Molybdic acid, hydrogen peroxide

V Kubelka, RC Erancis, CW Dence. Delignification with acidic hydrogen peroxide activated by molybdate. J Pulp Pap Sci 18 1108-1114, 1992. 

A thiourea such as (311) was oxidized with sodium molybdate and hydrogen peroxide to an amidine sulphonic acid (312). The sulphonic acid group was replaced by an amine to give the guanidine Scheme 5.70.) [374]. The avoidance of methyl mercaptan as a by-product was a considerable advantage. 

Oxidation. Maleic and fumaric acids are oxidized in aqueous solution by ozone [10028-15-6] (qv) (85). Products of the reaction include glyoxyhc acid [298-12-4], oxalic acid [144-62-7], and formic acid [64-18-6], Catalytic oxidation of aqueous maleic acid occurs with hydrogen peroxide [7722-84-1] in the presence of sodium tungstate(VI) [13472-45-2] (86) and sodium molybdate(VI) [7631-95-0] (87). Both catalyst systems avoid formation of tartaric acid [133-37-9] and produce i j -epoxysuccinic acid [16533-72-5] at pH values above 5. The reaction of maleic anhydride and hydrogen peroxide in an inert solvent (methylene chloride [75-09-2]) gives permaleic acid [4565-24-6], HOOC—CH=CH—CO H (88) which is useful in Baeyer-ViUiger reactions. Both maleate and fumarate [142-42-7] are hydroxylated to tartaric acid using an osmium tetroxide [20816-12-0]/io 2LX.e [15454-31 -6] catalyst system (89). 

Better results are obtained by transferring 25.0 mL of the diluted hydrogen peroxide solution to a conical flask, and adding 100 mL 1M(1 20) sulphuric acid. Pass a slow stream of carbon dioxide or nitrogen through the flask, add 10 mL of 10 per cent potassium iodide solution, followed by three drops of 3 per cent ammonium molybdate solution. Titrate the liberated iodine immediately with standard 0.1M sodium thiosulphate in the usual way. 

The use of molybdenum catalysts in combination with hydrogen peroxide is not so common. Nevertheless, there are a number of systems in which molybdates have been employed for the activation of hydrogen peroxide. A catalytic amount of sodium molybdate in combination with monodentate ligands (e.g., hexaalkyl phosphorus triamides or pyridine-N-oxides), and sulfuric acid allowed the epoxidation of simple linear or cyclic olefins [46]. The selectivity obtained by this method was quite low, and significant amounts of diol were formed, even though highly concentrated hydrogen peroxide (>70%) was employed. 

These and similar results can be explained if the simultaneous reduction of hydrogen peroxide is due to an induced reaction. To show the characteristic features of this reaction some results are presented in Table 19 and Table 20. The procedure for these measurements was as follows. The solution of peroxy compounds given in columns 1 and 2 was made up to 20 ml and the pH was adjusted to the given value. Then potassium thiocyanate solution was added and, after the reaction time noted, the process was quenched by adding potassium iodide solution (0.3 g KI). After 5 sec the solution was acidified with 1 ml 2 iV sulphuric acid then using, molybdate catalyst solution, the iodine liberated was titrated with standard thiosulphate. 

In 1948 Maxted and Walker studied the detoxification of catalyst poisons in the hydrogenation of aromatic hydrocarbons and found that the isomeric thienothiophenes 1 and 2 could be converted into the sul-fones of fully hydrogenated thienothiophenes 1 and 2, which do not poison the catalysts. This conversion is performed by brief preliminary hydrogenation and subsequent oxidation by hydrogen peroxide or per-molybdic acid. However, no data on the isolation or foe properties of these disulfones are available. It has been reported that direct oxidation of thienothiophenes 1 and 2 does not produce sulfones. 

Molybdenum and Tungsten Peroxide Compounds. Pour ammonium molybdate and sodium tungstate solutions into separate test tubes, acidify them with sulphuric acid, and add several drops of a 1 % hydrogen peroxide solution to each tube. How does the colour of the solutions change Write the equations of the reactions. 

Metallic potassium and sodium are explosively converted into the hydroxides when brought into contact with concentrated solutions of hydrogen peroxide many of the heavier metals such as zinc and iron, and especially aluminium,3 are readily changed into their respective hydroxides, whilst chromium, arsenic, and molybdenum are oxidised respectively to chromic, arsenic, and molybdic acids. Colloidal tellurium yields telluric acid with very dilute solutions of peroxide4 the crystalline modification reacts slowly with 60 per cent, peroxide at 100° C. 

An important current industrial process based on N-C cleavage using hydrogen peroxide is the manufacture of iV-phosphonomethylglycine (systemic herbicide, glyphosate) from AT-phosphonomethyl imido diacetic acid via the N-oxide (Figure 3.88).347 //-Oxidation is catalysed by molybdate or tungstate and the intermediate formed can be decomposed with a second catalyst such as iron(II) to form the product.348... 

Cysteic acid is obtained in nearly quantitative yield from cysteine with aqueous hydrogen peroxide in the presence of iron(II) ions.397 Molybdates and tungstates have also been used as effective catalysts for similar transformations.398 An excellent route for the oxidation of 2-thioethanol to isothionic acid has been developed.399 Heteropolyoxometallates supported on alumina400 can also be used to oxidize a range of organo-sulfur compounds. For example, alkyl monosulfides to sulfoxides and sulfones, and thiols to sulfonic acids are a few possibilities (Figure 3.98). 

If a solution of a molybdate be treated in acid solution with hydrogen peroxide, oxidation to permolybdic acid takes place, the solution becoming yellowA The colour remains on warming,- and cannot be extracted by ether. Moreover, when molybdic anhydride, M0O3, is dissolved in hydrogen peroxide, a yellow insoluble compound is deposited from the stable, dark yellow solution. ... 

In the presence of a small amount of ascorbic acid, the I2 formed is reduced back to iodide. When all the ascorbic acid is consumed, iodine is liberated, and the sudden appearance of iodine can be made visible with variamine blue (Landolt effect). The time to the appearance of iodine is measured. The reaction of hydrogen peroxide and iodide is much faster in the presence of molybdate, probably because of the reactions... 

Transition metal catalysts not only increase the reaction rate but may also affect the outcome of the oxidation, especially the stereochemistry of the products. Whereas hydrogen peroxide alone in acetonitrile oxidizes alkenes to epoxides [729], osmic acid catalyzes syn hydroxylation [736], and tungstic acid catalyzes anti hydroxylation [737]. The most frequently used catalysts are titanium trichloride [732], vanadium pentoxide [733,134], sodium vanadate [735], selenium dioxide [725], chromium trioxide [134], ammonium molybdate [736], tungsten trioxide [737], tungstic acid [737],... 

Hydrogen peroxide reacts with acidified molybdate solutions. Chaveau, Souchay and Tridot (1955) have shown the presence of the acid H2M02O44 in solutions of molybdate in concentrated perchloric acid to which HgOg has been added. The so-called permolybdic acid is regarded as a salt of this acid with the cation [HMo20g]+, not itself peroxidic. 

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