Sodium periodate preparation

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°. 

A solution of sodium methoxide, prepared from sodium (23 g) and dry methanol (500 mL), was added drop-wise at 0 °C to a stirred suspension of aminoacetonitrile hydrochloride (18, 100 g, 1.08 mol) in dry methanol (100 rnL). After stirring for 2 h at rt the precipitated sodium chloride was filtered off and the filtrate concentrated in vacuo. EtOAc (20 mL) was added and evaporated under reduced pressure to remove all traces of methanol. The oily residue was dissolved in dry EtOAc (100 mL) and anhydrous sodium sulfate added. After cooling, the precipitate was filtered off. The solution of crude aminoacetonitrile was used without further purification. This solution was added drop-wise during a period of 1 h to a vigorously stirred, ice-cooled solution of carbon disulphide (100 mL, 1.66 mol) in dry EtOAc (100 mL) under an N2 atmosphere. Continued mechanical stirring and water-free conditions were essential. The mixture was stirred at 0 °C for 1 h. The resultant precipitate was filtered off, washed with EtaO and dried, giving the product 50 as yellow crystals (99 g, 75 % on amount of sodium), m.p. 131 °C dec. IR (KBr) v max 1630, 1500 cm. ... 

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... 

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... 

Prepare a solution of 0.1 M sodium periodate in water. Protect from light. 

Dissolve sodium periodate in water at a concentration of 100 mM. Prepare fresh and protect from light. 

Other Methods of Preparation.—Ethyl 2-formyl-5-methyl-4-furoate has also been prepared by the oxidation of ethyl 2-(D-ara6ino-tetrahydroxybutyl)-5-methyl-4-furoate by means of periodic acid,8 sodium periodate,19 or minium ( red lead ) in acetic acid.66 It can also be prepared by the oxidation with sodium periodate of ethyl 2-(D-lyzo-tetrahydroxybutyl)-5-methyl-4-furoate,15 of ethyl 2-(D-fftreo-trihydroxy-propyl)-5-methyl-4-furoate,13 of ethyl 2-(o-erythro-trihydroxypropyl)-5-methyl-4-furoate,17 of ethyl 2-(L-eryfAro-trihydroxypropyl)-5-methyl-4-furoate,13 and of ethyl 2-(D-goIado-pentahydroxypentyl)-5-methyl-4-furoate.16... 

Microgels prepared in that way are hydrophilic, stable and do not tend to agglomerate. By oxidation of the diol group with sodium periodate a free aide-... 

Acyl nitroso compounds (3, Scheme 7.2) contain a nitroso group (-N=0) directly attached to a carbonyl carbon. Oxidation of an N-acyl hydroxylamine derivative provides the most direct method for the preparation of acyl C-nitroso compounds [10]. Treatment of hydroxamic acids, N-hydroxy carbamates or N-hydroxyureas with sodium periodate or tetra-alkyl ammonium periodate salts results in the formation of the corresponding acyl nitroso species (Scheme 7.2) [11-14]. Other oxidants including the Dess-Martin periodinane and both ruthenium (II) and iridium (I) based species efficiently convert N-acyl hydroxylamines to the corresponding acyl nitroso compounds [15-18]. The Swern oxidation also provides a useful alternative procedure for the oxidative preparation of acyl nitroso species [19]. Horseradish peroxidase (HRP) catalyzed oxidation of N-hydroxyurea with hydrogen peroxide forms an acyl nitroso species, which can be trapped with 1, 3-cyclohexanone, giving evidence of the formation of these species with enzymatic oxidants [20]. 

A stereoselective total synthesis of ( )-hirsutine has been developed by Brown et al. (179). Catalytic hydrogenation of hydroxycyclopentenone 327, prepared previously (180), afforded a mixture of isomeric diols 328, which were quantitatively cleaved by sodium periodate to supply 329. Reductive amination of 329 with tryptamine resulted in tetrahydropyridine 330, which upon treatment with aqueous methanol in the presence of hydrochloric acid gave indolo-[2,3-a]quinolizine 321 with pseudo stereochemistry. Conversion of 321 to ( )-hirsutine was accomplished in a similar manner by Wenkert et al. (161) via selective reduction with diisobutylaluminum hydride and methylation with methanol (179). 

