Double fluorides

Electrochemical oxidation of alkyl aryl ethers results in oxidative dealkylation and coupling of the intermediate radicals. Electro-oxidation of alkyl (4-fluorophenyl) ethers in the presence of a hydrogen fluoride double salt leads to 4,4-difluorocyclohexa-2,5-dienone in 50% yield (Table 10).182 In the electrochemical oxidation of methyl tetrafluorophenyl ethers with a hydrogen atom at the para position, coupled products 6 arc obtained.183 If the para position in the substrate is occupied by a fluorine substituent, then no reaction occurs. 

With alkali fluorides double salts are produced, the compositions of which are as yet unknown. They are less easily reduced, however, than the free octafluoride. Sodium hydroxide decomposes them with evolution of ozone. 

In the gold(lll) halides (except the fluoride) there is evidence for the formation of double molecules, AujXg (cf. chlorides of iron(III) and aluminium) so that the coordination is brought up to four, but with a planar structure ... 

It was originally separated from zirconium by repeated recrystallization of the double ammonium or potassium fluorides by von Hevesey and Jantzen. Metallic hafnium was first prepared by van Arkel and deBoer by passing the vapor of the tetraiodide over a heated tungsten filament. Almost all hafnium metal now produced is made by reducing the tetrachloride with magnesium or with sodium (Kroll Process). 

Several cortisone derivatives with glucocorticoid effects are most active, if they contain fluorine in the 9or-position together with an Il(9-OH group. Both substituents are introduced by the cleavage of a 9,11 -epoxide with hydrogen fluoride. The regio- and stereoselective formation of the -epoxide is achieved by bromohydrination of a 9,11-double bond and subsequent alkali treatment (J. Fried, 1954). 

Ammonium fluorides react with many metal oxides or carbonates at elevated temperatures to form double fluorides eg,... 

Once purification of the niobium has been effected, the niobium can be reduced to the metallic form. The double fluoride salt with potassium, K2NbFy, can be reduced using sodium metal. The reaction is carried out in a cylindrical iron vessel filled with alternating layers of K NbF and oxygen-free sodium ... 

Rubidium metal alloys with the other alkaU metals, the alkaline-earth metals, antimony, bismuth, gold, and mercury. Rubidium forms double haUde salts with antimony, bismuth, cadmium, cobalt, copper, iron, lead, manganese, mercury, nickel, thorium, and 2iac. These complexes are generally water iasoluble and not hygroscopic. The soluble mbidium compounds are acetate, bromide, carbonate, chloride, chromate, fluoride, formate, hydroxide, iodide. 

Catalysis. Catalytic properties of the activated carbon surface are useful in both inorganic and organic synthesis. For example, the fumigant sulfuryl fluoride is made by reaction of sulfur dioxide with hydrogen fluoride and fluorine over activated carbon (114). Activated carbon also catalyzes the addition of halogens across a carbon—carbon double bond in the production of a variety of organic haUdes (85) and is used in the production of phosgene... 

The fluorite stmcture, which has a large crystal lattice energy, is adopted by Ce02 preferentially stahi1i2ing this oxide of the tetravalent cation rather than Ce202. Compounds of cerium(IV) other than the oxide, ceric fluoride [10060-10-3] CeF, and related materials, although less stable can be prepared. For example ceric sulfate [13590-82-4] Ce(S0 2> certain double salts are known. 

The double bond of a, -unsaturated ketones reacts with nitrosyl fluoride but only at room temperature and in small yield. Cholestenone produces a 4.2% yield of a 4< -fluoro-5( -nitro-3-ketone (46) after alumina chromatography. Similarly, the A -20-ketone grouping in 3j5-acetoxypregna-5,16-dien-20-one (47) reacts to form after chromatography a 14% yield of the... 

The reaction of 9(1 l)-dehydro steroids with nitrosyl fluoride was studied by Grantz and Rosenthal in pursuit of an alternate source for the important 9a-fluoro-11-oxygenated steroids. As expected, reaction at the more hindered 9(1 l)-double bond proceeds more slowly than at either the 4- or 5-double bonds. After 10 days at 3°, 3 -acetoxy-5a-pregn-9(l l)-en-20-one (50) affords a 45% yield of the 9a-fluoro-ll-nitrimine (51). Other 9a-fluoro-ll-nitrimines were prepared and it was found that the presence of additional keto groups, particularly the 3-keto group gives rise to side products with a concomitant reduction in yield of the desired 9a-fluoro-ll-nitrimines. In the case of the A" -3-ketones the yield is reduced to 10 %. The steric hindrance... 

