Acid fluorides reduction

Alternative paths for decomposition of the metal carboxylate can lead to ketones, acid anhydrides, esters, acid fluorides (1,11,22,68,77,78), and various coupling products (21,77,78), and aspects of these reactions have been reviewed (1,11). Competition from these routes is often substantial when thermal decomposition is carried out in the absence of a solvent (Section III,D), and their formation is attributable to homolytic pathways (11,21,77,78). Other alternative paths are reductive elimination rather than metal-carbon bond formation [Eq. (36)] (Section III,B) and formation of metal-oxygen rather than metal-carbon bonded compounds [e.g., Eqs. (107) (119) and (108) (120). Reactions (36) and (108) are reversible, and C02 activation (116) is involved in the reverse reactions (48,120). 

The well-known reduction of carbonyl groups to alcohols has been refuted in recent studies to render the reaction more regtoselecbve and more stereoselective Per-fluorodiketones are reduced by lithium aluminum hydride to the corresponding diols, but the use of potassium or sodium borohydride allows isolation of the ketoalcohol Similarly, a perfluoroketo acid fluoride yields diol with lithium aluminum hydride, but the related hydroxy acid is obtainable with potassium borohydride [55] (equations 46 and 47)... 

After insertion of CO, the resulting metal acyl complex could undergo a reductive elimination of RCOX. Alternatively, it may react with a variety of nucleophilic counterparts, which is what makes this chemistry so valuable in organic synthesis. Depending on the reaction media and the conditions, it is possible to synthesize acids, esters, amides, or acid fluorides from the same starting material, as shown in Scheme 2 for aryl-X compounds [16]. 

The best described case is the one of potassium tantalum fluoride reduction. This salt is currently obtained in the Marignac separation, from the potassium columbium oxyfluoride, by crystallization. The fully dried salt is mixed with clean sodium chips, pressed lightly in a steel bomb which is sealed and heated externally with gas. After the flash the cooled bomb is drilled out and the cake is treated with alcohol, water, and various acids. The powder obtained is processed to compact metal by pressing in bars and high vacuum sintering. 

Salts of o-halogeno-N-heterocyclics, such as 2-fluoro-l-methylpyri-dinium tosylate, and related compounds have been used successfully in a variety of reactions, particularly as agents for esterification, lactoni-zation, and the preparation of amides and thiolic esters They have been used also for the preparation of iodides from alcohols and acid fluorides from the acids as well as for Beckmann rearrangements and reductions, e.g. of a-hydroxyketones to ketones . Various condensed heterocyclic salts have been prepared from l-acylmethyl-2-chloropyridinium salts 2-Dialkylaminopyridinium salts have been used as phase transfer catalysts... 

The plan was to assemble the first carbocyclic ring of 3 by intramolecular aldol condensation of the keto aldehyde 15. The enantiomericaUy-pure secondary methyl substituent of 15 derived from the commercial monoester 10. Activation as the acid fluoride followed by selective reduction led to the volatile lactone 11. Opening of the lactone with HjCONHCHj HCl gave, after protection, the Weinreb amide 12. Alkylation of the derived hydrazone 13, selectively on the methyl group, led, after deprotection, to 15. The intramolecular aldol condensation of 15 did dehver the imstable cyclohexenone 1. Under the acidic conditions of the aldol condensation, the enol derived from the piperidone added in a Michael sense, from the axial direction on the newly-formed ring, to give the frans-fused bicyclic diketone 2. 

Silyl enol ethers are other ketone or aldehyde enolate equivalents and react with allyl carbonate to give allyl ketones or aldehydes 13,300. The transme-tallation of the 7r-allylpalladium methoxide, formed from allyl alkyl carbonate, with the silyl enol ether 464 forms the palladium enolate 465, which undergoes reductive elimination to afford the allyl ketone or aldehyde 466. For this reaction, neither fluoride anion nor a Lewis acid is necessary for the activation of silyl enol ethers. The reaction also proceed.s with metallic Pd supported on silica by a special method[301j. The ketene silyl acetal 467 derived from esters or lactones also reacts with allyl carbonates, affording allylated esters or lactones by using dppe as a ligand[302]... 

The mote electropositive metals react with cryohte, Hberating aluminum or aluminum monofluotide (22,23). The reduction of cryohte by magnesium is a current method for removal of magnesium in the refining of aluminum. Upon contact with strong acids cryohte Hberates hydrogen fluoride. 

Re OPe . The final step in the chemical processing of rare earths depends on the intended use of the product. Rare-earth chlorides, usually electrolytically reduced to the metallic form for use in metallurgy, are obtained by crystallisation of aqueous chloride solutions. Rare-earth fluorides, used for electrolytic or metaHothermic reduction, are obtained by precipitation with hydrofluoric acid. Rare-earth oxides are obtained by firing hydroxides, carbonates or oxalates, first precipitated from the aqueous solution, at 900°C. 

Chromium (II) also forms sulfides and oxides. Chromium (II) oxide [12018-00-7], CrO, has two forms a black pyrophoric powder produced from the action of nitric acid on chromium amalgam, and a hexagonal brown-red crystal made from reduction of Cr202 by hydrogen ia molten sodium fluoride (32). Chromium (II) sulfide [12018-06-3], CrS, can be prepared upon heating equimolar quantities of pure Cr metal and pure S ia a small, evacuated, sealed quartz tube at 1000°C for at least 24 hours. The reaction is not quantitative (33). The sulfide has a coordination number of six and displays a distorted octahedral geometry (34). 

Fluorides. Most woddwide reductions in dental decay can be ascribed to fluoride incorporation into drinking water, dentifrices, and mouth rinses. Numerous mechanisms have been described by which fluoride exerts a beneficial effect. Fluoride either reacts with tooth enamel to reduce its susceptibihty to dissolution in bacterial acids or interferes with the production of acid by bacterial within dental plaque. The multiple modes of action with fluoride may account for its remarkable effectiveness at concentrations far below those necessary with most therapeutic materials. Fluoride release from restorative dental materials foUow the same basic pattern. Fluoride is released in an initial short burst after placement of the material, and decreases rapidly to a low level of constant release. The constant low level release has been postulated to provide tooth protection by incorporation into tooth mineral. 

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