Osmium tetroxide preparation

Selective chemical staining of the rubber phase of the samples using chlorosulphonic acid and osmium tetroxide, preparation of ultrathin sections (about 0.1 xm thick) in a cryoultramicro-tome, and investigation of the sections by conventional transmission electron microscopy (TEM). 

Cyclodecanediol has been prepared by the hydrogenation of sebacoin in the presence of Raney nickel or platinum, by the reduction of sebacoin with aluminum isopropoxide or lithium aluminum hydride, and by the oxidation of cyclodecene with osmium tetroxide and pyridine. ... 

Similar hydroxylation-oxidations can be carried out using a catalytic amount of osmium tetroxide with A-methylmorpholine oxide-hydrogen peroxide or phenyliodosoacetate." A recent patent describes the use of triethylamine oxide peroxide and osmium tetroxide for the same sequence. Since these reactions are of great importance for the preparation of the di-hydroxyacetone side-chain of corticoids, they will be discussed in a later section. 

Many of the reactions already discussed for the preparation of bis-oxygenated pregnanes can also be used for the synthesis of 17,20,21-tris-oxygenated pregnanes by proper choice of substrate. Thus, reaction of a 17-vinyl-17-hydroxy steroid or a A -21-hydroxypregnene with osmium tetroxide will give the 17,20,21-triol, and the Stork reaction can be applied to 17a-hydroxy-20-keto steroids. 

Method A Standardisation with arsenic (III) oxide. Discussion. The most trustworthy method for standardising cerium(IV) sulphate solutions is with pure arsenic(III) oxide. The reaction between cerium(IV) sulphate solution and arsenic(III) oxide is very slow at the ambient temperature it is necessary to add a trace of osmium tetroxide as catalyst. The arsenic(III) oxide is dissolved in sodium hydroxide solution, the solution acidified with dilute sulphuric acid, and after adding 2 drops of an osmic acid solution prepared by dissolving 0.1 g osmium tetroxide in 40mL of 0.05M sulphuric acid, and the indicator (1-2 drops ferroin or 0.5 mL /V-phenylanthranilic acid), it is titrated with the cerium(IV) sulphate solution to the first sharp colour change orange-red to very pale blue or yellowish-green to purple respectively. 

If a mixture of diphenyl sulphide and the corresponding sulphoxide are treated with osmium tetroxide in boiling ether for 48 hours the sulphide is unchanged whilst the sulphoxide is converted into the sulphone in 96% yield with concomitant production of osmium trioxide140. It thus seems that this method would be useful synthetically for the preparation of sulphones from sulphoxides containing sulphide functionalities. Ruthenium tetroxide may be used in place of osmium(VIII) oxide148. 

The preparation of Pans-1,2-cyclohexanediol by oxidation of cyclohexene with peroxyformic acid and subsequent hydrolysis of the diol monoformate has been described, and other methods for the preparation of both cis- and trans-l,2-cyclohexanediols were cited. Subsequently the trans diol has been prepared by oxidation of cyclohexene with various peroxy acids, with hydrogen peroxide and selenium dioxide, and with iodine and silver acetate by the Prevost reaction. Alternative methods for preparing the trans isomer are hydroboration of various enol derivatives of cyclohexanone and reduction of Pans-2-cyclohexen-l-ol epoxide with lithium aluminum hydride. cis-1,2-Cyclohexanediol has been prepared by cis hydroxylation of cyclohexene with various reagents or catalysts derived from osmium tetroxide, by solvolysis of Pans-2-halocyclohexanol esters in a manner similar to the Woodward-Prevost reaction, by reduction of cis-2-cyclohexen-l-ol epoxide with lithium aluminum hydride, and by oxymercuration of 2-cyclohexen-l-ol with mercury(II) trifluoro-acetate in the presence of ehloral and subsequent reduction. ... 

Harvested samples should be immediately prepared for the SEM by fixation in a 0.5% osmium tetroxide solution in the dark for 1 h. If the sample is collected in the field, store in buffered 3% glutaraldehyde solution (pH 7.2) until samples can be fixed. 

The cis form has been prepared by the syn hydroxylation of cyclopentene by osmium tetroxide as follows ... 

Osmium tetroxide is obtained as an intermediate during recovery of osmium metal from osmiridium or other noble metal minerals (See Osmium). In general, oxidation of an aqueous solution of an osmium salt or complex, such as sodium osmate with nitric acid, yields the volatile tetroxide which may be distilled out from the solution. In the laboratory, the compound can be prepared by oxidation of the osmium tetrachloride, OsCh, or other halide solutions with sodium hypochlorite followed by distdlation. 

