Periodate, sodium

Sodium Periodate In section 3.7.A.ii, a mixture of osmium tetroxide and periodic acid oxidatively cleaved alkenes. Sodium periodate can cleave diols directly. In the Chida et al. synthesis of pironetin, for example, 371 was cleaved to dialdehyde 372 using an aqueous acetone solution of NalOq. l Sodium periodate in dichloromethane, in the presence of sodium bicarbonate, has also been used.5l9 

Solubility sol H2O (14.4g/100111LH2O at 25 °C 38.9 g/100 mL at 51.5 °C), H2SO4, HNO3, acetic acid insol organic solvents. 

Form Supplied in colorless to white tetragonal, efflorescent crystals readily available. 

Handling, Storage, and Precautions irritant gloves and safety goggles should be worn when bandting this oxidant avoid inhalation of dust and avoid contact of oxidant with combustible matter. 

Introduction. Sodium periodate is widely used for the oxidation of a variety of organic substrates and as a cooxidant in other oxidation reactions (see Sodium Periodate-Osmium Tetroxide and Sodium Periodate-Potassium Permanganate) f The Nal04 oxidation is usually conducted in water however, for organic substrates that are insoluble in water, an organic cosolvent (e.g. MeOH, 95% EtOH, 1,4-dioxane, acetone, MeCN) is used. Alternatively, the oxidation can be conducted either with phase-transfer catalysis (PTC) using quaternary ammonium or phosphonium salts in a two-phase system, or in an organic solvent if the oxidant is first coated on an inert support.  

Oxidative Cleavage of 1,2-Diols. NaI04 is widely used for the oxidative cleavage of a variety of 1,2-diols to yield aldehydes or ketones (eq 1). In this respect, it complements the Lead(IV) Acetate method for oxidation. 1,2-Diols have been shown to be chemoselectively cleaved by NaI04 in the presence of a sulfide group.NaI04 coated on wet silica gel efficiently oxidizes 1,2-diols to the aldehydes (eq 2). This method is particularly useful for the preparation of aldehydes which readily form hydrates, and it is also convenient to conduct because isolation of the product involves simple filtration of the reaction mixture and evaporation. 

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Dissolve I g. of pinacol (preparation, p. 148) in 20 ml. of water, and add 20 ml. of the 5% aqueous sodium periodate solution. After 15 minutes, distil the clear solution, collecting the first 5 ml. of distillate. Treat this distillate with 2,4-dinitro-phenylhydrazine solution A (p. 263). Acetone 2,4-dinitrophenyl-hydrazone rapidly separates from the solution when filtered off, washed with a small quantity of ethanol, and dried, it has m.p. 126-127°, and after recrystallisation from ethanol it has m.p. 128°. 

Dissolve 0 5 ml. of glycerol in 20 ml. of w ater, and add 20 ml. of the above 5% aqueous sodium periodate solution. After 15-20 minutes add 12 ml. of the above 10% ethanolic dimedone solution, and stir well at intervals for another 15 minutes. The addition of the dimedone solution may cause a rapid precipitation of some of the dimedone itself, which is only slightly soluble in water, whereas the formaldehyde-dimedone compound separates more slowly from the solution. 

A mixture of 100 ml of water and 0.10 mol of methylthioallene (see Chapter IV, Exp. 23) was placed in the flask and 24 g of sodium periodate were added in five portions at intervals of 4 min. The mixture was agitated vigorously and the temperature was kept between 25 and 30°C by occasional cooling. After 1 h twenty extractions with 10-ml portions of chloroform were carried out. The combined extracts were dried (without previous washing) over magnesium sulfate. Removal of the chloroform by evaporation in a water-pump vacuum gave the reasonably pure (> 9i%) le... 

Chemical degradation studies carried out on streptovaricias A and C, which are the primary components of the cmde complex, yielded substances shown ia Figure 1. Streptovaricia A (4), consumes two moles of sodium periodate to yield variciaal A [21913-68-8] (1), 0 2 200, which accounts for the ahphatic portion of the molecule, and prestreptovarone [58074-37-6] (2), C2C)H2C)N02, which accounts for the aromatic chromophore of the streptovaricias (Fig. 2). Streptovaricia G (9) is the only other streptovaricia that yields prestreptovaroae upoa treatmeat with sodium periodate. Treatmeat of streptovaricias A (4), B (5), C (6), E (8), and G (9) with sodium periodate and osmium tetroxide yields streptovarone [36108-44-8] (3), C24H23NO2, which is also produced by the reaction of prestreptovarone with sodium periodate and osmium tetroxide (4,65). A number of aliphatic products were isolated from the oxidation of streptovaricia C and its derivatives (66). 

A second method uses sodium periodate (NaI04) as the oxidant in the presence of the readily available protein bovine serum albumin. In this procedure, the sulfide is complexed in the chiral envirorunent of the protein. Although the oxidant is achiral, it encounters the sulfide in a chiral envirorunent in which the two faces of the sulfide are differentiated. 

A 1-liter three-necked flask equipped with a mechanical stirrer and two dropping funnels is charged with a solution of 42 g (0.176 mole) of sodium periodate in 145 ml of acetone and 180 ml of water. To the stirred solution, camphene (6.7 g, 0.049 mole) is added in small portions. The reaction vessel is then flushed with nitrogen and is main-... 

