Periodic acid oxidant

Periodic acid oxidation (Section 15 12) finds extensive use as an analytical method m carbohydrate chemistry Structural information is obtained by measuring the number of equivalents of periodic acid that react with a given compound and by identifying the reaction products A vicinal diol consumes one equivalent of penodate and is cleaved to two carbonyl compounds... 

CEBSSS Give the products of periodic acid oxidation of each of the fol lowing How many moles of reagent will be consumed per mole of substrate in... 

The use of periodic acid oxidation in structure determination can be illustrated by a case in which a previously unknown methyl glycoside was obtained by the reaction of D-arabinose with methanol and hydrogen chloride. The size of the ring was identified as five-membered because only one mole of periodic acid was consumed per mole of glycoside and no formic acid was produced. Were the ring six-membered, two moles of periodic acid would be required per mole of glycoside and one mole of formic acid would be produced. 

Periodic acid oxidation (Section 25.23) Vicinal diol and a-hydroxy carbonyl functions in carbohydrates are cleaved by periodic acid. Used analytically as a tool for structure determination. 

All the nitrogen atoms of M were thus accounted for, together with the provisional placement of two of the oxygen atoms. An acetylation experiment, under mild conditions, showed that the metabolite has five to six acetylable groups, at least four of which would be hydroxyl. This observation led to periodic acid oxidations which... 

Redox (reduction-oxidation) titrimetry is used primarily for nitrate detns. Five systems are in current use ferrous sulfate—dichromate, io dome trie, periodic acid oxidation (NaOH titrant), K permanganate, and titanous chloride-ferric ammonium sulfate. The ferrous sulfate— dichromate system is used for MNT DNT detns (Vol 2, C162-Lff Vol 6, F17-Rff Ref 17). In the iodometric procedure, the sample (ie, NG) is treated in a C02 atm with a satd soln of Mn chloride in coned HC1, the vol reaction products are bubbled thru a K iodide soln, and the liberated iodine is titrated with standard thiosulfate soln (Refs 1 17). The periodic... 

Catalytic hydrogenation of 146 and oxidation with PCC gave the 3-C-pro-panoyl derivative 147. Selective hydrolysis of the 5,6-0-isopropylidene group, followed by periodic acid oxidation, provided the aldehyde 148. 

Benzylation of 153, followed by hydrolysis and reduction, furnished compound 154. Periodic acid oxidation of 154 gave the aldehyde 155. 

Periodic acid oxidation will also act on a-hydroxy aldehydes and ketones, a-diketones, a-keto aldehydes, and glyoxal. If the two neighboring hydroxyl groups are on an aromatic ring, the carbon-carbon bond is not cleave but the reactant is still oxidized. Thus, catechol is oxidized to the corresponding quinone. 

Periodic acid oxidation has proved to be a very useful tool in enzymology since a wide variety of biochemicals contain hydroxyl groups on adjacent carbon atoms. For example, periodate-oxidized ATP (also called adenosine 5 -triphosphate 2, 3 -dialdehyde) has often been used as an alternative substrate or an irreversible inhibitor for a wide variety of ATP-utilizing enzymes. This compound, and many others, are now commercially available, even though they are readily synthesized e.g., periodic acid oxidized ADP, AMP, adenosine, P, P -di(adenosine-5 )pentaphosphate, P, P -di(adenosine-5 )tetraphos-phate, GTP, GDP, GMP, guanosine, CTP, CDP, CMP, etc. In the case of the nucleosides, commercial sources also can supply the dialcohol form of the nucleoside i.e., the nucleoside has first been oxidized with periodic acid and then reduced to the dialcohol with borohydride. 

Periodic acid oxidation of cyclic phenylhydrazine derivatives [125] (Eq. 66). 

Pentafluoronitrosobenzene, 363, 410 Pentyl azide, 271 Peracid oxidation of amines, 323, 363,409 of azo compounds, 355-356 of hydrazones, 362 of hydroxylamines, 364,415 of imines, 406 of oxaziranes, 407 Perchloryl fluoride, 336 Perfluoroalkylureas, 162 Perfluoro-2-azopropene, oxidation of, 432 Periodic acid oxidation, 338 Permonosulfuric acid, see Caro s acid Phenazines, 321... 

Indeed, it is not necessary for the central atom of the oxyanion to be a transition metal another atom with two different oxidation states is also effective. Recently, it has been found that, in trifluoroacetic acid solution, periodic acid oxidizes alkanes to low carbon number carboxylic acids (55). 

Hercules Method D90-3e (Ref 17, pll). Nitroglycerin by Periodic Acid Oxidation. NG and some other nitrate nitrogen esters which may be present in expl oils can be quantitatively denitrated to their, respective alcohols by action of methanol and coned HCl. On oxidizing the residue of polyhydric alcohols with periodic acid, H5I06, the secondary carbon and alcohol group in glycerin are oxidized to formic acid,... 

