Oxidation electrolytic

Electrolytic oxidation of laudanosine (16) in TEA leads to a 17%o yield of glaucine (17), the presumed intermediate again being a morphinandienone.  

A novel preparative synthesis of aporphines which should prove of appreciable utility in the future involves the cathodic cyclization of a l-(o-iodo-benzyl)isoquinoline methiodide salt. Gottlieb and Neumeyer have shown that electrolysis of l-(o-iodobenzyl)isoquinoline methiodide in dry acetonitrile containing tetraethylammonium bromide, and using a mercury cathode, furnished an 867o yield of the yellow didehydroaporphine which was reduced over Adams catalyst in methanolic hydrochloric acid to produce aporphine hydrochloride. The formation of didehydroaporphine proceeds via two one-electron reduction steps as shown below. 10,11-Dimethoxyaporphine was also prepared by this route. 

As long as depolarizer oxidation at the anode proceeds in a reversible manner the process can be explained as simply as at oathodie reversible reduction. Thus e. g. the oxidation of the ion Fe begins to proceed at an exactly reproducible 

In a similar way in which the oxidation of the bivalent iron cations to the trivalent is explained by the direct transfer of electrons from the solution to the electrode, also the oxidation of some anions can be explained by this simple reaction mechanism, e. g. 

The polymerization of anions is a special type of irreversible anodic processes. Of these the oxidation of sulphate to persulphate ions has been studied in the deepest detail. In the production of pcrsulphuric acid the yield is increased to a certain limit by a higher concentration of the initial sulphuric acid and an increased current density at the anode of smooth platinum. In too concentrated sulphuric acid the pcrsulphuric acid is already hydrolysed to a considerable extent to monopersulphuric acid (Caro s acid), which then acts as a depolarizer and lowers the required high potential at the anode. Electrolysis of sulphate solutions also gives persulphates and in this reaction the current efficiency will depend on the nature of the cation the efficiency increasing in the order of Na+, K+ and NHj. 

Formerly the formation of persulphate was attributed to the polymerization of HS04 radicals, formed by the discharge of bisulphate ions  

This theory accounts for the dependence between the current efficiency and the concentration of HSO ions present in the solution. It cannot explain, however, why the yields at the electrolysis of solutions of sulphates, in which the concentration of HSO ions is very low, are even greater than when electrolysing solutions of sulphuric acid alone or its mixture with a sulphate. This deficiency is not found in the recent explanation of the reaction mechanism, according to which the sulphate ions SO - are primarily oxidized by hydrogen peroxide or by hydroxyl radicals formed, according to equations  

In 1931, Isbell and Frush reported the electrolytic oxidation of aldoses in the presence of calcium carbonate and a small amount of bromide, which served as a catalyst. The main solutes in the reaction mixture are the aldose and the calcium salt of the aldonic acid. The latter is easily crystallized from solution. The salts of D-gluconic, D-xylonic, lactobionic and maltobionic acids were prepared. A description of the process was published in 1932 and a patent was issued in 1934. German and French patents were issued in 1931 to the Rohm and Haas Co.  

The electrolytic method is an indirect oxidation, as the small amount of bromide present is constantly converted to bromine, the actual oxidant. Essentially the reaction is the same as the action of bromine in weakly acidic buffered solution. The presence of only a small amount of extraneous salts is of advantage in processing the reaction mixture. The 

Kiliani reported very favorably on the electrolytic method and was quick to apply it to the preparation of calcium D-galactonate. In 1935, the electrolytic preparation of calcium D-xylonate was reported by Isbell and Frush the earlier work had been delayed by failure to obtain the salt in crystalline condition. The preparation of calcium lactobionate-calcium bromide was reported by Isbell the double salt was suggested as a sedative in place of calcium bromide. 

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Cobali in) fluoride, C0F3. Brown powder (C0F3 plus F2) also forms a green hydrate by electrolytic oxidation. C0F3 is widely used in the fluorinalion of organic derivatives. Gives complexes e.g. MjCoFg. 

CoS04,7H20. Few cobalt(III) oxy acid salts are known. 002(504)3,ISHjO is formed by electrolytic oxidation and forms alums Co(N03)3 contains co-ordinated nitrate (C0F3 plus NjOs). 

Lead(IV) oxide, PbOj. Chocolate brown (electrolytic oxidation of Pb(II) salts). Used as an oxidizing agent. 

