding to the transition state of the reaction being considered. 

The names fluorine and fluorospar are derived from the Latin fluere meaning flow or flux. In 1529 the use of fluorspar as a flux was described. In 1670 the etching of glass by acid-treated fluorspar was reported. Elemental fluorine was isolated by Moissan ia 1886 (7). 

Because PTFE resins decompose slowly, they may be heated to a high temperature. The toxicity of the pyrolysis products warrants care where exposure of personnel is likely to occur (120). Above 230°C decomposition rates become measurable (0.0001% per hour). Small amounts of toxic perfiuoroisobutylene have been isolated at 400°C and above free fluorine has never been found. Above 690°C the decomposition products bum but do not support combustion if the heat is removed. Combustion products consist primarily of carbon dioxide, carbon tetrafluoride, and small quantities of toxic and corrosive hydrogen fluoride. The PTFE resins are nonflammable and do not propagate flame. 

Antimony pentafluoride is a strong Lewis acid and a good oxidizing and fluorinating agent. Its behavior as a Lewis acid leads to the formation of numerous simple and complex adducts. It reacts vigorously with water to form a clear solution from which antimony pentafluoride dihydrate [65277-49-8], SbF 2H2O, may be isolated. This is probably not a tme hydrate, but may well be better formulated as [H O] [SbF OH]. 

Chlorine and fluorine in beryUium metal are isolated by pyrohydrolysis or by distUlation (21). Fluoride and chloride in the condensate are determined by ion-selective electrode or colorimetricaUy. 

When there is an a-hydrogen in the sulfide, the sulfuranes are unstable and cannot be isolated [775]. Sulfoxides [776] and sulfinyl fluorides [777] are oxidatively fluorinated with tluorine to give hexavalent sulfur compounds in yields up to 90%. 

In radical reactions not involving bromine or chlorine on the substrate, rearrangements are much rarer One example is the fluorination of di-tert butyl ketone which produces perfluormated / rt-buty isobutyl ketone [J5] Although isolated yields are poor only the rearranged ketone could be isolated This is perhaps only the second example of a 1,2-acyl shift Low fluorine substrate ratios show that this rearrangement occurs after monofluorination... 

The product from fluonnation of sodium acetate is acetyl hypofluorite [64], which IS isolated and characterized [65] The value of this reagent lies in its relative mildness, because it reacts cleanly with most olefins adding the elements of acetoxyl and fluorine [66] Tnfluoroacetyl hypofluorite adds cleanly only to benzylic or electron-rich double bonds... 

Up to 20 products with different numbers of fluorine atoms and double bonds have been isolated from the fluonnation of benzene with silver difluoride [d], manganese trifluoride [7], potassium tetrafluoroargentate [d], and potassium hexafluoronickelate [24] The composition of the products depends on the fluorinating agents and on the temperature (Table 1)... 

Similarly complex is the fluorination of the Ihtes methylpyridines (a-, ()-, and 7-picolmes) with cesium tetrafluorocobaltate. 2-Methylpyridme was fluorinated at 270 °C for 180-200 mm, 3- and 4-methylpyridmes were fluorinated at 330 to 340 °C for 150 min All of them afforded the respective polyjluorinated pyridines and perfiuoro-1,2-, 1,3-dimethyl-, and 1-ethylpyrrolidine In addition, perfluoro-2-aza-2-hexene and bis(tnfluoromethyl)amine were isolated m variable yields [27] All the isolated products of the fluorination of 3-methylpyridme (3-picoline) are shown in equation 9. 

Fluorination of aliphatic hydrocarbons with cobalt trifluoride gives complex mixtures Isobutane (2-methylpropane) fluorinated at 140-200 °C affords a mixture of 30 products of different degrees of fluorination and of isobutane as well as butane skeletons. The tertiary hydrogen is replaced preferentially Products containing 5-10 atoms of fluorine including a small amount of perfluoroisobutane were isolated [10]. 

