Sodium borohydride with metal compounds

Complex aluminum and boron hydrides can contain other cations. The following compounds are prepared by metathetical reactions of lithium aluminum hydride or sodium borohydride with the appropriate salts of other metals sodium aluminum hydride [55], magnesium aluminum hydride [59], lithium borohydride [90], potassium borohydride [9i], calcium borohydride [92] and tetrabutylammonium borohydride [95]. 

Satoh, T., Suzuki, S., Suzuki, Y., Miyaji, Y., and Imai, Z., Reduction of organic compound with sodium borohydride-transition metal salt systems reduction of organic nitrile, nitro and amide compounds to primary amines, Tetrahedron Lett., 10, 4555 4558, 1969. 

When an aqueous effluent stream containing organomercurials cannot be recycled, it may be treated with chlorine to convert the organomercury to inorganic mercury. The inorganic compounds thus formed are reduced to metallic mercury with sodium borohydride. The mercury metal is drained from the reactor, and the aqueous solution discarded. The process utilising sodium borohydride is known as the Ventron process (27). 

AletalHydrides. Metal hydrides can sometimes be used to prepare amines by reduction of various functional groups, but they are seldom the preferred method. Most metal hydrides do not reduce nitro compounds at all (64), although aUphatic nitro compounds can be reduced to amines with lithium aluminum hydride. When aromatic amines are reduced with this reagent, a2o compounds are produced. Nitriles, on the other hand, can be reduced to amines with lithium aluminum hydride or sodium borohydride under certain conditions. Other functional groups which can be reduced to amines using metal hydrides include amides, oximes, isocyanates, isothiocyanates, and a2ides (64). 

Sodium Tetrahydroborate, Na[BH ]. This air-stable white powder, commonly referred to as sodium borohydride, is the most widely commercialized boron hydride material. It is used in a variety of industrial processes including bleaching of paper pulp and clays, preparation and purification of organic chemicals and pharmaceuticals, textile dye reduction, recovery of valuable metals, wastewater treatment, and production of dithionite compounds. Sodium borohydride is produced in the United States by Morton International, Inc., the Alfa Division of Johnson Matthey, Inc., and Covan Limited, with Morton International supplying about 75% of market. More than six million pounds of this material suppHed as powder, pellets, and aqueous solution, were produced in 1990. 

The nitrated model compound, 9, proved even more resistant to reduction than the polymeric analog the dissolving metal technique used to reduce 15 failed on 9, but finally the amino model, 10, was produced by treatment of with a 25-fold excess of sodium borohydride. Compound 1 serves as a difunctional initiator for NCA polymerization. 

Ventron A process for removing mercury from aqueous wastes containing organic mercury compounds. Chlorine is passed in, converting organic mercury compounds to inorganic compounds, and the mercury is then reduced to the metallic state with sodium borohydride. 

Cationic rings are readily reduced under relatively mild conditions. 1-Methylpyridinium ion with sodium borohydride (in H20, 15°C) gives the 1,2-dihydro derivative (330) at pH > 7 and the 1,2,3,6-tetrahydro derivative (331) at pH 2-5. The tetrahydro compound is probably formed via (332) which results from proton addition to (330). Pyridine cations are also reduced to 1,2-dihydropyridines by dissolving metals, e.g. Na/Hg. 

Sodium borohydride (160) was found to serve as a hydrogen donor in the asymmetric reduction of the presence of an a,pi-unsaturated ester or amide 162 catalyzed by a cobalt-Semicorrin 161 complex, which gave the corresponding saturated carbonyl compound 163 with 94-97% ee [93]. The [i-hydrogen in the products was confirmed to come from sodium borohydride, indicating the formation of a metal enolate intermediate via conjugate addition of cobalt-hydride species (Scheme 2.17). 

If the species of interest happens to be volatile, it can be collected in the head space or atmosphere of a closed system, and subsequently determined by gas chromatography (GC), MS, or a combination of these (GC-MS). In some circumstances it is possible to convert non-volatile compounds into a volatile form by appropriate derivativisation (e.g. by alkylation, or formation of a metal chelate). Separation and analysis can then be based on GC. Species containing elements such as Sn, Pb, Hg, As, Sb, Bi, Se or Te can be separated from the matrix by conversion into a chemically stable and volatile hydride (e.g. by treatment in acid solution, with sodium borohydride, NaBH4). Mixtures of hydrides can be separated by GC and detected by an electron capture unit, or if only one element is of interest, the volatile hydride(s) can be fed to an element-specific detector such as an AAS unit (fitted with a heated quartz tube cell). 

Cerutti and Schmid105 employed the principles of metal hydride reduction as a structural confirmation for the products obtained from the photo-reduction of a series of indolenine type compounds. The reduction product of 9,4a-diethyld,2,3,4-tetrahydrocarbazolinium chloride (95) with sodium borohydride was found to be identical with the photo-reduction product obtained from mercury sensitized irradiation of 95, confirming the structure of the product as 96. 

The reduction of 1-hydroxymethyl- and 1-benzoyloxymethyl-benzotriazole (138) with lithium aluminum hydride and sodium borohydride has been investigated by Gaylord and Kay.148 The hydroxymethyl compound failed to undergo reduction with lithium aluminum hydride, apparently as a result of the immediate formation of an insoluble complex by reaction of the metal hydride with the... 

A number of metals salts can be used as the source of electrophiles in reactions with alkenes. One of the most interesting of these involves the attack of mercury(II) acetate in acetic acid. Reductive cleavage of the organomercury compound with sodium borohydride leads to the overall hydration of the alkene in a Markownikoff sense. There are a number of preparative advantages, such as a reduced tendency to rearrange, associated with this and similar relatively mild procedures when compared to the direct protonation of a double bond (Scheme 3.14)... 

---