Reaction of nitromethane and monosaccharide-derived dialdehydes is a useful tool that has been broadly used for the preparation of nitro and amino sugars, and carbocycles.30 Dialdehydes can easily be obtained by oxidative cleavage of conveniently protected monosaccharides with sodium periodate. Their subsequent Henry reaction with a nitroalkene, commonly nitromethane, usually gives isomeric mixtures that require the isolation of the major isomer.31 Thus, treatment of the D-ribose derivative 27 with sodium periodate gave dialdehyde 28, which was subjected to a Henry reaction with nitromethane, to afford nitrosugar 29 as an epimeric mixture (Scheme 11).32... 

Quaternary ammonium periodates, prepared either from periodic acid and the quaternary ammonium hydroxide [21, 22] or by metathesis from sodium periodate and a quaternary ammonium salt [e.g. 23-25], have been used for a range of oxidations at stoichiometric levels in two-phase systems [21-33], The tetra-n-butyl-ammonium and hexadecyltrimethylammonium salts are both highly soluble in organic solvents (considerably less so in water), whereas benzyltriethylammonium periodate has a lower solubility and stability than either salt. 

Saturated solution of sodium mcto-periodate prepared daily in deionized glass-distilled water. 

Saturated aqueous solution of sodium mefa-periodate prepare daily. 

The title compound, prepared by the oxidation of the eorresponding teUuroxide with sodium periodate, exhibits some peculiarities compared to the described reactivity of the teUuroxide. ... 

Daily doses studied have ranged from 9 to 22.6 mg of fluoride over time periods of 1-4 years [98]. These trials were particularly concerned with the use of slow-release NaF [112,113] or sodium monofluorophosphate preparations [114,115], and they generally led to reductions in the incidence of bone fracture, as shown in Table 3. In addition, they typically caused increased bone density at the neck of the femur, the femoral condyle and the lower spine [98] (Table 3). 

Tetra>/i-butylammonium periodate, (C4H9)4NI04. Mol. wt. 433.4, m.p. 158-159°, water insoluble, unstable to light. The reagent is prepared in quantitative yield by reaction of sodium periodate with tetrabutylammonium hydrogen sulfate in aqueous solution. 

The l,3-dithiane-l,3-dioxides can also be prepared by sodium periodate oxidation of the 1,3-dithiane, and the irons isomer was thus obtained in a 58% recrystallized yield [81]. Chiral molecules of this type (C2 symmetry ) are particularly suitable for use as chiral acyl anion equivalents [11,82]. 

Aldehydes and ketones often can be prepared by oxidation of alkenes to 1,2-diols (Sections 11-7C and 11-7D), followed by oxidative cleavage of the 1,2-diols with lead tetraethanoate or sodium periodate. For example,... 

Exercise 16-37 An elegant modification of the two-step procedure to prepare ketones from alkenes by hydroxylation and oxidative cleavage of the diol formed uses a small amount of potassium permanganate (or osmium tetroxide, 0s04) as the catalyst and sodium periodate as the oxidizing agent ... 

Then began, and continued for more than twenty years, a long series of analytical and structural researches on carbohydrates by P. Fleury, J. E. Courtois, and their coworkers. It may be recalled that sodium periodate was not then readily available and, especially during the sad years of the Second World War, had to be prepared in the laboratory. 

The use of cyclic sulfates in synthetic applications has been limited in the past because, although cyclic sulfites are easily prepared from diols, a convenient method for oxidation of the cyclic sulfites to cyclic sulfates had not been developed. The experiments of Denmark [70] and of Lowe and co-workers [71 ] with stoichiometric ruthenium tetroxide oxidations and of Brandes and Katzenellenbogen [72a] and Gao and Sharpless [68] with catalytic ruthenium tetroxide and sodium periodate as cooxidant have led to an efficient method for this oxidation step. Examples of the conversion of several diols (67) to cyclic sulfites (68) followed by oxidation to cyclic sulfates (69) are listed in Table 6D.7. The cyclic sulfite/cyclic sulfate sequence has been applied to 1,2-, 1,3-, and 1,4-diols with equal success. Cyclic sulfates, like epoxides, are excellent electrophiles and, as a consequence of their stereoelectronic makeup, are less susceptible to the elimination reactions that usually accompany attack by nucleophiles at a secondary carbon. With the development of convenient methods for their syntheses, the reactions of cyclic sulfates have been explored, Most of the reactions have been nucleophilic displacements with opening of the cyclic sulfate ring. The variety of nucleophiles used in this way is already extensive and includes H [68], [68,73-76], F" [68,72,74], PhCOCT [68,73,74], NOJ [68], SCN [68],... 

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