Chemical sodium borohydride

Hydrazine—borane compounds are made by the reaction of sodium borohydride and a hydrazine salt in THF (23,24). The mono-(N2H4 BH ) and di-(N2H4 2BH2) adducts are obtained, depending on the reaction conditions. These compounds have been suggested as rocket fuels (25) and for chemical deposition of nickel—boron alloys on nonmetallic surfaces (see Metallic COATINGS) (26). 

Although a few simple hydrides were known before the twentieth century, the field of hydride chemistry did not become active until around the time of World War II. Commerce in hydrides began in 1937 when Metal Hydrides Inc. used calcium hydride [7789-78-8J, CaH2, to produce transition-metal powders. After World War II, lithium aluminum hydride [16853-85-3] LiAlH, and sodium borohydride [16940-66-2] NaBH, gained rapid acceptance in organic synthesis. Commercial appHcations of hydrides have continued to grow, such that hydrides have become important industrial chemicals manufactured and used on a large scale. 

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. 

M. M. Cook and co-workers, "Sodium Borohydride Reductions—Novel Approaches to Decolorization and Metals Removal iu Dye Manufacturiug and Textile Effluent Applications," 203rd National Meeting of the American Chemical Society, San Erancisco, Apr. 5—10,1992. 

J. A. Ulman and M. M. Cook, Sodium Borohydride Reductions—"Removal of Color and Metals Erom Paper Dyes," 204th National Meeting of the American Chemical Society, Washiagton, D.C., Aug. 23—28,1992. 

Catalytic reduction of folic acid to 5,6,7,8-tetrahydrofolic acid (225) proceeds fast in trifluoroacetic acid (66HCA875), but a modified method using chemical reductants leads with sodium dithionite to 7,8-dihydrofolic acid (224). Further treatment with sodium borohydride gives (225) which has been converted into 5-formyl-(6i ,S)-5,6,7,8-tetrahydro-L-folic acid (leucovorin) (226) by reaction with methyl formate (equation 70) (80HCA2554). 

Greater selectivity in purification can often be achieved by making use of differences in chemical properties between the substance to be purified and the contaminants. Unwanted metal ions may be removed by precipitation in the presence of a collector (see p. 54). Sodium borohydride and other metal hydrides transform organic peroxides and carbonyl-containing impurities such as aldehydes and ketones in alcohols and ethers. Many classes of organic chemicals can be purified by conversion into suitable derivatives, followed by regeneration. This chapter describes relevant procedures. 

This group of reagents is commercially available in large quantities some of its members - notably lithium aluminium hydride (LiAlH4), calcium hydride (CaH2), sodium borohydride (NaBH4) and potassium boro-hydride (KBH4) - have found widespread use in the purification of chemicals. 

Fructose bisphosphate aldolase of animal muscle is a Class I aldolase, which forms a Schiff base or imme intermediate between the substrate (fructose-1,6-bisP or dihydroxyacetone-P) and a lysine amino group at the enzyme active site. The chemical evidence for this intermediate comes from studies with the aldolase and the reducing agent sodium borohydride, NaBH4. Incubation of fructose bisphosphate aldolase with dihydroxyacetone-P and NaBH4 inactivates the enzyme. Interestingly, no inactivation is observed if NaBH4 is added to the enzyme in the absence of substrate. 

Step D Chemical Reduction Preparation of 3-Morpholino-4-(3-tert-Butylamino-2-Hydroxy-propoxyl-l,2,5-Thiadiazole — The 3-morpholino-4-(3-tert-butylamino-2-oxopropoxy)-1,2,5-thiadiazole (0.01 mol) is dissolved in isopropanol (10 ml). To the solution is added sodium borohydride in portions until the initial evolution of heat and gas subsides. The excess sodium borohydride is destroyed by addition of concentrated hydrochloric acid until the mixture remains acidic. The precipitate of sodium chloride is removed, ether is added, and the solution is concentrated to crystallization. The solid material is removed by filtration and dried thus providing 3-morpholino-4-(3-tert-butylamino-2-hydroxypropoxy)-1,2,5-thiadiazole, MP 161° to 163°C (as hydrochloride). 

Sodium borohydride has been manufactured commercially by this process for many years. It is of interest that a chemical discovered in the course of war research has found its chief application in the manufacture of pharmaceuticals. 