Addition of fluorohalides to double bonds preparation of 9a-bromo-ll/3-fluoro-17q , 21-dihydroxypregn-4-ene-3, 20-dione 21-acetate by reaction with N-bromoacetamide-hy drogen fluoride, 458... 

Anhydrous hydrogen fluoride adds across carbon-carbon double and triple bonds and to other unsaturated systems, but wide variations of solvent, catalyst, temperature, and conditions are required with different substrates. 

Hydrogen fluoride adds to more complex molecules, such as unsaturated steroids, to give fluorinated derivatives [/, 8] Low temperatures and inert diluents, such as tetrahydrofuran or methylene chloride, are generally employed. With bicyclic unsaturated terpenes, rearrangements often accompany addition to the double bond [/]. 

With very electrophilic olefins, an alternative hydrogen fluoride addition process is often preferred This process, involving reaction of the olefin with fluoride ion in the presence of a proton donor, is applicable to certain perhalogen ated alkenes [/] and substrates with other electron attracting groups attached to the double bond [i5, 36] (equations 4 and 5)... 

Reactions of the halogen iluorides with other unsaturated functional groups are generally reported only with highly fluorinated substrates Hexafluorobenzene and denvatives [118] and octaflvoronaphthalene [119] react with mixtures of bromine and bromine trifluoride by 1,4 addition of fluorine followed by addition of bromine fluoride across a reniatning double bond (equation 22)... 

Hydrolysis of geminal fluorides requires activation by per- or polyfluoroalkyl or perfluoroaryl groups and by double bonds linked to the same or adjacent carbon The activation is the result of reducing the electron density at the fluorinated carbon, facilitating attack by, primarily, nucleophilic reagents... 

Conjugated terminal fluoroenynes add water to the double bond at -5 C to form a-fluoro allemc acid fluondes. At 20 C, the allenic acid fluorides and concentrated sulfunc acid give y- and 8-laaones (equation 1) In the presence of concentrated sulfuric acid, conjugated nontermmal fluoroenynes add water to the triple bond and then to the double bond to form a-fl uoro-P-diketones and exocyclic a-fluoroenones [/] (equation 2). 

Examples of perfluoroalkyl iodide addition to the triple bond include free radical addition of perfluoropropyl iodide to 1 -heptyne [28] (equation 21), thermal and free radical-initiated addition of lodoperfluoroalkanesulfonyl fluorides to acetylene [29] (equation 22), thermal addition of perfluoropropyl iodide to hexa-fluoro 2 butyne [30] (equation 23), and palladium-catalyzed addition of per-fluorobutyl iodide to phenylacetylene [31] (equation 24) The E isomers predominate in these reactions Photochemical addition of tnfluoromethyl iodide to vinylacetylene gives predominantly the 1 4 adduct by addition to the double bond [32] Platinum catalyzed addition of perfluorooctyl iodide to l-hexyne in the presence of potassium carbonate, carbon monoxide, and ethanol gives ethyl () per fluorooctyl-a-butylpropenoate [JJ] (equation 25)... 

Double dehydrobromination of cis- and tranj-l-(bromodifluoromethyl)-2-bromocyclohexane with potassium hydroxide gives, as the final product, 1 -cyclohexene-1-carboxylic acid as a result of the hydrolysis of the intermediate, 1-cyclohexenecarbonyl fluoride 4 (equation 4)... 

Dehydrofluormation of A/,0-bis(tnfluoromethyl)hydroxylamine with potassium fluoride gives an excellent yield of a perfluorinated oxime ether [25] with a carhon-nitrogen double bond (equation 23)... 

Isomerization of fluoroolefins by a shift of a double bond is catalyzed by halide 10ns [7] The presence of crown ether makes this reaction more efficient [74] Prolonged reaction time favors the rearranged product with an internal double bond (equations 3-5) Isomerization of perfluoro-l-pentene with cesium fluoride yields perfluoro-2-pentenes in a Z ratio of 1 6 [75] Antimony pentafluoride also causes isomenzation of olefins leading to more substituted products [76]... 

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