Primary alkyl chlorides are fairly stable to fluorine displacement. When fluorinated, 1-chloropropane is converted to 1-chloroheptafluoropropane and 1-chloto-2-methylbutane produces 39% l-chlorononafluoro-2-methylbutane and 19% perfluoro-2-methylbutane. Secondary and tertiary alkyl chlorides can undergo 1,2-chlorine shifts to afford perfluonnated primary alkyl chlorides 2-Chloro-2-methylpropane gives l-chlorononafluoro-2-methylpropane, and three products are obtained by the fluorination of 3-chloropentane [7] (equation 1). Aerosol fluorina-tion of dichloromethane produces dichlorodifluoromethane which is isolated in 98% purity [4 (equation 2). If the molecule contains only carbon and halogens, the picture is different. Molecular beam analysis has shown that the reaction of fluorine with carbon tetrachlonde, lodotrichloromethane, or bromotrichloromethane proceeds first by abstraction of halogen to form a trichloromethyl radical [5]... 

An ipso attack on the fluorine carbon position of 4-fIuorophenol at -40 °C affords 4-fluoro-4-nitrocyclohexa-2 5-dienone in addtion to 2-nitrophenol The cyclodienone slowly isomenzes to the 2-nitrophenol Although ipso nitration on 4-fluorophenyl acetate furnishes the same cyclodienone the major by-product is 4 fluoro-2,6-dinitrophenol [25] Under similar conditions, 4-fluoroanisole pnmar ily yields the 2-nitro isomer and 6% of the cyclodienone The isolated 2 nitro isomer IS postulated to form by attack of the nitromum ion ipso to the fluorine with concomitant capture of the incipient carbocation by acetic acid Loss of the elements of methyl acetate follows The nitrodienone, being the keto tautomer of the nitrophenol, aromatizes to the isolated product [26] (equation 20) Intramolecular capture of the intermediate carbocation occurs in nitration of 2-(4-fluorophenoxy)-2-methyIpropanoic acid at low temperature to give the spiro products 3 3-di-methyl-8 fluoro 8 nitro-1,4 dioxaspiro[4 5]deca 6,9 dien 2 one and the 10-nitro isomer [2d] (equation 21)... 

Polyfluoroalkyl- andperfluoroalkyl-substituted CO and CN multiple bonds as dipolarophiles. Dmzo alkanes are well known to react with carbonyl compounds, usually under very mild conditions, to give oxiranes and ketones The reaction has been interpreted as a nucleophilic attack of the diazo alkane on the carbonyl group to yield diazonium betaines or 1,2,3 oxadiazol 2 ines as reaction intermediates, which generally are too unstable to be isolated Aromatic diazo compounds react readily with partially fluorinated and perfluorinated ketones to give l,3,4-oxadiazol-3-ines m high yield At 25 °C and above, the aryloxa-diazolines lose nitrogen to give epoxides [111]... 

Enamines from steroidal ketones have been fluorinated by means of perchloryl fluoride (119,120) to give the a-fluorinated ketones. Theenamino ketone (49) was brominated to give a salt from which the bromoenamino ketone (175) was isolated on treatment with dilute carbonate solution (121). 

Consistent with this, dissolution of KF increases the conductivity and KIFe can be isolated on removal of the solvent. Likewise NOF affords [NO]+[IF6] . Antimony compounds yield ISbFio, i-2. [IF4]+[SbF6], which can be titrated with KSbFfi. However, the milder fluorinating power of IF5 frequently enables partially fluorinated adducts to be isolated and in some of these the iodine is partly oxygenated. Complete structural identification of the products has not yet been established in all cases but typical stoichiometries are as follows ... 

IF7 is a stronger fluorinating agent that IF3 and reacts with most elements either in the cold or on wanning. CO enflames in IF7 vapour but NO reacts smoothly and SO2 only when warmed. IF7 vapour hydrolyses without violence to HIO4 and HF with small amounts of water at room temperature the oxyfluoride can be isolated ... 

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