Toxic pollutants found in the mercury cell wastewater stream include mercury and some heavy metals like chromium and others stated in Table 22.8, some of them are corrosion products of reactions between chlorine and the plant materials of construction. Virtually, most of these pollutants are generally removed by sulfide precipitation followed by settling or filtration. Prior to treatment, sodium hydrosulfide is used to precipitate mercury sulfide, which is removed through filtration process in the wastewater stream. The tail gas scrubber water is often recycled as brine make-up water. Reduction, adsorption on activated carbon, ion exchange, and some chemical treatments are some of the processes employed in the treatment of wastewater in this cell. Sodium salts such as sodium bisulfite, sodium hydrosulfite, sodium sulfide, and sodium borohydride are also employed in the treatment of the wastewater in this cell28 (Figure 22.5). 

The structure of narlumidine (119) was established by Dasgupta et al. (117,119) on the basis of spectral data, particularly by comparison with spectra of bicucullinine (108), and also on chemical grounds. On hydrolysis followed by oxidation-methylation, narlumidine (119) was converted to ester 147, which was also obtained from 108 by N.O-methylation. Sodium borohydride reduction gave lactone 145, identical to the lactone obtained from 108. 

The rather labile Schiff base interaction can be chemically stabilized by reduction. The addition of sodium borohydride or sodium cyanoborohydride to a reaction medium containing an aldehyde compound and an amine-containing molecule will result in reduction of the Schiff... 

In an irreversible metal hydride, hydrogen is generated through a chemical reaction, which is not easily reversible onboard a vehicle. Common reactant is water or an alcohol. For example, sodium borohydride can produce hydrogen as... 

Typically, the imine linkages can be reduced chemically (for example, using sodium borohydride in methanol), catalytically (for example, using H2 in the presence of a catalyst such as Pd/C) or electrochemically. The reduced ligands can normally be removed from their respective metal ions using one of a number of procedures. 

The reverse reaction, namely hydrogenation, has also frequently been used to decrease the degree of unsaturation present in macrocyclic systems - typically converting imine linkages to amine groups. Such hydrogenations have usually been performed catalytically (for example, using H2 in the presence of Raney nickel or a precious metal catalyst) or by means of chemical reductants such as sodium borohydride. 

Andreae [324,325] has described a gas chromatographic method for the determination of nanogram quantities of dimethyl sulfoxide in natural waters, seawater, and phytoplankton culture waters. The method uses chemical reduction with sodium borohydride to dimethyl sulfide, which is then determined gas-chromatographically using a flame photometric detector. 

Dimethylformamide (DMF), dioxane, piperidine, methylene chloride, acetonitrile, trimethyl orthoformate (TMOF), sodium borohydride, diisopropylcarbodiimide, and trifluoroacetic acid (TFA) were purchased from Aldrich Chemical Company, Inc. and used without further purification. All of the diversity reagents were purchased from Aldrich except for Fmoc-glycine-OH, which was purchased from Novabiochem. 

Additional research in the company library, including both company reports and the external literature does not lead to any new information, but a lunchtime conversation with a colleague who recently returned from vacation does. Joanne remembered reading some sales literature from a company describing uses of sodium borohydride as an antioxidant, including its use in fatty chemicals. Could this be the culprit ... 

Additional library work, and a discussion with one of the company s organic chemists, leads to Hypothesis 3 sodium borohydride decomposing to form hydrogen gas. Chemically, this hypothesis may be written as reaction 21.5. 

Fractionation Methods. Ultrafiltration and gel filtration are nondestructive methods which, based on limited experience, can be used for fractionation of mineral complexes from digests. In earlier studies mineral absorption on the gel material was a problem. Lonnerdal (30) introduced a method of treating dextran gels with sodium borohydride in order to eliminate the mineral-binding sites on the gel. In preliminary studies we have recovered more than 90 of Ca, Mg, Fe, Zn and P in samples applied to a borohydride-treated gel column (Sephadex G-50, Pharmacia Fine Chemicals, Piscataway, NJ). Recovery of Ca (Table IV) and Mg, Fe and Zn from ultrafiltration was also good. 

Various solutions have been proposed for the reduction or elimination of autofluorescence. One way is to chemically suppress the autofluorescence signal with some reagents such as sodium borohydride, glycine or toluidine blue. However, in many cases, these approaches are either infeasible or ineffective, and none of them fully eliminates the problem. The second way is to use spectral unmixing algorithms subtracting the background fluorescence. This is only possible if you have at your disposal complicated, expensive confocal optics with sophisticated automated software (http //www.cri-inc.com/applications/fluorescence-microscopy.asp). 

The hydride generation technique is a technique in which volatile metal hydrides are formed by chemical reaction of the analyte solutions with sodium borohydride. The hydrides are guided to the path of the light, heated to relatively low temperatures, and atomized. It is useful because it provides an improved method for arsenic, bismuth, germanium, lead, antimony, selenium, tin, and tellurium. 

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