Sodium borohydride copper hydride

Common catalyst compositions contain oxides or ionic forms of platinum, nickel, copper, cobalt, or palladium which are often present as mixtures of more than one metal. Metal hydrides, such as lithium aluminum hydride [16853-85-3] or sodium borohydride [16940-66-2] can also be used to reduce aldehydes. Depending on additional functionahties that may be present in the aldehyde molecule, specialized reducing reagents such as trimethoxyalurninum hydride or alkylboranes (less reactive and more selective) may be used. Other less industrially significant reduction procedures such as the Clemmensen reduction or the modified Wolff-Kishner reduction exist as well. 

Braman et al. [34] used sodium borohydride to reduce arsenic and antimony in their trivalent and pentavalent states to the corresponding hydrides. Total arsenic and antimony are then measured by their spectral emissions, respectively, at 228.8 nm and 242.5 nm. Limits of detection are 0.5 ng for antimony and 1 ng for arsenic, copper, and silver. Oxidants interfere in this procedure. 

Reduction of cuprous chloride with sodium borohydride gives copper hydride which is a highly selective agent for the preparation of aldehydes from acyl chlorides [775]. 

Alkyl chlorides are with a few exceptions not reduced by mild catalytic hydrogenation over platinum [502], rhodium [40] and nickel [63], even in the presence of alkali. Metal hydrides and complex hydrides are used more successfully various lithium aluminum hydrides [506, 507], lithium copper hydrides [501], sodium borohydride [504, 505], and especially different tin hydrides (stannanes) [503,508,509,510] are the reagents of choice for selective replacement of halogen in the presence of other functional groups. In some cases the reduction is stereoselective. Both cis- and rrunj-9-chlorodecaIin, on reductions with triphenylstannane or dibutylstannane, gave predominantly trani-decalin [509]. 

Reduction of unsaturated ketones to saturated alcohols is achieved by catalytic hydrogenation using a nickel catalyst [49], a copper chromite catalyst [50, 887] or by treatment with a nickel-aluminum alloy in sodium hydroxide [555]. If the double bond is conjugated, complete reduction can also be obtained with some hydrides. 2-Cyclopentenone was reduced to cyclopentanol in 83.5% yield with lithium aluminum hydride in tetrahydrofuran [764], with lithium tris tert-butoxy)aluminium hydride (88.8% yield) [764], and with sodium borohydride in ethanol at 78° (yield 100%) [764], Most frequently, however, only the carbonyl is reduced, especially with application of the inverse technique (p. 21). 

Usually alcohols accompany aldehydes in reductions with lithium aluminum hydride [1104] or sodium bis 2-methoxyethoxy)aluminum hydride [544], or in hydrogenolytic cleavage of trifluoroacetylated amines [7772]. Thus terr-butyl ester of. -(. -trifluoroacetylprolyl)leucine was cleaved on treatment with sodium borohydride in ethanol to rerr-butyl ester of A7-prolylleucine (92% yield) and trifluoroethanol [7772]. During catalytic hydrogenations over copper chromite, alcohols sometimes accompany amines that are the main products [7775]. 

Since sodium borohydride usually does not reduce the nitrile function it may be used for selective reductions of conjugated double bonds in oc,/l-un-saturated nitriles in fair to good yields [7069,1070]. In addition some special reagents were found effective for reducing carbon-carbon double bonds preferentially copper hydride prepared from cuprous bromide and sodium bis(2-methoxyethoxy)aluminum hydride [7766], magnesium in methanol [7767], zinc and zinc chloride in ethanol or isopropyl alcohol [7765], and triethylam-monium formate in dimethyl formamide [317]. Lithium aluminum hydride reduced 1-cyanocyclohexene at —15° to cyclohexanecarboxaldehyde and under normal conditions to aminomethylcyclohexane, both in 60% yields [777]. 

Considerable inter-element interference effects have been reported on the actual hydride-forming step. Elements easily reduced by sodium borohydride (e.g. silver, gold, copper, nickel) give rise to the greatest suppressions. These interfering ions may be removed by the addition of masking agents that complex with them. 

Other reagents that have been used to reduce support-bound aromatic nitro compounds include phenylhydrazine at high temperatures (Entry 5, Table 10.12), sodium borohydride in the presence of copper(II) acetylacetonate [100], chromium(II) chloride [196], Mn(0)/TMSCl/CrCl2 [197], lithium aluminum hydride (Entry 3, Table... 

Esters may alternatively be reduced to primary alcohols either using hydrogen under pressure in the presence of a copper chromite catalyst,56 or with lithium aluminium hydride (Expt 5.38), but not with sodium borohydride which is insufficiently reactive. However it has been found recently that sodium borohydride in mixed solvents (methanol/tetrahydrofuran) reduces /1-ketoesters to 1,3-diols, and this method offers a convenient route to this type of compound.57... 

Sodium aluminum chloride, 435 Sodium amalgam, 310, 416-417 Sodium amide-Sodium r-butoxide, 417-418 Sodium azide-Triphenylphosphine, 418 Sodium bis(2-methoxyethoxy)aluminum hydride, 166,418-420 Sodium borohydiidc, 323,420-421 Sodium borohydride-Alumina, 421 Sodium borohydride-Bis(2,4-pentane-dionato)copper(ll), 421 Sodium borohydride-Cerium(Ill) chloride,... 

