Sodium, reduction methods

The sodium reduction process was first implemented in Germany by Siemens and Halske A.G. and it remained a principally European method, while the American tantalum industry was founded exclusively on the electrolysis of molten fluorides [28, 576]. The production of tantalum by sodium reduction has gained worldwide acceptance and currently, nearly 90% of the world s tantalum is produced by the sodium reduction method [538]. 

The original top of the Washington Monument was aluminum, made in 1884 by the sodium-reduction method. 

Hydroisoquinolines. In addition to the ring-closure reactions previously cited, a variety of reduction methods are available for the synthesis of these important ring systems. Lithium aluminum hydride or sodium in Hquid ammonia convert isoquinoline to 1,2-dihydroisoquinoline (175). Further reduction of this intermediate or reduction of isoquinoline with tin and hydrochloric acid, sodium and alcohol, or catalyticaHy using platinum produces... 

Berlin Institute Method. This method is for determination of invert sugar in products containing not more than 10% invert in the presence of sucrose. It is a copper reduction method that utilizes MbUer s solution, which contains sodium carbonate. 

Finally in this section on deracemization via cyclic oxidation/reduction methods, there has been some limited work carried out on the deracemization of secondary alcohols. Soda et al. [22] employed lactate oxidase in combination with sodium borohydride to deracemize D/i-lactate (18) via the intermediate pyruvate (19) (Figure 5.12). 

Sulfonamides are very difficult to hydrolyze. However, a photoactivated reductive method for desulfonylation has been developed.240 Sodium borohydride is used in conjunction with 1,2- or 1,4-dimethoxybenzene or 1,5-dimethoxynaphthalene. The photoexcited aromatic serves as an electron donor toward the sulfonyl group, which then fragments to give the deprotected amine. The NaBH4 reduces the radical cation and the sulfonyl radical. 

The anchoring and the reduction methods of precious metal precursors influence the particle size, the dispersion and the chemical composition of the catalyst. The results of SEM and H2 chemisorption measurements are summarised in Table 3. The XPS measurements indicate that the catalysts have only metallic Pd phase on their surface. The reduction of catalyst precursor with sodium formate resulted in a catalyst with lower dispersion than the one prepared by hydrogen reduction. The mesoporous carbon supported catalysts were prepared without anchoring agent, this explains why they have much lower dispersion than the commercial catalyst which was prepared in the presence of a spacing and anchoring agent (15). 

Some of the reports are as follows. Mizukoshi et al. [31] reported ultrasound assisted reduction processes of Pt(IV) ions in the presence of anionic, cationic and non-ionic surfactant. They found that radicals formed from the reaction of the surfactants with primary radicals sonolysis of water and direct thermal decomposition of surfactants during collapsing of cavities contribute to reduction of metal ions. Fujimoto et al. [32] reported metal and alloy nanoparticles of Au, Pd and ft, and Mn02 prepared by reduction method in presence of surfactant and sonication environment. They found that surfactant shows stabilization of metal particles and has impact on narrow particle size distribution during sonication process. Abbas et al. [33] carried out the effects of different operational parameters in sodium chloride sonocrystallisation, namely temperature, ultrasonic power and concentration sodium. They found that the sonocrystallization is effective method for preparation of small NaCl crystals for pharmaceutical aerosol preparation. The crystal growth then occurs in supersaturated solution. Mersmann et al. (2001) [21] and Guo et al. [34] reported that the relative supersaturation in reactive crystallization is decisive for the crystal size and depends on the following factors. 

Titanium (IV) iodide may be prepared by a variety of methods. High-temperature methods include reaction of titanium metal with iodine vapor,1-3 titanium carbide with iodine,4 titanium(IV) oxide with aluminum (III) iodide,5 and titanium (IV) chloride with a mixture of hydrogen and iodine. At lower temperatures, titanium (IV) iodide has been obtained by the combination of titanium and iodine in refluxing carbon tetrachloride7 and in hot benzene or carbon disulfide 8 a titanium-aluminum alloy may be used in place of titanium metal.9 It has been reported that iodine combines directly with titanium at room temperature if the metal is prepared by sodium reduction of titanium (IV) chloride and is heated to a high temperature before iodine is... 

In contrast, the sodium complex [Na(AsPh2)(dioxane)]x is polymeric in the solid state [Na-As = 2.962(4), 2.937(4) A] (25). This complex was synthesized by the rather unusual method of sodium reduction of a diarsine ... 

Thermal reduction processes are not being practiced anywhere in the world at present for large-scale production of sodium. Such methods, however, can he conveniently adapted for laboratory preparation of metalhc sodium. Sodium can be prepared by thermal reduction of its hydroxide, carbonate, or chloride at elevated temperatures. These salts are heated with carbon, calcium carbide, iron carbide, ferrosilicon, or other reducing agents at temperatures above 800°C under vacuum ... 

Fairly selective reduction of certain alkenes can be achieved using the sodium-hexamethylphosphoramide (HMPA)-tm-butyI alcohol system,193 despite the general trend, that nonconjugated alkenes are usually quite resistant to the dissolving metal reduction method (see Section 11.3.2). In the case of 9(10)-octalin, the transformation leads to a nearly equilibrium product distribution ... 

Thioindoxyls are readily oxidized to thioindigo dyes.584 They may be reduced to benzo[6]thiophenes (Table XI) with zinc (Clemmensen reduction) or tin and acid (method a) (use of mossy zinc is preferred for the reduction of halothioindoxyls and also minimizes reduction of the thiophene ring),315 sodium borohydride (method b),222,424,432 or... 

Peptide aldehydes 1 can be synthesized effectively by the oxidation of peptide alcohols 15, which are readily available without racemization by reduction of peptide esters 9 with sodium borohydride-lithium chloride (Scheme 5). The peptide alcohols 15 can be readily oxidized to afford enantiomerically pure aldehydes using Parikh-Doering or Dess-Martin reagents. This route is less popular than the previously described reductive methods due to (1) the sensitivity of the aldehydes to further oxidation, (2) racemization under the reaction conditions, and (3) instability of the products under the reaction conditions. 

The consumption of sodium borohydride (reduction method) upon reduction of carbonyl groups can also be used for their quantification. Remaining NaBH4 is quantified by the amount of hydrogen formed after reaction with acid [86,87]. 

In 1979, Pelletier and co-workers reported (203) a method for selective reduction of the oxazolidine ring of C20-diterpenoid alkaloids in the presence of a ketone or an a,/ -unsaturated carbonyl group. Reduction of atisinone (225) with sodium cyanoborohydride at pH 6-7 at room temperature furnished dihydroatisinone (441) in almost quantitative yield. They generalized this reduction method by using various alkaloid derivatives containing either an a,/l-unsaturated ketone or a simple ketone moiety. 

The first commercial production of fatty alcohols in the 1930 s employed a sodium reduction process (Bouveault-Blanc) (2). However, the high usage (4 mol/mol alcohol) of expensive sodium soon led to replacement of this method of reduction by catalytic hydrogenation. 

This important fragrance material probably was introduced in commercial perfumery during the first decade of the twentieth century with the discovery of the Bouveault-Blanc reduction of esters by sodium and an alcohol (10). This is the first of several methods of preparation shown in Figure 16. Large quantities of phenylethyl alcohol were made by sodium reduction of butyl phenylacetate in normal butanol. The basic raw materials were readily available at low cost from benzyl chloride, sodium cyanide and fermentation butanol. 

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