Thallium III sulfate

Thallium (TTT) nitrate in nitric acid and thallium (III) sulfate in sulfuric acid are also effective. 

Thallium(III) sulfate can effect a similar a-hydroxylation of straight chain saturated ketones. The vigorous conditions employed together with the apparently limited substrate effectiveness suggests that the procedure will find little synthetic application. 

While the above examples demonstrate that product control to a significant extent is possible in oxythallation by careful choice of substrate or reaction conditions, the synthetic utility of oxythallation has been illustrated most convincingly by the results obtained with highly ionic thallium(III) salts, especially the nitrate (hereafter abbreviated TTN). Unlike the sulfate, perchlorate, or fluoroborate salts (165), TTN can easily be obtained as the stable, crystalline trihydrate which is soluble in alcohols, carboxylic acids, ethers such as dimethoxyethane (glyme), and dilute mineral acids. Oxidations by TTN can therefore be carried out under a wide variety of experimental conditions. 

Symmetrical and unsymmetrical benzoins have been rapidly oxidized to benzils in high yields using solid reagent systems, copper(II) sulfate-alumina [105] or Oxone-wet alumina [105, 106] under the influence of microwaves (Scheme 6.32). Conventionally, the oxidative transformation of a-hydroxy ketones to 1,2-diketones is accomplished by reagents such as nitric acid, Fehling s solution, thallium(III) nitrate (TTN), ytterbium(III) nitrate, ammonium chlorochromate-alumina and dayfen. In addition to the extended reaction time, most of these processes suffer from drawbacks such as the use of corrosive acids and toxic metals that generate undesirable waste products. 

Thallium(I) acetate, 24 630-632 Thallium compounds, in organic reactions, 24 635 Thallium formate, 24 630 Thallium halides, 24 632 Thallium ion, 24 629 Thallium nitrate, uses for, 24 636 Thallium salts, 24 630, 632 Thallium sulfate, uses for, 24 636 Thallium (III) compounds, in organic reactions, 24 635-636 Thallium(III) fluoride, 24 632 Thallium(III) ion, 24 630 Thallium(III) salts, 24 632 Thallium(III) trifluoroacetate, 24 635 Thallium (Tl), 24 627-641... 

Sulfonation. Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of S03 or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Thphenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thallium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

Production and Economic Aspects. Thallium is obtained commercially as a by-product in the roasting of zinc, copper, and lead ores. The thallium is collected in the flue dust in the form of oxide or sulfate with other by-product metals, eg, cadmium, indium, germanium, selenium, and tellurium. The thallium content of the flue dust is low and further enrichment steps are required. If the thallium compounds present are soluble, ie, as oxides or sulfates, direct leaching with water or dilute acid separates them from the other insoluble metals. Otherwise, the thallium compound is solubilized with oxidizing roasts, by sulfatization, or by treatment with alkali. The thallium precipitates from these solutions as thallium(I) chloride [7791-12-0]. Electrolysis of the thallium(I) sulfate [7446-18-6] solution affords thallium metal in high purity (5,6). The sulfate solution must be acidified with sulfuric acid to avoid cathodic separation of zinc and anodic deposition of thallium(III) oxide [1314-32-5]. The metal deposited on the cathode is removed, kneaded into lumps, and dried. It is then compressed into blocks, melted under hydrogen, and cast into sticks. 

In addition to the halide systems there are a number of thallium(I) salts of thallium(III) complex anions in which the overall stoichiometry implies, incorrectly, the presence of thallium(II) species. These include the sulfate, selenate,369 acetate370 and oxalate371 derivatives. An X-ray determination has confirmed that Tl(OAc)2 is indeed Tl[Tl(OAc)4], in which the anions are linked through seven-coordinate Tl+, with some evidence for a stereochemically active inert pair.370 In T1[T1(0H)(S04)2], the structure consists of sheets of linked anions with Tl+ ions.372... 

The Cr1 ion readily forms complexes it exists in aqueous solution as CrfH 0)j. and forms other complexes wilh anions, such asCr(H 0).CI , Crother properties due to variation in the bonding. Compounds or the trichloride have been reported with the following arrangements CrtHjOlsClj. [CrfHiOlsCljCIi- HiO. and [Cr(HiO)4Cf CU2 H 0 Trivalenl chromium also forms double salts, notably the chromium alums, hydrated double salts of Cr(III) sulfate and the alkali metal (or thallium or ammonium) sulfates. 

Since T1 dissolves more easily in hot, dilute HNO3, it is advantageous to prepare the sulfate by evaporating a nitric acid solution containing a small excess of concentrated HgSO. The small amounts of Tl(III) sulfates formed are reduced with SOg (see also Purification of Technical Grade Thallium, p. 869). 

Potassium permanganate. Dimethyl sulfide-Chlorine. Dimethyl sulfoxide. Dimethyl sulfoxide-Chlorine. Dimethylsulf-oxide Sulfur trioxide. Dipyridine chro-mium(VI) oxide. Iodine. Iodine-Potassium iodide. Iodine tris(trifluoroacetate). Iodosobenzene diacetate. Isoamyl nitrite. Lead tetraacetate. Manganese dioxide. Mercuric acetate. Mercuric oxide. Osmium tetroxide—Potassium chlorate. Ozone. Periodic acid. Pertrifluoroacetic acid. Potassium ferrate. Potassium ferricyanide. Potassium nitrosodisulfonate. Ruthenium tetroxide. Selenium dioxide. Silver carbonate. Silver carbonate-Celite. Silver nitrate. Silver oxide. Silver(II) oxide. Sodium hypochlorite. Sulfur trioxide. Thalli-um(III) nitrate. Thallium sulfate. Thalli-um(III) trifluoroacetate. Triphenyl phosphite ozonide. Triphenylphosphine dibromide. Trityl fluoroborate. 

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