Combi notion of Explosive Oils in Which NG May Be Determined by the Periodic Acid Oxidation Method... 

Note SON (Nitrosugar) must be separated chromatographically before NG can be detd by the periodic acid oxidation procedure A detailed description of periodic acid oxidation procedure is given in Hercules pamphlet D90 (Ref 17), Rev 5-10-61, ppl2-13 periodic Acid Oxidation Method... 

The Malaprade Periodic Acid Oxidation Reaction oxidizes 1,2 diols or 2-amino alcohols with periodic acid ... 

Several analytical procedures are baaed on the hydration rather than hydrohalogenation of epoxide . Tlie resultittg 1,2-diols are assayed by oxidative titration with periodic acid in aqueous sulfurio acid or perchloric acid.4711 Alternatively, carbonyl compounds formed on periodic acid oxidation of 1,2-diola may be determined color imetricajlv wkh phenylbydrwine or other suitable reagents.247 374... 

The chemical researches were directed towards three main aims. The first dealt with periodic acid oxidation. In 1928, L. Malaprade, at the University of Nancy, hoping to specify the effect of D-mannitol upon the acidity of periodic acid, observed that the carbon-carbon linkages of the polyol were cleaved, and showed that this was a general feature of the specific reaction of periodic acid with a-glycols. Then, P. Fleury had the premonition that this acid should be an invaluable reagent for analytical purposes. He described the utilization and determination of this remarkably selective oxidant, working under mild conditions of pH and temperature. 

Their main results may be summarized as follows. The periodic acid oxidation of polyols afforded a method for quantitative determination of these compounds, and it was demonstrated that the first reaction products are carbonyl compounds, themselves in turn degraded from their reducing end. After complete oxidation, it is possible to make an estimate of the consumption of oxidant, as well as of the formic acid and formaldehyde that are produced. The monosaccharides are attacked preferentially at the neigh-... 

Applying periodic acid oxidation to reducing di- and oligo-saccharides having (1 — 4) linkages, J. E. Courtois observed the overoxidation phenomenon, which was further extended by study of the oxidation of malonic, malic, and citric acids. Two heteroside structures, amygdaloside and vician-oside, were also studied with this reagent. 

In the 1-electron reduction of A1 4-3-ketosteroids (164), various stereoisomers of pinacols are formed according to the pH. The protonized form of the ketosteroid, reduced in acidic solution, gives rise to a pinacol with hydroxyl groups in the a-position. In alkaline media, the unprotonized ketosteroid is reduced with the formation of the isomer with the hydroxyls in the p-position. The structure of the products prepared by controlled potential electrolysis, are supported by the rates of dehydration and periodic acid oxidations. For A4-3-ketosteroids, the difference in the composition of products obtained in acidic and alkaline media is less pronounced. 

O-Benzylation of 148 with benzyl bromide in the usual manner yielded the tri-0-benzyl derivative (149), [a]p7 —0.8° (chloroform). On hydrolysis with aqueous acetic acid, 149 gave the compound (150), which was further converted to the compound (151) by sodium borohydride reduction. Periodic acid oxidation of 151 and successive sodium borohydride reduction gave 5,6-di-<9-acetyl-2,3,4-tri-0-benzyl-pseudo-a-L-altropyranose (152), [a] 6 —25.7° (chloroform), after conventional acetylation. Reductive cleavage of 152 with sodium in liquid ammonia and subsequent acetylation afforded pseudo-a-L-altropyranose pentaacetate (153), m.p. 84-85 °C, [ ]q6 —13.7° (chloroform). Hydrolysis of 153 gave 154, [ot] —43.6° (methanol) [35] (Scheme 24). 

O-Deacetylation of J58 and successive O-benzylation gave the tri-O-benzyl derivative (159), [a]p +36.7° (chloroform). When 159 was hydrolyzed with aqueous acetic acid and subsequently hydrogenated with sodium borohydride, the compound (160), [a] + 4.4° (chloroform), was obtained. Periodic acid oxidation of 160 and reduction with sodium borohydride afforded 4,6-di-0-acetyl-l,2,3-tri-0-benzyl-pseudo-(3-L-allopyr-anose (161), [a] —40.2° (chloroform), after acetylation. Catalytic hydrogenolysis of 161 and successive acetylation gave pseudo-P-L-allopyranose pentaacetate (162), m.p. 135-136 °C, [a] f +3.7° (chloroform) [36]. (Scheme 25). 

The aldehyde (163), which was prepared from 160 by periodic acid oxidation, was further converted into pseudo-a-D-mannopyranose as follows. Dehydration of 163 with mesyl chloride and pyridine, and subsequent reduction with lithium aluminium hydride gave (3S, 4R, 5S)-3,4,5-tris(benzyloxy)-l-cyclohexene-1-methanol (164). Hydroxyla-tion of 164 with diborane and hydrogen peroxide yielded 4,6-di-0-acetyl-l,2,3-tri-0-... 

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