From Tellurium Tetrachlorides

Tellurium tetrachloride and four molar equivalents of potassium arenethiosulfonates reacted in ethanol-free chloroform to form tellurium bis[arenethiosulfonates].  

Tellurium Bis[benzenethiosulfonate] 5.4 g (20 mmol) of tellurium tetrachloride are suspended in 30 ml of ethanol-free chloroform, the suspension is stirred with ice cooling, and 20 g (94 mmol) of potassium benzenethiosulfonate are added in portions. After completion of the addition, the mixture is stirred with cooling for 10 min, the cold yellow suspension is filtered, and the filtrate is discarded. The solid on the filter is treated with two 10 m/portions of ice-cold chloroform and with 10 m/of diethyl ether, the solid is dried under reduced pressure over sulfuric acid, treated with three 30 ml portions of water, two 5 ml portions of diethyl ether, and dried again. This crude product (8 g) is dissolved in 80 ml of boiling chloroform, the mixture is filtered, the filtrate is concentrated to half its volume, and the concentrate is cooled in an ice bath with stirring. The crystals are collected and can be further purified by recrystallization from boiling chloroform (25 m//2 g) crude yield 8 g (84%) m.p. 170° (dec.). 

Tellurium bis 4-methylbenzenethiosulfonate was similarly prepared in 50% yield. The compound melted at 215°, depositing tellurium after a few seconds in the liquid state.  

Addition of twice the stoichiometrically required amount of potassium 4-methylbenzene thiosulfonate to tellurium bis[methanethiosulfonate] in bromoform or tellurium bis[benzenethiosulfonate] in chloroform gave a precipitate of tellurium bis[4-methylbenz enethiosulformte] in yields higher than 90%.  

Irgolic Organo-tellurium Compounds without a C,Te-Bond 

TeCl4 reacts with 1,4-dilithiotetraphenyl-l,3-butadiene to give tetraphenyltellurophene.  

Tetraphenyltellurophene To a suspension of 1,4-dilithiotetraphenyl-l,3-butadiene in 100 mL of ether, prepared from 10 g (56 mmol) of diphenyl acetylene and excess of lithium, is added over 15 min a solution of TeCl4 (5.3 g, 19.7 mmol). The green mixture is poured into a mixture of CH2CI2 and water, the organic phase is separated, filtered through anhydrous MgS04, filtered and evaporated. The residue is recrystallized from dichloromethane/ethanol, giving tetraphenyltellurophene 5.35 g (56%), m.p. 239°C. 

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Tellurium nitride was first obtained by the reaction of TeBt4 with liquid ammonia more than 100 years ago. The empirical formula TeN was assigned to this yellow, highly insoluble and explosive substance. However, subsequent analytical data indicated the composition is Tc3N4 which, in contrast to 5.6a and 5.6b, would involve tetravalent tellurium. This conclusion is supported by the recent preparation and structural determination of Te6N8(TeCl4)4 from tellurium tetrachloride and tris(trimethylsilyl)amine (Eq. 5.5). The TceNs molecule (5.12), which is a dimer of Tc3N4, forms a rhombic dodecahedron in which the... 

Organyltellurium trichlorides from tellurium tetrachloride and organic substrates... 

From tellurium tetrachloride and ketones and carboxylic anhydrides... 

Condensation Products from Tellurium Tetrachloride and Aryl Alkyl Ethers. 

The same products were obtained from tellurium tetrachloride and the sulfonic acid anhydrides or the sulfonic acids2. 

Tellurium tetrathiolates were claimed to be formed from tellurium tetrachloride and stoichiometric amounts of thiols and dithiols at low temperature with ethanol as the reaction medium1. A reinvestigation of these reactions2 showed that tellurium tetrathiolates could not be isolated under these conditions. The products were mixtures of bis[organothio] tellurium and diorgano disulfides (see p. 38). 

Table 6 2-Chloroalkyl Tellurium Trichlorides from Tellurium Tetrachloride and Alkenes...

When tellurium tetrachloride and acetone (1 2 molar ratio) are refluxed in dry chloroform, 2-methyl-4-oxo-2-penten-l-yl tellurium trichloride is formed in 43% yield. This compound can be obtained in quantitative yield from tellurium tetrachloride and mesityl oxide. The reaction of tellurium tetrachloride and acetone in the presence of sodium hydrogen carbonate gives only acetonyl tellurium trichloride and diacetonyl tellurium dichloride5. 

Table 16 Diaryl Tellurium Dichlorides from Tellurium Tetrachloride and Aromatic Compounds...

Upon pyrolyses, bis[2-chloroalkyl] tellurium dichlorides, obtained from tellurium tetrachloride and propene or 1-butene, yielded v/r.-dichloroalkanes among other products1-3. 

Treatment of diaryl tellurium dichlorides, obtainable from tellurium tetrachloride and aromatic compounds, with carbon monoxide in the presence of palladium(II) chloride/lithium chloride gives arenecarboxylic acids. Biaryls are formed as by-products1,2. Similar products were obtained when the diaryl tellurium dichlorides were reacted with nickel tetracarbonyl3. 

Tetraaryl tellurium compounds were prepared from tellurium tetrachloride and lithium halide-free organo lithium compounds3 7. Lithium halide-free organic lithium compounds were synthesized from diaryl mercury and lithium8. 

Tetrabutyl tellurium and tetramethyl tellurium were formed from tellurium tetrachloride and the appropriate alkyl lithium. 

Tetravinyl tellurium was prepared from tellurium tetrachloride and vinyl magnesium bromide in tetrahydrofuran6. 

The 2-acetylamino-l,3-benzenetellurols required as the precursors of 1,3-benzotellur-azoles, can be prepared from tellurium tetrachloride and 2-aminophenyl mercury chlorides. This method allows the synthesis of 1,3-benzotellurazoles with substituents in the para-position to the nitrogen atom2. 

Tab.21 Phenoxatellurin 10,10-dichlorides from tellurium tetrachloride and diphenyl ethers... 

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