Chloro-2-(3-methyl-4H-1,2,4-triazol-4-yDbenzophenone (Oxidation of 7solution prepared by adding sodium periodate (2 g) to a stirred suspension of ruthenium dioxide (200 mg) in water (35 ml). The mixture became dark. Additional sodium periodate 18 g) was added during the next 15 minutes. The ice-bath was removed and the mixture was stirred for 45 minutes. Additional sodium periodate (4 g) was added and the mixture was stirred at ambient temperature for 18 hours and filtered. The solid was washed with acetone and the combined filtrate was concentrated in vacuo. The residue was suspended in water and extracted with methylene chloride. The extract was dried over anhydrous potassium carbonate and concentrated. The residue was chromatographed on silica... 

Fluoro-2-Methyl-1-(p-Methyisuifinyibenzylidene)-3-lndeny acetic Acid To a solution of 3.4 grams (0.01 mol) 5-fluoro-2-methyl-1-(p-methylthiobenzylidene)-3-indenylacetic acid in a 250 ml mixture of methanol and 100 ml acetone is added a solution of 3.8 grams (0.018 mol) of sodium periodate in 50 ml water with stirring. 

Acetylation of kasuganobiosamine with acetic anhydride in methanol gave N,N -diacetylkasuganobiosamine which contained no titrable group and reduced 6.6 moles of sodium periodate, affording 4.7 moles of formic acid, 0.5 mole of carbon dioxide, and a reducing substance —i.e., N,N -diacetylkasugamine. 

The Cg-amine, originally obtained by the methanolysis of kasugamycin, on treatment with lead tetraacetate or sodium periodate afforded a nitrile amine, with evolution of carbon dioxide, showing a maximum at 2200 cm.-1. This reaction is explained only by the structure (13). The -N-C=N group of the product can be formed by oxidative decarboxylation and can be easily rationalized by the present understanding of such reagents (2, 13) as shown below. On the other hand, the treatment... 

Periodate Oxidation of C9-Amine (3). C9-Amine hydrochloride (268 mg., 1 mmole) was treated with a solution of sodium periodate (235 mg.,... 

We examined the reaction of triose reductone with both periodate and iodate (55,56), and found that, whereas iodine was invariably set free from both sodium periodate and sodium iodate if the concentration of the reductone were greater than 10 3M, no iodine was liberated at lower concentrations (e.g. 6 x 10 4M) of substrate, even in the presence of relatively large amounts of the oxidants. 

The oxidation of diethyl 3,6-hexanooxepin-4,5-dicarboxylate with a mixture of sodium periodate and potassium permanganate as oxidizing agent gives diethyl 3-[(formyioxy)methylene]-l 0-oxocyclodec-l-en-l,2-dicarboxylate (2) in 91 % yield.130 A minor modification of the reaction conditions gives two products 2 (35 %) and a product which retains the oxepin structure (23 %) identified as the same lactone described in Section 1.2.1.1.129... 

When the hexamethylene bridge already contains a ketone function, the corresponding cyclo-decenedione derivative 3 is obtained upon regioselective oxidation of the C-C double bond a with potassium permanganate and sodium periodate.38... 

Oxidation of diethyl 3,6-hexanooxepin-4,5-dicarboxylate with ruthenium(VIII) oxide, generated from ruthenium(III) chloride and sodium periodate in situ, gives the corresponding hexa-no-bridged furan 1 a with loss of two carbon atoms (see Houben-Weyl, Vol. E6a, p 77).200 201 One of the central methylene groups can be replaced by a carbonyl group to give lb.200... 

Only sulfoxidation, and no elimination, occurs when the hydrochloride of 2 (R = Me) is treated with sodium periodate at room temperature.3 Ketone 4, which represents the tautomeric form of dibenzo[6,/]thiepin-10-ol, can be sulfoxidized with hydrogen peroxide at room temperature to provide sulfoxide 5 in 56% yield however, at reflux temperature oxidation occurs additionally at the carbon atom next to the oxo group and sulfone 6 is isolated in 79% yield.3... 

The oxidation of 3-benzothiepin to its S -oxide 9 (R = H) was unsuccessful with 3-chloroper-oxybenzoic acid or sodium periodate.68 Also, the route which uses the formation of the di-bromosulfuranes 8, known to be sensitive to hydrolysis (vide infra), was ultimately unsuccessful because 8 is only available if the C — C double bonds of the thiepin ring are deactivated towards bromine addition by ester substituents (R = C02Me), concurrently providing the compound with stability towards hydrolysis.65... 

Dihydro-l-benzothiepin 1-oxide (21) is obtained in 77% yield when 19 is treated with sodium periodate in glacial acetic acid at 0 °C, while a second method ultilizing sulfuryl chloride at — 70°C gives the dichlorosulfurane intermediate 20 and ultimately the sulfoxide 21 in 79% yield.86... 

Aziridine-2-carboxylates 12 (Scheme 3.4) have also been prepared from 3-hy-droxy-a-amino esters 9 by treatment with sulfuryl chloride in place of tosyl or mesyl chloride. Treatment of 9 with thionyl chloride in the presence of triethylamine, followed by oxidation of 10 with sodium periodate and a catalytic amount of... 

Identify the oxidation number of the halogen atoms in (a) iodine heptafluoride (b) sodium periodate (c) hypobromous acid (d) sodium chlorite. 

A number of other reagents have been used to cleave C=N bonds, especially those not easily hydrolyzable with acidic or basic catalysts or which contain other functional groups that are attacked under these conditions. In particular, oximes have been converted to the corresponding aldehyde or ketone by treatment with, among other reagents, microwave irradiation on clay (Clayan), on wet sodium periodate... 

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