Manganates V f), [MnOJ", permanganates. Dark purple tetrahedral anion (electrolyte oxidation of [Mn04]. Powerful oxidizing agent... 

Blue manganese lV) fluoride, Mnp4 (Mn plus Fj), is immediately hydrolysed by water complex hexafluoromanganales containing [MnF j] " ions are yellow (electrolytic oxidation of lower fluorides or use of BrFs). 

Prepared by use of HjOj or by electrolytic oxidation. Persulphuric acids, perborates, are of importance. (Permanganates, perchlorates and periodates are not salts of per-acids.) Organic per-acids are prepared similarly. The... 

These can be prepared by electrolytic oxidation of chlorates(V) or by neutralisation of the acid with metals. Many chlorates(VII) are very soluble in water and indeed barium and magnesium chlorates-(VII) form hydrates of such low vapour pressure that they can be used as desiccants. The chlorate(VII) ion shows the least tendency of any negative ion to behave as a ligand, i.e. to form complexes with cations, and hence solutions of chlorates (VII) are used when it is desired to avoid complex formation in solution. 

These are acids which can be regarded, in respect of their formulae (but not their properties) as hydrates of the hypothetical diiodine heptoxide, liO-j. The acid commonly called periodic acid , I2O7. 5H2O, is written HglO (since the acid is pentabasic) and should strictly be called hexaoxoiodic(VII) acid. It is a weak acid and its salts are hydrolysed in solution. It can be prepared by electrolytic oxidation of iodic(V) acid at low temperatures ... 

However the Mn (aq) ion can be stabilised by using acid solutions or by complex formation it can be prepared by electrolytic oxidation of manganese(II) solutions. The alum CaMn(S04)2.12H2O contains... 

Subject Phenyl acetones by electrolytic oxidation From "guest" ... 

Appendix - Phenyl acetones by electrolytic oxidation. Process for 3,4-dimethoxyphenyl-acetone preparation. European Patent Application 0247526, Filed 02.12.87 to LARK S.p.a. Milan. 

Electrolytic oxidation gives acetylene dicarboxyhc acid [142-45-0] (2-butynedioic acid) in good yields (49) chromic acid oxidation gives poor yields (50). Oxidation with peroxyacetic acid gives malonic acid [141-82-2] (qv) (51). 

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. 

Tetravalent lead is obtained when the metal is subjected to strong oxidizing action, such as in the electrolytic oxidation of lead anodes to lead dioxide, Pb02 when bivalent lead compounds are subjected to powerful oxidizing conditions, as in the calcination of lead monoxide to lead tetroxide, Pb O or by wet oxidation of bivalent lead ions to lead dioxide by chlorine water. The inorganic compounds of tetravalent lead are relatively unstable eg, in the presence of water they hydrolyze to give lead dioxide. 

Electrolytic Oxidation. Electrolytic oxidation of ferromanganese or manganese metal is a one-stage process that circumvents the problem of ore impurities. Moreover, this procedure can be used with low caustic concentrations at room temperature. This process is based on the following... 

Oxidation. Nitroparaffins are resistant to oxidation. At ordinary temperatures, they are attacked only very slowly by strong oxidi2ing agents such as potassium permanganate, manganese dioxide, or lead peroxide. Nitronate salts, however, are oxidi2ed more easily. The salt of 2-nitropropane is converted to 2,3-dimethyl-2,3-dinitrobutane [3964-18-9], acetone, and nitrite ion by persulfates or electrolytic oxidation. With potassium permanganate, only acetone is recovered. 

Ttinitroparaffins can be prepared from 1,1-dinitroparaffins by electrolytic nitration, ie, electrolysis in aqueous caustic sodium nitrate solution (57). Secondary nitroparaffins dimerize on electrolytic oxidation (58) for example, 2-nitropropane yields 2,3-dimethyl-2,3-dinitrobutane, as well as some 2,2-dinitropropane. Addition of sodium nitrate to the anolyte favors formation of the former. The oxidation of salts of i7k-2-nitropropane with either cationic or anionic oxidants generally gives both 2,2-dinitropropane and acetone (59) with ammonium peroxysulfate, for example, these products are formed in 53 and 14% yields, respectively. Ozone oxidation of nitroso groups gives nitro compounds 2-nitroso-2-nitropropane [5275-46-7] (propylpseudonitrole), for example, yields 2,2-dinitropropane (60). 

