Lithium aluminium hydride reaction with water

Heating (5)-2-hydroxybutyric acid with methanol and an acid catalyst gives compound E. On reaction of E with lithium aluminium hydride followed by water, compound F is formed, which reacts with periodic acid (HI04) to give G. Finally, on reaction of... 

Chemical drying of liquids often involves reaction, with or without heating, of a solid which will react selectively with water. Calcium or lithium aluminium hydrides are often used evolved hydrogen needs safe venting. For the lithal, careful stirring and temperature control is essential to prevent formation of extremely... 

Solid lithium aluminium hydride can be solublized in non-polar organic solvents with benzyltriethylammonium chloride. Initially, the catalytic effect of the lithium cation in the reduction of carbonyl compounds was emphasized [l-3], but this has since been refuted. A more recent evaluation of the use of quaternary ammonium aluminium hydrides shows that the purity of the lithium aluminium hydride and the dryness of the solvent are critical, but it has also been noted that trace amounts of water in the solid liquid system are beneficial to the reaction [4]. The quaternary ammonium aluminium hydrides have greater hydrolytic stability than the lithium salt the tetramethylammonium aluminium hydride is hydrolysed slowly in dilute aqueous acid and more lipophilic ammonium salts are more stable [4, 5]. 

The reduction of methyl 6-methoxy-2-naphthyl acetate with lithium aluminium hydride in refluxing ether gives 2-(6-methoxy-2-naphthyl)ethanol, which by treatment with PBr3 in refluxing benzene is converted into 2-(6-methoxy-2-naphthyl)ethyl bromide. Further reaction with KCN in refluxing ethanol-water affords 3-(6-methoxy-2-naphthyl) propionitrile, which is finally treated with methylmagnesium iodide in refluxing ethanol. 

Metal hydrides. Lithium hydride, sodium hydride, potassium hydride and lithium aluminium hydride all react violently with water liberating hydrogen the heat of reaction may cause explosive ignition. Excess metal hydride from a reaction must be destroyed by the careful addition of ethyl acetate or acetone. 

Method B.104 In a 1-litre flask equipped with a condenser, a thermometer and a dropping funnel is placed 0.3 mol of lithium aluminium hydride (CAUTION, see Section 4.2.49, p. 445) in dry ether (300 ml). A nitrogen atmosphere is maintained throughout the reaction. To this stirred solution 0.45 mol of ethyl acetate is added over a period of 75 minutes maintaining the temperature at 3-7 °C. The reaction is stirred for an additional 30 minutes. To this solution at —10 °C is added 29.1 g (0.3 mol) of hexanenitrile in 5 minutes. The reaction temperature rises to 12°C in 10 minutes with the formation of a viscous solution. It is allowed to stir for another 50 minutes at 3 °C. The reaction mixture is decomposed by the addition of 300 ml of 2.5 m sulphuric acid. The ether layer is separated and the aqueous layer is extracted with ether. The combined ether extracts are washed with sodium hydrogen carbonate solution and water and dried over anhydrous sodium sulphate (1). 

Note. (1) Reaction of lithium borohydride with water may be rapid and violent do not expose to high humidity and avoid contact with eyes, skin and clothing (contact with cellulosic material may cause combustion). It should be handled with the same caution as is afforded to lithium aluminium hydride (Section 4.2.49, p. 445). 

Sodium borohydride is one of the weakest hydride donors available. The feet that it can be used in water is evidence of this as more powerful hydride donors such as lithium aluminium hydride, LiAlI-fe, react violently with water. Sodium borohydride reacts with both aldehydes and ketones, though the reaction with ketones is slower for example, benzaldehyde is reduced about 400 times faster than acetophenone in isopropanol. 

The reactions are commonly initiated with AIBN at ca. 80 °C in a solvent such as benzene or toluene, but alkyl halides have also been reduced at -60 °C with tributyltin hydride under sonication conditions.133-134 Some reductions of halides have been carried out by generating the tin hydride in situ from a molar equivalent of the reducing agent [lithium aluminium hydride, sodium borohydride, or poly(methylhydrosiloxane)] and a catalytic amount of organotin hydride, halide, or oxide. Reduction of halides has also been carried out under aqueous conditions, using 4,4 -azobis(4-cyanovaleric acid) (ACVA) as a water-soluble radical initiator.60... 

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