Reducing agents Aluminum hydride. Bis-3-methyl-2-butylborane. n-Butyllithium-Pyridine. Calcium borohydride. Chloroiridic acid. Chromous acetate. Chromous chloride. Chromous sulfate. Copper chromite. Diborane. Diborane-Boron trifluoride. Diborane-Sodium borohydride. Diethyl phosphonate. Diimide. Diisobutylaluminum hydride. Dimethyl sulfide. Hexamethylphosphorous triamide. Iridium tetrachloride. Lead. Lithium alkyla-mines. Lithium aluminum hydride. Lithium aluminum hydride-Aluminum chloride. Lithium-Ammonia. Lithium diisobutylmethylaluminum hydride. Lithium-Diphenyl. Lithium ethylenediamine. Lithium-Hexamethylphosphoric triamide. Lithium hydride. Lithium triethoxyaluminum hydride. Lithium tri-/-butoxyaluminum hydride. Nickel-aluminum alloy. Pyridine-n-Butyllithium. Sodium amalgam. Sodium-Ammonia. Sodium borohydride. Sodium borohydride-BFs, see DDQ. Sodium dihydrobis-(2-methoxyethoxy) aluminate. Sodium hydrosulflte. Sodium telluride. Stannous chloride. Tin-HBr. Tri-n-butyltin hydride. Trimethyl phosphite, see Dinitrogen tetroxide. 

Syntheses of ( )-canadine, ( )-thalictricavine, ( )-corydaline, and berlambine have been achieved from dimethoxyhomophthalic anhydride (88). The anhydride reacts with hydrastinine (87 R R = CH2) and its dimethoxy-analogue (87 R = r2 = Me) to give the lactam acids (89 R R CH2) and (89 R = R = Me) the methyl esters of which, on reduction with lithium aluminium hydride, yield the alcohols (90 R R = CH2, R = CH2OH) and (90 R = R = Me, R = CH2OH). The conversion of these alcohols into their methanesulphonyl esters, followed by reduction with sodium borohydride, then affords ( )-thalic-tricavine(90 R R = CHa,R = Me) and( )-corydaline(90 R = R = R = Me). Oxidation of the lactam acid (89 R R = CH2) with lead tetra-acetate and copper(ii) acetate in acetic acid and dimethylformamide gives the unsaturated lactam berlambine (91), which can be reduced by lithium aluminium hydride in the presence of aluminium chloride to ( )-canadine (90 R R = CH2, R" = H). ... 

Related Reagents. Calcium Hydride Iron(III) Chloride-Sodium Hydride Lithium Aluminum Hydride Potassium Hydride Potassium Hydride-5-Butyllithium-(V,(V,(V, (V -Tetra-methylethylenediamine Potassium Hydride-Hexamethylphos-phoric Triatnide Sodium Borohydride Sodium Hydride-copper(II) Acetate-Sodium t-Pentoxide Sodium Hydride-nickel(II) Acetate-Sodium t-Pentoxide Sodium Hydride-palladium(II) Acetate-Sodium t-Pentoxide Tris(cyclopenta-dienyl)lanthanum-Sodium Hydride Lithium Hydride Sodium Telluride. 

A very useful variant of the hydrazone reduction is the deoxygenation of aldehydes and ketones via the hydride reduction of tosylhydrazones (Caglioti reaction) The method is mild, convenient and widely applicable. While sodium borohydride was used in the earlier procedures, considerable improvements have been achieved through the uses of sodium cyanoborohydride, catecholborane, diborane, his-benzoyloxy borane and copper borohydride as reducing agents and HMPA, DMF, sulpholane, etc. as solvents. Use of the sterically crowded 2,4,6-triisopropyl tosylhydrazone derivative has greatly facilitated the reduction in some cases (equations 61-64). ... 

Using sodium borohydride, selenium ions are reduced to selenium hydride, transferred to a heated quartz cuvette with the aid of a current of inert gas, decomposed thermally, and the absorption of the atoms is measured in the beam of an atomic-absorption spectrometer. In the hydride technique, the element which is to be determined is volatilized as a gaseous hydride and separated off from the matrix. Interferences may occur if there is a considerable excess of elements such as antimony, arsenic, tin, bismuth, mercury, or tellurium, which may also be volatilized using this technique. Above all, heavy metals such as copper and nickel have a disturbing effect during the hydride formation itself. These interferences may be diminished by adding 300 mg of solid 2-pyridine aldoxime to the solution for measurement. 

Potassium trisiamylborohydride can now be made in a convenient manner and the reaction of cyclic boronic esters possessing a wide variety of sterlc requirements with potassium hydride gives rise to the corresponding borohydrides. These represent a new class of reducing agents whose stability and reactivity have been explored. Copper(I) alkylborohydrldes are obtained from 1 1 mixtures of cuprous chloride and sodium borohydride on reaction with alkenes in THF. 

The transfonnations of gm-dihalocyclopropanes are synthetically useful because the cyclopropanes are readily prepared by the addition of dihalocarbene to olefins. In most of dehalogenation reactions to monohalocyclopropanes, the reagents are limited to metallic reductants such as organotin hydride, lithium aluminum hydride, sodium borohydride, Grignard reagent, and zinc-copper couple [1-9]. A versatile method for the reduction of gm-dibromocyclopropanes 3 with an organic reductant is achieved by use of diethyl phosphonate (commercially named diethyl phosphite) and triethylamine to give the monobromocyclopropanes 4 (Scheme 2.2) [10]. 

Other Preparations.—Carboxylic acids have been converted into aldehydes through di-isobutylaluminium hydride reduction of 3-acylthiazolidine or 2-thiazoline-2-thiol ester intermediates. Bis(triphenylphosphine)copper(l) tetrahydroborate, (Ph3P)2CuBH4, shows promise as a new reagent for the reduction of acid chlorides to aldehydes. The same conversion can be accomplished using sodium borohydride in a mixture of acetonitrile and hexamethyl-phosphoramide containing a cadmium(il) chloride-dimethylformamide complex. ... 

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