Periodate or periodic acid

The oxidation of 1,2-glycols by sodium periodate or periodic acid generally is considered to proceed by way of an intermediate complex between the periodate ion and the glycol.84 Studies by Duke and Bremer26 of the reaction kinetics support the hypothesis that the periodate ion reacts with a coordination number of two and that the reacting complex is exclusively between one mole of glycol and one periodate ion. 

Phenolic oxidation is known to be effected with sodium periodate or periodic acid to yield o- and p-quinols, quinones and other products, depending on substituents attached to the aromatic ring. 2,4,6-Trimethylphenol (221) was subjected to NaI04 oxidation in 80% aq. AcOH to afford the four products 383, 599, 600 and 601 (10, 17, 28 and 31%, respectively). Of these products, the dimer 601 must be formed from the corresponding cyclohexadienone 602 (Scheme 115) °. ... 

SCHEME 115. Oxidation of phenols with sodium periodate or periodic acid... 

The pinacol hydrate may be used (i) for conversion to pina-colone (see below), and (ii) to illustrate the oxidation of 1,2-diols to aldehydes or ketones by periodic acid (p. 145),... 

Add 1 drop (0 05 ml.) of concentrated nitric acid to 2 0 ml. of a 0 5 per cent, aqueous solution of paraperiodic acid (HjIO,) contained in a small test-tube and shake well. Then introduce 1 op or a small crystal of the compound. Shake the mixture for 15 seconds and add 1-2 drops of 5 per cent, aqueous silver nitrate. The immediate production of a white precipitate (silver iodate) constitutes a positive test and indicates that the organic compound has been oxidised by the periodic acid. The test is based upon the fact that silver iodate is sparingly soluble in dilute nitric acid whereas silver periodate is very soluble if too much nitric acid is present, the silver iodate will not precipitate. 

Periodic acid has a selective oxidising action upon compounds having two hydroxyl groups or a hydroxyl and an amino group attached to adjacent carbon atoms and is characterised by the cleavage of the carbon - carbon bond (Malaprade reaction) ... 

Place 2 ml. of the periodic acid reagent in a small test tube, add one drop (no more—otherwise the silver iodate, if formed, will fail to precipitate) of concentrated nitric acid, and shake well. Add one drop or a small crystal of the compound to be tested, shake the mixture for 15-20 seconds, and then add 1-2 drops of 3 per cent, silver nitrate solution. The instantaneous formation of a white precipitate of silver iodate is a positive test. Failure to form a precipitate, or the appearance of a brown precipitate which redissolves on shaking, constitutes a negative test. 

Section 15 12 Periodic acid cleaves vicinal diols two aldehydes two ketones or an aldehyde and a ketone are formed... 

Oxidation of a glycol can lead to a variety of products. Periodic acid quantitatively cleaves 1,2-glycols to aldehydes and is used as an analysis method for glycols (12,13). The oxidation of propylene glycol over Pd/C modified with Pb, Bi, or Te forms a mixture of lactic acid, hydroxyacetone, and pymvic acid (14). Air oxidation of propylene glycol using an electrolytic crystalline silver catalyst yields pymvic aldehyde. 

Alkaline solutions of mononitroparaffins undergo many different reactions when stored for long periods, acidified, or heated. Acidification of solutions of mononitro salts is best effected slowly at 0°C or lower with weak acids or buffered acidic mixtures, such as acetic acid—urea, carbon dioxide, or hydroxyl ammonium chloride. If mineral acids are used under mild conditions, eg, dilute HCl at 0°C, decomposition yields a carbonyl compound and nitrous oxide (Nef reaction). 

Thermal polymerization is not as effective as catalytic polymerization but has the advantage that it can be used to polymerize saturated materials that caimot be induced to react by catalysts. The process consists of the vapor-phase cracking of, for example, propane and butane, followed by prolonged periods at high temperature (510—595°C) for the reactions to proceed to near completion. Olefins can also be conveniendy polymerized by means of an acid catalyst. Thus, the treated olefin-rich feed stream is contacted with a catalyst, such as sulfuric acid, copper pyrophosphate, or phosphoric acid, at 150—220°C and 1035—8275 kPa (150—1200 psi), depending on feedstock and product requirement. 

