Hexacyanoferrate , oxidation

A dione (522) was also the major product from a hexacyanoferrate oxidation of 2,4,5 -trihydroxy-2 -methoxy-3-methylbenzophenone. Its conversion to the xanthone by the action of base occurred in only moderate yield. However, zinc and acetic acid gave a quantitative conversion (76JCS(P1)1377). 

A-Methylpyridinium or A-methylquinolinium salts [246] may be oxidized to the N-methyl-2-pyridone or A-methyl-2-quinolone, respectively, in alkaline medium containing some potassium hexacyanoferrate (III). The reaction is probably an indirect electrolysis in which the hexacyanoferrate oxidizes the pseudobase and is, in turn, reoxidized at the anode. 

Yao and Wasa [41] used hexacyanoferrate(III) as a mediator for oxidation of NADH with an oxidation potential of 0.4 V versus Ag/AgCl. To catalyze this reaction, a well-known diaphorase compound was immobilized on a platinum electrode with bovine serum albumin. The current produced by hexacyanoferrate oxidation was proportional to the LA concentration. For the LA determination, a flow injection system was used with a sample splitting zone after injection (10 J.L) in a carrier stream containing NAD / Fe(CN) . After the split, each sample plug passed through one of the immobilized enzyme reactors (l-LDH and d-LDH). After the enzymatic reactor, each part of the sample containing of NADH, moved by different residence time, were proportioned by coil... 

Examples P2O5, diphosphorus pentaoxide or phosphorus)V) oxide Hgj, mercury(I) ion or dimercury(2-l-) ion K2[Fe(CN)g], potassium hexacyanoferrate(II) or potassium hexacyanofer-rate(4—) PbJPb 04, dilead(II) lead(IV) oxide or trilead tetraoxide. 

Manganese(II) can be titrated directly to Mn(III) using hexacyanoferrate(III) as the oxidant. Alternatively, Mn(III), prepared by oxidation of the Mn(II)-EDTA complex with lead dioxide, can be determined by titration with standard iron(II) sulfate. 

Probably the most extensively applied masking agent is cyanide ion. In alkaline solution, cyanide forms strong cyano complexes with the following ions and masks their action toward EDTA Ag, Cd, Co(ll), Cu(ll), Fe(ll), Hg(ll), Ni, Pd(ll), Pt(ll), Tl(lll), and Zn. The alkaline earths, Mn(ll), Pb, and the rare earths are virtually unaffected hence, these latter ions may be titrated with EDTA with the former ions masked by cyanide. Iron(lll) is also masked by cyanide. However, as the hexacy-anoferrate(lll) ion oxidizes many indicators, ascorbic acid is added to form hexacyanoferrate(ll) ion. Moreover, since the addition of cyanide to an acidic solution results in the formation of deadly... 

Hexa.cya.no Complexes. Ferrocyanide [13408-63 ] (hexakiscyanoferrate-(4—)), (Fe(CN) ) , is formed by reaction of iron(II) salts with excess aqueous cyanide. The reaction results in the release of 360 kJ/mol (86 kcal/mol) of heat. The thermodynamic stabiUty of the anion accounts for the success of the original method of synthesis, fusing nitrogenous animal residues (blood, horn, hides, etc) with iron and potassium carbonate. Chemical or electrolytic oxidation of the complex ion affords ferricyanide [13408-62-3] (hexakiscyanoferrate(3—)), [Fe(CN)g] , which has a formation constant that is larger by a factor of 10. However, hexakiscyanoferrate(3—) caimot be prepared by direct reaction of iron(III) and cyanide because significant amounts of iron(III) hydroxide also form. Hexacyanoferrate(4—) is quite inert and is nontoxic. In contrast, hexacyanoferrate(3—) is toxic because it is more labile and cyanide dissociates readily. Both complexes Hberate HCN upon addition of acids. 