Osmium tetroxide reacts with phenyl Grignard reagent to produce a reactive intermediate, serving as a synthetic route to prepare polyphenyl osmium complexes. For example, reaction with o-tolyl magnesium bromide, o-tolMgBr, forms a purple, tetracoordinated osmium ort/io-tolyl complex, Os(o-tol)4, which reacts with trimethylphosphine or carbon monoxide to yield osmium n-aryl complexes. 

The first useful asymmetric synthesis with a-halo boronic esters utilized (S)-pinanediol [1S-(la,2/1.3//,5a)]-2,6,6-trimethylbicyclo[3.1.1]heptane-2,3-diol as the chiral director39,40. This diol is easily prepared from ( + )-a-pinene by a catalytic hydroxylation with osmium tetroxide, and its enantiomer (i )-pinanediol is available from (-)-(a)-pinene41,42. Pinanediol esters remain useful in view of their excellent stability as well as the ease of preparation of the diol. and their stereoselectivity is very high even though it is no longer the state of the art. 

Diammino-osmo-hydroxide, [OsO(NH3)2](OH)2, is prepared from osmium tetroxide and excess of concentrated aqueous ammonia. The yellow liquid obtained is heated in a closed vessel at 50° C. till it becomes dark brown in colour and a black powder is deposited. It is then exposed to the atmosphere and evaporated at low temperature, when a blackish-brown powder is deposited. The dry powder decomposes explosively on heating, with evolution of nitrogen. It dissolves in acids yielding the corresponding salts, and from these the base may be precipitated on the addition of aqueous alkali hydroxide. On boiling with a solution of alkali, however, the base is decomposed, ammonia is liberated, and a precipitate of osmium dioxide remains.1... 

Preparation of cis-Diols by Catalytic Oxidation of Olefins with Osmium Tetroxide... 

Organometallic reagents and catalysts continue to be of considerable importance, as illustrated in several procedures CAR-BENE GENERATION BY a-ELIMINATION WITH LITHIUM 2,2,6,6-TETRAMETHYLPIPERIDIDE l-ETHOXY-2-p-TOL-YLCYCLOPROPANE CATALYTIC OSMIUM TETROXIDE OXIDATION OF OLEFINS PREPARATION OF cis-1,2-CYCLOHEXANEDIOL COPPER CATALYZED ARYLA-TION OF /3-DICARBONYL COMPOUNDS 2-(l-ACETYL-2-OXOPROPYL)BENZOIC ACID and PHOSPHINE-NICKEL COMPLEX CATALYZED CROSS-COUPLING OF GRIG-NARD REAGENTS WITH ARYL AND ALKENYL HALIDES 1,2-DIBUTYLBENZENE. 

Furo[3,2-c][l]benzopyran-4-ones have been prepared either by acid catalyzed condensation of 4-hydroxycoumarin with a benzoin derivative (equation 11) (81IJC(B)614) or from 3-allyl-4-hydroxycoumarins on oxidation with osmium tetroxide/potassium periodate followed by cyclization of the intermediary aldehyde with PPA (equation 12) (79G109). 

Miscellaneous. Aside from the oxidation chemistry described, only a few catalytic applications are reported, including hydrogenation of olefins (114,115), a, [3-unsaturated carbonyl compounds (116), and carbon monoxide (117) and the water gas shift reaction (118). This is so owing to the kinetic inertness of osmium complexes. A 1% by weight osmium tetroxide solution is used as a biological stain, particulady for preparation of samples for electron microscopy. In the presence of pyridine or other heterocyclic amines it is used as a selective reagent for single-stranded or open-form B-DNA (119) (see Nucleic acids). Osmium tetroxide has also been used as an indicator for unsaturated fats in animal tissue. Osmium tetroxide has seen limited if controversial use in the treatment of arthritis (120,121). 

An epoxide is formed from alkene and peroxymethanoic acid (H202 -l- HC02H) but is cleaved by the HC02H present to a frans-diol. Alternatively, osmium tetroxide may be used in fe/t-butyl alcohol and leads to the c/ s-diol. Potassium permanganate in neutral can be useful for preparation of c/ s-glycols. (See Section 11-70.)... 

Diols are prepared from alkenes by oxidation with reagents such as osmium tetroxide, potassium permanganate, or hydrogen peroxide (Section 11-7C). However, ethylene glycol is made on a commercial scale from oxacy-clopropane, which in turn is made by air oxidation of ethene at high temperatures over a silver oxide catalyst (Section 11-7D). 

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 ... 

The focus of this chapter is to acquaint the reader with details of catalytic asymmetric dihydroxylation with osmium tetroxide and the scope of results that one can expect to achieve with current optimum conditions. The literature through mid-1992 has been reviewed in compiling this chapter. Osmium tetroxide catalyzed hydroxy]ations of olefins and acetylenes are the subject of an extensive review by Schroder published in 1980 [2a]. A comprehensive review of research and industrial applications of asymmetric dihydroxylations is in preparation [2b]. 

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