The electrolytic oxidation of chlorate to perchloric acid is also feasible (27). Perchlorates are commonly prepared by electrolytic oxidation of chlorates ... 

The pyrazole ring is resistant to oxidation and reduction. Only ozonolysis, electrolytic oxidations, or strong base can cause ring fission. On photolysis, pyrazoles undergo an unusual rearrangement to yield imidazoles via cleavage of the N —N2 bond, followed by cyclization of the radical iatermediate to azirine (27). 

Polypyrroles. Highly stable, flexible films of polypyrrole ate obtained by electrolytic oxidation of the appropriate pyrrole monomers (46). The films are not affected by air and can be heated to 250°C with Htde effect. It is beheved that the pyrrole units remain intact and that linking is by the a-carbons. Copolymerization of pyrrole with /V-methy1pyrro1e yields compositions of varying electrical conductivity, depending on the monomer ratio. Conductivities as high as 10 /(n-m) have been reported (47) (see Electrically conductive polymers). 

Diacetone-L-sorbose (DAS) is oxidized at elevated temperatures in dilute sodium hydroxide in the presence of a catalyst (nickel chloride for bleach or palladium on carbon for air) or by electrolytic methods. After completion of the reaction, the mixture is worked up by acidification to 2,3 4,6-bis-0-isoptopyhdene-2-oxo-L-gulonic acid (2,3 4,6-diacetone-2-keto-L-gulonic acid) (DAG), which is isolated through filtration, washing, and drying. With sodium hypochlorite/nickel chloride, the reported DAG yields ate >90% (65). The oxidation with air has been reported, and a practical process was developed with palladium—carbon or platinum—carbon as catalyst (66,67). The electrolytic oxidation with nickel salts as the catalyst has also... 

Ketopantolactone (19) is conveniently prepared by oxidation of (R,5)-pantolactone (18). Various oxidising agents have been patented for the oxidation of pantolactone, such as MnO ( 1)> DMSO—AC2O (32), and hypohahtes (33). An improved yield of ketopantolactone (19) via electrolytic oxidation of pantolactone with an aqueous solution containing an alkaH metal salt was reported (34). Ketopantolactone (19) has been prepared in good yield via cyclocondensation of the 2-keto-3-methylbutyrate (20) with formaldehyde (35). 

Piperidine, l-(2-hydroxythiobenzoyI)-neutron diffraction, 2, 116 Piperidine, 4-hydroxy-2,2,6-trimethyI-as local anaesthetic, 1, 179 Piperidine, JV-methoxycarbonyl-electrolytic oxidation, 2, 374 Piperidine, 2-methyl-synthesis, 2, 524 Piperidine, 3-methyI-mass spectrometry, 2, 130 Piperidine, C-methyl-NMR, 2, 160 Piperidine, JV-methyl- C chemical shifts, 2, 15 catalyst... 

Beyer synthesis, 2, 474 electrolytic oxidation, 2, 325 7r-electron density calculations, 2, 316 1-electron reduction, 2, 282, 283 electrophilic halogenation, 2, 49 electrophilic substitution, 2, 49 Emmert reaction, 2, 276 food preservative, 1,411 free radical acylation, 2, 298 free radical alkylation, 2, 45, 295 free radical amidation, 2, 299 free radical arylation, 2, 295 Friedel-Crafts reactions, 2, 208 Friedlander synthesis, 2, 70, 443 fluorination, 2, 199 halogenation, 2, 40 hydrogenation, 2, 45, 284-285, 327 hydrogen-deuterium exchange, 2, 196, 286 hydroxylation, 2, 325 iodination, 2, 202, 320 ionization constants, 2, 172 IR spectra, 2, 18 lithiation, 2, 267... 

Electrolytic oxidation, 1.4-1.7 V, At3N, CH3CN, CH2CI2, LiC104, luti-dine. ... 

Electrolytic oxidation Ar3N, CH3CN, LiC104, 20 , 1.4-1.7 V, 80-90% yield. Benzyl ethers are not affected by these conditions. 

Electrolysis 1.5 V, CH3CN, H2O, UCIO4 or Bu4N-"C104, 50-75% yield. " 1,3-Dithiolanes were not cleaved efficiently, by electrolytic oxidation. 

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