Tripotassium hexakiscyanoferrate [13746-66-2] K2[Fe(CN)g], forms anhydrous red crystals. The crystalline material is dimorphic both orthorhombic and monoclinic forms are known. The compound is obtained by chemical or electrolytic oxidation of hexacyanoferrate(4—). K2[Fe(CN)g] is soluble in water and acetone, but insoluble in alcohol. It is used in the manufacture of pigments, photographic papers, leather (qv), and textiles and is used as a catalyst in oxidation and polymerisation reactions. 

The methyl group of -nitrotoluene is activated by the para nitro group. -Nitrotoluene is oxidized to -nitrobenzoic acid [62-23-7] by potassium hexacyanoferrate(III) in alkaline solution, potassium permanganate, or potassium dichromate. -Nitrotoluene is converted to -nitrobenzaldehyde... 

The Stock Oxidation-Number System. Stock sought to correct many nomenclature difficulties by introducing Roman numerals in parentheses to indicate the state(s) of oxidation, eg, titanium(II) chloride for TiCl2, iron(II) oxide for FeO, titanium(III) chloride for TiCl, iron(III) oxide for Fe203, titanium(IV) chloride for TiCl, and iron(II,III) oxide for Fe O. In this system, only the termination -ate is used for anions, followed by Roman numerals in parentheses. Examples are potassium manganate(IV) for K2Mn02, potassium tetrachloroplatinate(II) for K PtCl, and sodium hexacyanoferrate(III) for Na3Fe(CN)3. Thus a set of prefixes and terminations becomes uimecessary. 

Ana.lytica.1 Methods. Various analytical methods involve titration with oxidants, eg, hexacyanoferrate (ferricyanide), which oxidize dithionites to sulfite. lodimetric titration to sulfate in the presence of formaldehyde enables dithionite to be distinguished from sulfite because aldehyde adducts of sulfite are not oxidized by iodine. Reductive bleaching of dyes can be used to determine dithionite, the extent of reduction being deterrnined photometrically. Methods for determining mixtures of dithionite, sulfite, and thiosulfates have been reviewed (365). Analysis of dithionite particularly for thiosulfate, a frequent and undesirable impurity, can be done easily by Hquid chromatography (366). 

Because of the time and expense involved, biological assays are used primarily for research purposes. The first chemical method for assaying L-ascorbic acid was the titration with 2,6-dichlorophenolindophenol solution (76). This method is not appHcable in the presence of a variety of interfering substances, eg, reduced metal ions, sulfites, tannins, or colored dyes. This 2,6-dichlorophenolindophenol method and other chemical and physiochemical methods are based on the reducing character of L-ascorbic acid (77). Colorimetric reactions with metal ions as weU as other redox systems, eg, potassium hexacyanoferrate(III), methylene blue, chloramine, etc, have been used for the assay, but they are unspecific because of interferences from a large number of reducing substances contained in foods and natural products (78). These methods have been used extensively in fish research (79). A specific photometric method for the assay of vitamin C in biological samples is based on the oxidation of ascorbic acid to dehydroascorbic acid with 2,4-dinitrophenylhydrazine (80). In the microfluorometric method, ascorbic acid is oxidized to dehydroascorbic acid in the presence of charcoal. The oxidized form is reacted with o-phenylenediamine to produce a fluorescent compound that is detected with an excitation maximum of ca 350 nm and an emission maximum of ca 430 nm (81). 

Calcium hexacyanoferrate (II) (IIH2O) [ 13821 -08-4] M 490.3. Recrystd three times from conductivity H2O and air dried to constant weight over partially dehydrated salt. [Trans Faraday Soc 45 855 1949.] Alternatively the Ca salt can be purified by pptn with absolute EtOH in the cold (to avoid oxidation) from an air-free saturated aqueous soln. The pure lemon yellow crystals are centrifuged, dried in a vacuum desiccator first over dry charcoal for 24h, then over partly dehydrated salt and stored in a dark glass stoppered bottle. No deterioration occurred after 18 months. No trace of Na, K or NH4 ions could be detected in the salt from the residue after decomposition of the salt with cone H2SO4. Analyses indicate 1 Imols of H2O per mol of salt. The solubility in H2O is 36.45g (24.9 ) and 64.7g (44.7 ) per lOOg of solution. [J Chem Soc 50 1926.]... 

