Purification, general halides

In the instances of phosphorous and phosphonous acid systems, the generation of a new C-P bond via the classical Michaelis-Arbuzov reactions as noted above leads to products that are esters themselves. Isolation of the free acid product requires cleavage of the ester linkage in a separate reaction step, generally after isolation and purification of the initial product. The advent of silyl phosphorus reagents for the Michaelis-Arbuzov reaction allowed free acid products to be isolated simply by water workup of the reaction system. Further, since the byproduct was a silyl-halide, the general concern that the by-product halide would participate in an extraneous Michaelis-Arbuzov reaction was obviated. 

White [7] gives a general review that includes information about the preparation and purification of a variety of alkali and alkaline earth halide melts. Information about fluorides can also be found in an earlier review article by Bamberger [8]. Many different halide melts have been used as solvents for electrochemistry, and a complete discussion of all of these melts is outside the scope of this chapter. However, two systems that have generated continuous interest over the years are the LiCl-KC1 eutectic (58.8-41.2 mol%, mp = 352°C) [9] and the LiF-NaF-KF (46.5-11.5-42.0 mol%, mp = 454°C) also known as FLINAK [10]. The former is an electrolyte commonly used in thermal batteries, whereas the latter molten salt is of interest for refractory metal plating. 

Though not a general rule, it is worthwhile pointing out that ionic liquids with halide anions often give good or superior activities than, for example, [BF4] , [PF6] or [Tf2N] salts. In this respect C-C coupling reactions stand out from other catalysed transformations in ionic liquids where the presence of halide (often due to insufficient purification of the ionic liquid used) is frequently found to inhibit catalytic activity. 

The most generally applicable method of forming the transition- and inner transition-metal 7t-cyclopentadienyl bond involves the reaction of Na[Cp] with the appropriate anhydrous metal halide or complex halide in an ethereal solvent such as THF or glyme under a dry, inert atmosphere. The complexes are usually isolated by evaporation of the solvent and extraction into an aromatic or aliphatic hydrocarbon solvent. Purification is achieved by crystallization or sublimation. 

Anhydrous lanthanide trihalides, particularly the trichlorides, are important reactants for the formation of a variety of lanthanide complexes, including organometallics. Routes for the syntheses of anhydrous lanthanide trihalides generally involve high temperature procedures or dehydration of the hydrated halides.The former are inconvenient and complex for small scale laboratory syntheses, while dehydration methods may also be complex and have limitations, for example, use of thionyl chloride. - Moreover, the products from these routes may require purification by vacuum sublimation at elevated temperatures. Redox transmetalation between lanthanide metals and mercury(II) halides was initially carried out at high temperatures. However, this reaction can be carried out in tetrahydrofuran (THF, solvent) to give complexes of lanthanide trihalides with the solvent. These products are equally as suitable as reactants for synthetic purposes as the uncomplexed... 

The most common procedure for preparing bismuth alkoxides is the substitution reaction of bismuth halides with alkali metal alkoxides. The alternative is treatment of bismuth amides with alcohols. Bismuth alkoxides such as trimethoxide, triethoxide and triisopropoxide were first prepared in 80-93% yields by the reaction between BiCl3 and alkali metal alkoxides by Mehrotra et al. in 1966. Bismuth alkoxides are less soluble in organic solvents and the yields after purification by sublimation are generally very low (10-20%) [66IJC537]. Known aliphatic alkoxides include Bi(OEt)3... 

As a general procedure if the olefin is impure, the oxymercura-tion-reduction process may include an olefin purification step. Alternatively, this process may be used to purify the olefin for other purposes. - In such cases, acetone is substituted for ether and, after oxymercuration for the same length of time as suggested above, the solution is poured with stirring into two volumes of water containing one equivalent each of sodium bicarbonate and sodium chloride. The mercury derivative is filtered, recrystallized from ethanol-water, ether, dioxane, or ethyl acetate-heptane and then either reduced as described above (in 70-80% yield) to produce pure alcohol, or deoxy-mercurated with cold 6N HCl, with ethereal lithium aluminum hydride (added cautiously), or high concentrations of alkali halides - to produce the pure olefin. 

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