I Acetate

Tlie purity of metal(Il) chromium(III) oxides was checked by chemical analysis. Chromium and divalent metal contents agree with the calculated values within less than 1%. Divalent metal chromium(III) oxides crystallize in the cubic spinel system. Chemical analysis data, cubic lattice constants and powder diffraction lines are given in Table III. 

Divalent metal chromium(III) oxides produced by a double-decomposition reaction between LiCr02 and a molten metal(II) salt are fine powders. Electron microscopic examination shows that these powders are constituted of grains, the repartition size of which is heterogeneous (500-3000 A), but each grain is made of smaller crystallites. The average diameter of the crystallites, determined by a radiocrystallographical method (measurement of the widening of X-rays 220 and 335), is about 250 A. 

Submitted by S. J. K1RCHNER and QUINTUS FERNANDO Checked by DANA DARBYt and J. A. DILTSt 

The thermal decomposition of copper(II) acetate has been proposed by several workers as a useful method for the synthesis of pure copper(I) acetate.1-3 This method, however, suffers from several drawbacks. The major products of the decomposition are copper(I) oxide and acetic acid in contrast, the copper(I) acetate is obtained in low yields ( 5%) together with some acetone and carbon 

All the synthetic methods described above give products that require extensive purification. Moreover, the copper(I) acetate often undergoes rapid oxidation on exposure to the atmosphere because any solvent in contact with the copper(I) acetate absorbs water vapor, which promotes the conversion of copper(I) to copper(II) in air. 

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Silver compounds, available from commercial suppHers, are expensive. Reagent grades of sHver(I) carbonate, cyanide, diethjldithiocarbamate, iodate, nitrate, oxide, phosphate, and sulfate are available. Standardized solutions of silver nitrate are also available for analytical uses. Purified grades of sHver(I) acetate, bromide, cyanide, and iodide can be purchased silver nitrate is also made as a USP XX grade for medicinal uses (6). 

Further versatihty was added to the range of substituents available for introduction into the 6a-position by use of the 6a(succinimido-oxy) derivative (18) prepared by treatment of the 6a-(methylthio) derivative (17) with A/-hydroxy-succinimide and silver(I) acetate in dimethylformamide in virtually quantitative yield. In this way the 6a-cyanopeniciILin (19, X = CN), 6a-viny1penici11in (19, X = CH=CH2) and 6a-pheny1penici11in (19, X = C H ) could be prepared in high yield (43). 

Merkuro-. mercurous, mercury (I), -azetat, n. mercurous acetate. mercury(I) acetate, -chlorld, n. mercurous chloride, mercury(I) choride. -chrom, n. (Pharm.) mercuro chrome, -jodid, n. n ercurous iodide, mer-cury(I) iodide. -nitrat, n. mercurous nitrate, mercury(I) nitrste. -oxyd, n. mercurous oxide, mercury(I) oxide, -salz, n. mercurous salt, mercury (I) salt, -sulfat, n. mercurouasulfate, mercury(I) sulfate, -sulfid, n. mercurous sulfide, mercury(I) sulfide, -verbindung, /. mercurous compound, mercury (I) compound. 

Similarly, a nickel(II) 2,3,9,10,16,17,23,24-octacyanophthalocyanine can be produced in 86% yield from the corresponding metal-free phthalocyanine and nickel(I I) acetate in dimethylform-amidc at 100 C for two hours.427... 

There have been relatively few detailed kinetic studies of the decompositions of metal acetates, which usually react to yield [1046] either metal oxide and acetone or metal and acetic acid (+C02 + H2 + C). Copper(II) acetate resembles the formate in producing a volatile intermediate [copper(I) acetate] [152,1046,1047]. 

A. trans-l,2-Cyclohexanediol. In a 100-ml., round-bottomed flask equipped with a reflux condenser protected with a drying tube are placed a magnetic stirring bar, 17.56 g. (0.0667 mole) of thallium (I) acetate (Note 1), and 40 ml. of dried acetic acid (Note 2). The mixture is stirred and heated at reflux for 1 hour. To the cooled mixture are added 2.84 g. (3.5 ml., 0.0346 mole) of cyclohexene (Note 3) and 8.46 g. (0.0333 mole) of iodine (Note 4). The resulting suspension is stirred and heated at reflux for 9 hours (Note 5), and then cooled to room temperature. The yellow precipitate of thallium(I) iodide is filtered and washed thoroughly with ethyl ether. The filtrates are comhined, the solvents are removed under reduced pressure with a rotary evaporator (Note 6), and the residual liquid is dissolved in dry ethyl ether. The turbid solution is dried with anhydrous potassium carbonate, and the solvent is again removed by rotary evaporation (Note 6), affording 5.4-6.3 g. of trans-1,2-cyclohexanediol diacetate as a mobile, brown liquid (Note 7). 

The mechanisms of these reactions are presumably analogous to those of the Pr6vost and Woodward-Prevost reactions. In the first step of the reaction of iodine and thallium(I) acetate with cyclohexene in both parts A and B of this procedure, trans-2-iodocyclohexyl acetate is formed. The second equivalent of thal-lium(I) acetate scavenges iodide ion during formation of the 1,3-... 

Thallium(I) acetate Acetic acid, thallium salt (8, 9) (15843-14-8) Acetic acid, thallium (H-) salt (8,9) (563-68-8)... 

STEREOSELECTIVE HYDROXYLATION WITH THALLIUM(I) ACETATE AND IODINE trans- AND cis-l,2-CYCLOHEXANEDIOLS... 

Thallium(I) acetate purchased from BDH Chemicals Ltd., Poole, England, or Fluka AG, Buchs, Switzerland, was used without further purification. This reagent is also available from Alfa Division, Ventron Corporation. 

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