On oxidation by potassium hexacyanoferrate(III) adrenaline is converted into adrenochrome which then condenses with ethylenediamine ... 

Methyl-thiazolo[4,5-/]quinoline 19 was methylated by methyl iodide on the nitrogen atom of pyridine giving the appropriate methodide. A subsequent oxidation with potassium hexacyanoferrate in alkaline media gave the 2,6-dimethyl-7-0x0-6,7-dihydrothiazolo[4,5-/]quinoline 21 (37LA60). 

The nitration of l,2,5-selenadiazolo[3,4-/] quinoline 77 with benzoyl nitrate affords the 8-nitro derivative 78, whereas methylation with methyl iodide or methyl sulfate afforded the corresponding 6-pyridinium methiodide 79 or methosulfate 80, respectively (Scheme 29). The pyridinium salt 80 was submitted to oxidation with potassium hexacyanoferrate and provided 7-oxo-6,7-dihydro derivative 81 or, by reaction of pyridinium salt 79 with phenylmagnesium bromide, the 7-phenyl-6,7-dihydro derivative 82. Nucleophilic substitution of the methiodide 79 with potassium cyanide resulted in the formation of 9-cyano-6,9-dihydroderivative 83, which can be oxidized by iodine to 9-cyano-l,2,5-selenadiazolo [3,4-/]quinoline methiodide 84. All the reactions proceeded in moderate yields (81IJC648). 

The actual catalyst is a complex formed from osmium tetroxide and a chiral ligand, e.g. dihydroquinine (DHQ) 9, dihydroquinidine (DHQD), Zj -dihydroqui-nine-phthalazine 10 or the respective dihydroquinidine derivative. The expensive and toxic osmium tetroxide is employed in small amounts only, together with a less expensive co-oxidant, e.g. potassium hexacyanoferrate(lll), which is used in stoichiometric quantities. The chiral ligand is also required in small amounts only. For the bench chemist, the procedure for the asymmetric fihydroxylation has been simplified with commercially available mixtures of reagents, e.g. AD-mix-a or AD-mix-/3, ° containing the appropriate cinchona alkaloid derivative ... 

Heating with the following solids, their fusions, or vapours (a) oxides, peroxides, hydroxides, nitrates, nitrites, sulphides, cyanides, hexacyano-ferrate(III), and hexacyanoferrate(II) of the alkali and alkaline-earth metals (except oxides and hydroxides of calcium and strontium) (b) molten lead, silver, copper, zinc, bismuth, tin, or gold, or mixtures which form these metals upon reduction (c) phosphorus, arsenic, antimony, or silicon, or mixtures which form these elements upon reduction, particularly phosphates, arsenates,... 

Crucibles fitted with permanent porous plates are cleaned by shaking out as much of the solid as possible, and then dissolving out the remainder of the solid with a suitable solvent. A hot 0.1 M solution of the tetrasodium salt of the ethylenediaminetetra-acetic acid is an excellent solvent for many of the precipitates [except metallic sulphides and hexacyanoferrates(III)] encountered in analysis. These include barium sulphate, calcium oxalate, calcium phosphate, calcium oxide, lead carbonate, lead iodate, lead oxalate, and ammonium magnesium phosphate. The crucible may either be completely immersed in the hot reagent or the latter may be drawn by suction through the crucible. 

In strongly acid solution the reaction proceeds from left to right, but is reversed in almost neutral solution. Oxidation also proceeds quantitatively in a slightly acid medium in the presence of a zinc salt. The very sparingly soluble potassium zinc hexacyanoferrate(II) is formed, and the hexacyanoferrate(II) ions are removed from the sphere of action ... 

Important organic applications are to the determination of quinine and the vitamins riboflavin (vitamin B2) and thiamine (vitamin Bj). Riboflavin fluoresces in aqueous solution thiamine must first be oxidised with alkaline hexacyanoferrate(III) solution to thiochrome, which gives a blue fluorescence in butanol solution. Under standard conditions, the net fluorescence of the thiochrome produced by oxidation of the vitamin Bj is directly proportional to its concentration over a given range. The fluorescence can be measured either by reference to a standard quinine solution in a null-point instrument or directly in a spectrofluorimeter.27... 

