Thallium -oxide-based

Friedel-Crafts reactions involving electrophilic substitution of aromatic compounds have been reported on solid base catalysts such as thallium oxide and MgO. The rates of benzylation of toluene by benzyl chloride over MgO nanocrystals were found to be of the order CP-MgO > CM-MgO > AP-MgO.56 An important observation in the study was that x-ray diffraction of the spent catalyst... 

Crystal growth of these compounds is complicated by the high volatility of thallium oxides and thallium-containing compounds at elevated temperatures and the toxicity of thallium. Also, the similarity in structures leads to problems controlling phase purity and samples which appear to be single crystals based on their morphology can be shown to be complicated intergrowths by X-ray diffraction studies. 

A porcelain Gooch filter crucible with a perforated base is supported on a series of indentations made in the middle of the tube. The oxygen inlet tube is located some 4-5 cm. below the indentations and is bent upwards so that the end of the tube is approximately 1 cm. below the crucible. The perforated base of the Gooch crucible is covered with a pad of glass wool to retain black particles of thallium oxide or metal, and then thallium shot is dried by pressing between wads of filter paper, and lOOg. of dried metal is placed in the crucible. 

It takes place at atmospheric pressure, between 450 and 550 C in the presence of a silver oxide based catalyst deposited on silica or of earth alkali metal oxides, thallium and lead, and with excess propylene. An inert (nitrogen, steam, etc.) is used as diluent, in order to absorb the heat generated daring the conversion, whose molar yield is 7Q per cent in relation to propylene. 

Monoalkylthallium(III) compounds can be prepared easily and rapidly by treatment of olefins with thallium(III) salts, i.e., oxythallation (66). In marked contrast to the analogous oxymercuration reaction (66), however, where treatment of olefins with mercury(II) salts results in formation of stable organomercurials, the monoalkylthallium(III) derivatives obtained from oxythallation are in the vast majority of cases spontaneously unstable, and cannot be isolated under the reaction conditions employed. Oxythallation adducts have been isolated on a number of occasions (61, 71,104,128), but the predominant reaction pathway which has been observed in oxythallation reactions is initial formation of an alkylthallium(III) derivative and subsequent rapid decomposition of this intermediate to give products derived by oxidation of the organic substrate and simultaneous reduction of the thallium from thallium(III) to thallium(I). The ease and rapidity with which these reactions occur have stimulated interest not only in the preparation and properties of monoalkylthallium(III) derivatives, but in the mechanism and stereochemistry of oxythallation, and in the development of specific synthetic organic transformations based on oxidation of unsaturated systems by thallium(III) salts. 

Perez Ruiz et al. [26] determined penicillamine and tiopronin in pharmaceutical preparations by flow injection fluorimetry. The procedure is based on the oxidation of these drugs by thallium(III), whereupon the fluorescence of T1(T) produced in the oxidation of penicillamine is monitored using excitation at 227 nm and emission at 419 nm. A linear calibration graph for penicillamine was obtained between 3 x 10-7 and 8 x 10 5 6 M. 

The layer-type structures and chemical nature of the constituents of the bismuth and thallium-based cuprate superconductors - notably the lone-pair stereochemistry of Bis+, variable valence of copper, and considerable exchange among some of the cation sites - combine to make structural non-ideality, nonstoichiometry, and phase intergrowth the rule rather that the exception in these families of materials. These features, as well as the probable metastability of the phases (and possibly all high-temperature oxide superconductors), also contribute to the difficulties typically encountered in preparing single-phase samples with reproducible properties and compositions. 

Transfer of a methyl group from methyl vitamin B12 to Hg(II), Tl(III), Pt(II), and Au(I) was found to occur (334). An acid-base reaction path was proposed for mercury and thallium, whereas an oxidation-reduction sequence involving Pt(IV) and Au(lII) intermediates was suggested. 

Methyla-arylacetates. These esters have been obtained by oxidative rearrangement of alkyl aryl ketones with thallium(III) nitrate in acidic methanol or trimethyl orthoformate (4,496 5, 656 7, 362). A new method, which avoids the toxic TTN, is based on the Woodward version of the Prevost reaction. Thus, treatment of the ketone with iodine (or bromine) and silver nitrate (2 equiv.) in refluxing methanol containing trimethyl orthoformate results in methyl a-arylacetates in 90% yield from simple substrates. Yields are lowered by electron-withdrawing substituents on the aromatic group and by a-branching in the alkyl group.2... 

The norbelladine derivative 408, which served as the starting material for the synthesis of ( )-oxocrinine (415) (Scheme 35), may be readily prepared from the reductive animation of piperonal with tyramine followed by acylation with trifluoroacetic anhydride (191,192). When the N-acylated monophenol 408 was treated with excess thallium tris(trifluoroacetate) in methylene chloride, the di-enone 412 was obtained in 19% yield (191), whereas use of the oxidant vanadium oxyfluoride in trifluoroacetic acid/trifluoroacetic anhydride afforded 412 in 88% yield (192). Base-induced N-deacylation of 412 was accompanied by spontaneous cyclization to furnish racemic oxocrinine (415). Attempts to oxidize the free amine derived from 408 led to the formation of a number of products, some of which resulted from oxidation at nitrogen. 

Silver salts are also common activators in numerous Suzuki coupling reactions. The earliest example could probably be found in the Kishi s palytoxin synthesis. Silver oxide as well as thallium hydroxide provided dramatic rate enhancements in the couplings of vinylboronic acids (Scheme 10.41).69 Both thallium and silver ions are most probably abstracting halide in palladium intermediates, but silver is clearly the most efficient. Moreover, with the right counterion, the silver salt also acts as a mild base and activator. 

The dibenzazonine (21), related to a biosynthetic precursor of Erythrina alkaloids, was obtained in 36% yield by intramolecular oxidative coupling of tetramethoxytrifluoroacetamide (20) by thallium(in) trifluoroacetate in tri-fluoroacetic acid at 25 °C.17 The trifluoroacetyl group was readily removed by alkaline hydrolysis, and the H n.m.r. spectrum of the free base confirmed that coupling had taken place para-para (with respect to the 3-methoxy-group of each aromatic ring). 

In a first approximation supra-Cp metal complexes can be prepared the same way as normal or other Cp-metal and organo-metal bonds in general. The methods used most often (see Appendix) are the metathesis reaction [Eq. (1)] followed in number by oxidative additions (Eq. (2)] and metallation/deprotonation reactions [Eq. (3)]. The latter is especially important for the cyclpentadienyl alkali metal compounds. A useful variation of reaction (3) is the formation of CpTl in an acid/base reaction from cyclopentadiene and thallium ethoxide [Eq. (3b)]. This represents a convenient route to cyclopentadienylthallium compounds, which are also valued (in place of Cp alkalis) as mild Cp-transfer reagents for the synthesis of difficultly isolable cyclopentadienyl derivatives (77). 

Related Topics II Thallium-Based High-Tc Superconducting Oxides... 

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