For in = 2, 3) H5IO5, ether, THF, 77-99% yield. This method also cleaves oxathioacetals, but did not affect the acid-sensitive acetonide or 1,3-diox-olane. Note that ethereal periodic acid has been used to cleave terminal acetonides with subsequent glycol cleavage. ... 

Since 1,5-enediones are usually obtained via pyrylium salts, syntheses of the type found in Section B, 2, a have a rather theroetical interest, save for a few special syntheses. There exist several direct syntheses of l,5-enediones, e.g., from j8-chlorovinyl ketones and j8-diketones or j8-keto esters special pathways to 1,5-enediones have also been described, namely, oxidation with lead tetraacetate or with periodic acid of cyclopentene-l,2-diols. ... 

The oxidative cleavage of the central carbon-carbon bond in a vicinal diol 1, by reaction with lead tetraacetate or periodic acid, yields two carbonyl compounds 2 and 3 as products. 

Unique methods based on new principles have been developed within the past 10 years. Threonine (27,28,249) is oxidized by lead tetraacetate or periodic acid to acetaldehyde, which is determined by photometric analysis of its p-hydroxydiphenyl complex or iodometric titration of its combined bisulfite. Serine is oxidized similarly to formaldehyde, which is determined gravimetrically (207) as its dimedon (5,5-dimethyldihydro-resorcinol) derivative or photometric analysis (31) of the complex formed with Eegriwe s reagent (l,8-dihydroxynaphthalene-3,5-disulfonic acid). It appears that the data obtained for threonine and serine in various proteins by these oxidation procedures are reasonably accurate. [Block and Bolling (26) have given data on the threonine and serine content of various proteins. ]... 

Periodic Acid. HIO4.2H2O, mw 227.96. mono-clinic hygr crysts, loses 2HjO at about 100°, mp 122°, decomps at 130—140°. Sol in w and ale si sol in eth (Refs 5 6), Prepd by electrolytic oxidation of iodic acid or from Ba periodate according to the equation... 

Some manufacturers of this type of boiler claim that water treatment of any kind is not necessary and that no chemicals are required, especially with smaller units below, say, 240 kWh (800 lb/hr). Instead they rely on the on-off expansion-contraction cycles within the vessel to drop scale from the heating elements, or on a daily manual flush of the boiler vessel together with frequent replacement of elements and periodic acid cleaning. (Some improved design models thankfully have an automatic flush system that is actuated upon boiler shutdown.)... 

The two reagents (periodic acid and lead tetraacetate) are complementary, since periodic acid is best used in water and lead tetraacetate in organic solvents. When three or more OH groups are located on adjacent carbons, the middle one (or ones) is converted to formic acid. 

Note Like sulfuric acid (q.v.) ort/io-phosphoric add is a universal reagent, with which almost all classes of substance can be detected at high temperatures (150-180 °C) by charring e.g. high molecular weight hydrocarbons (mineral oils) [20]. The colors and fluorescences produced at lower temperatures (<120°C) and their intensities are very dependent on the temperature and period of heating. It is not possible to use meta- or pyrophosphoric acid in place of or/Ao-phosphoric add, since, for instance, amanita toxins react well with alcoholic phosphoric add only weakly with aqueous phosphoric add and not at all with meta- or pyrophosphoric acid [17]. 

Because esters 745 a, b of imidazole-acetic acid are unstable when stored for long periods, owing to intramolecular catalysis by the imidazole moiety, the esters should be converted into their salts or free acids and stored as such. Only tert-butyl imidazole-(4,5)acetates derived from tert-butyl 4-chloroacetoacetate seem to be stable [232, 233]. N-alkyl-substituted amidines give rise to a mixture of alkyl N-alkylimidazole-4- and 5-acetates [232, 233]. 

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