Such free radicals may be stabilized by binding to proteins. Redox reactions may also occur between ionic species, for example the oxidation of reduced cytochrome c by hexacyanoferrate (ferricyanide) ions. 

When oxidized by iron(III) ions 4-aminoantipyrine reacts with phenols to yield colored quinonoid derivatives (cf. 4-aminoantipyrine — potassium hexacyanoferrate(III) reagent in Volume 1 a). It is an oxidative coupling based on the Emerson reaction. 

An iodine solution can be employed as oxidizing agent in place of potassium hexacyanoferrate(lll). 4-Aminoantipyrine also produces colored zones with 1- and 1,4-unsaturated 3-ketosteroids (pregnadienediol derivatives) in the absence of oxidizing agents. 

Until now examples for catalytic reactions involving ferrates with iron in the oxidation state of -l-3 are very rare. One example is the hexacyanoferrate 8-catalyzed oxidation of trimethoxybenzenes 7 to dimethoxy-p-benzoquinones 9/10 by means of hydrogen peroxide which was published by Matsumoto and Kobayashi in 1985 [2]. Using hexacyanoferrate 8 product 9 was favored while other catalysts like Fe(acac)3 or Fe2(S04)3 favored product 10 (Scheme 2). The oxidation is supposed to proceed via the corresponding phenols which are formed by the attack of OH radicals generated in the Fe/H202 system. 

Cobalt nitrate has the typical dangerous reactions of metal nitrates. Two accidents during which violent detonations occurred were reported. One of them happened when a mixture of this nitrate with powder carbon was ground up. The other took place when a tetraammonium hexacyanoferrate/cobalt nitrate mixture was heated to 220°C. It typifies incompatibiiity of the cyano group with oxidants. 

Copper nitrate reacts with sodamide and ammonia by forming explosive copper amides. The oxidising properties of this nitrate have led to violent detonations with ammonium hexacyanoferrates heated to 220 C in the presence of water traces, or dry at the same temperature, but in the presence of an excess of hexacyanoferrate. These accidents illustrate once more the incompatibility between compounds with a cyano group (or cyanide anion) and oxidants. An accident also occurred with a potassium hexacyanoferrate. 

The industrial production of Prussian blue is based on the reaction in aqueous solution of sodium hexacyanoferrate(n), Na4Fe(CN)6, with iron(n) sulfate, FeS04-7H20 in the presence of an ammonium salt, which results initially in the formation of the colourless insoluble iron(n) hexa-cyanoferrate(n) (Berlin white). Prussian blue is generated by subsequent oxidation with a dichromate or chlorate. 

Chrome green is produced by mechanically mixing chrome yellow and iron blue pigments in water. An iron blue, [Fe(NH4) (FeCN6)], is an oxidized precipitate product of the reaction between an aqueous solution of iron sulfate and ammonium sulfate with sodium hexacyanoferrate. 

The effects of various metal oxides and salts which promote ignition of amine-red fuming nitric acid systems were examined. Among soluble catalysts, copperQ oxide, ammonium metavanadate, sodium metavanadate, iron(III) chloride (and potassium hexacyanoferrate(II) with o-toluidine) are most effective. Of the insoluble materials, copper(II) oxide, iron(III) oxide, vanadium(V) oxide, potassium chromate, potassium dichromate, potassium hexacyanoferrate(III) and sodium pentacyanonitrosylferrate(II) were effective. 

Nickel hexacyanoferrate (NiHCF) films can be prepared by electrochemical oxidation of nickel electrodes in the presence of hexacyanoferrate(III) ions,141 or by voltammetric cycling of inert substrate electrodes in solutions containing nickel(II) and hexacyanoferrate(III) ions.142 NiHCF films do not possess low-energy intervalent CT bands, however, when deposited on ITO they are observed to reversibly switch from yellow to colorless on electroreduction.143... 

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