Aluminium lithium hydride

LiAlH4, lithium tetrahydridoaluminate ("lithium aluminium hydride . so-called) is an excellent reducing agent in ether solution for both organic and inorganic compounds it may be used to prepare covalent hydrides SiH ether, for example... 

Boron forms a whole series of hydrides. The simplest of these is diborane, BjH. It may be prepared by the reduction of boron trichloride in ether by lithium aluminium hydride. This is a general method for the preparation of non-metallic hydrides. 

Silicon, unlike carbon, does notiorm a very large number of hydrides. A series of covalently bonded volatile hydrides called silanes analogous to the alkane hydrocarbons is known, with the general formula Si H2 + 2- I uf less than ten members of the series have so far been prepared. Mono- and disilanes are more readily prepared by the reaction of the corresponding silicon chloride with lithium aluminium hydride in ether ... 

Pure phosphine can be prepared by the reduction of a solution of phosphorus trichloride in dry ether with lithium aluminium hydride ... 

Lithium aluminium hydride, LiAlH, is a very active reducing agent, and is used particularly for the ready reduction of carboxylic acids (or their esters) to primary alcohols R-COOH -> R CH,OH. 

Lithium aluminium hydride if carelessly manipulated may be dangerous for two distinct reasons. The material is caustic, and should not be allowed to touch the skin it is particularly important that the finely divided material should be kept away from the lips, nostrils and eyes, and consequently pulverisation in a mortar must be carried out with the mortar in a fume-cupboard, and with the window drawn down as far as possible in front of the operator. This danger from handling has however been greatly reduced, for the hydride is now sold in stated amounts as a coarse powder enclosed in a polythene bag in a metal container this powder dissolves readily in ether, and preliminary pulverisation is unnecessary. 

Required Salicylic acid, 6 0 g. lithium aluminium hydride, 2 5 g. dry ether, 165 ml. 

To meet the needs of the advanced students, preparations have now been included to illustrate, for example, reduction by lithium aluminium hydride and by the Meerwein-Ponndorf-Verley method, oxidation by selenium dioxide and by periodate, the Michael, Hoesch, Leuckart and Doebner-Miller Reactions, the Knorr pyrrole and the Hantzsch collidine syntheses, various Free Radical reactions, the Pinacol-Pinacolone, Beckmann and Arbusov Rearrangements, and the Bart and the Meyer Reactions, together with many others. 

For reduction with lithium aluminium hydride, see Section VI,10. 

Note. Both tetramethylene glycol (1 4-butanediol) and hexamethylene glycol (1 6 hexaiiediol) may be prepared more conveniently by copper-chromium oxide reduction (Section VI,6) or, for small quantities, by reduction with lithium aluminium hydride (see Section VI,10). 

Trimethylene dibromide (Section 111,35) is easily prepared from commercial trimethj lene glycol, whilst hexamethylene dibromide (1 O dibromohexane) is obtained by the red P - Br reaction upon the glycol 1 6-hexanediol is prepared by the reduction of diethyl adipate (sodium and alcohol lithium aluminium hydride or copper-chromium oxide and hydrogen under pressure). Penta-methylene dibromide (1 5-dibromopentane) is readily produced by the red P-Brj method from the commercially available 1 5 pentanediol or tetra-hydropyran (Section 111,37). Pentamethylene dibromide is also formed by the action of phosphorus pentabromide upon benzoyl piperidine (I) (from benzoyl chloride and piperidine) ... 

It is of interest to note that reduction of p-nitrostyrene with lithium aluminium hydride (compare Section VI, 10) gives p-phenylethylamine CgHgCHjCHjNHj. 

Lithium aluminium hydride LiAlH is a useful and conveuient reagent for the selective reduction of the carbonyl group and of various other polar functional groups. It is obtained by treatment of finely powdered lithium hydride with an ethereal solution of anhydrous aluminium chloride ... 

Some of the functional groups which are reduced by lithium aluminium hydride, the reduction product together with the theoretical mols of reducing agent required (in parenthesis) are listed below —... 

The following intermediate compounds in some reductions with lithium aluminium hydride have been formulated ... 

Potassium and sodium borohydride show greater selectivity in action than lithium aluminium hydride thus ketones or aldehydes may be reduced to alcohols whilst the cyano, nitro, amido and carbalkoxy groups remain unaffected. Furthermore, the reagent may be used in aqueous or aqueous-alcoholic solution. One simple application of its use will be described, viz., the reduction of m-nitrobenzaldehyde to m-nitrobenzyl alcohol ... 

The synthetic equivalents of the synthon H" are the hydride donors sodium borohydride NaBH4, and lithium aluminium hydride LiAIHi. How might you make TM 21 using this disconnection ... 

Hydroxyalkylthiazoles are also obtained by cyclization or from alkoxyalkyl-thiazoles by hydrolysis (36, 44, 45, 52, 55-57) and by lithium aluminium hydride reduction of the esters of thiazolecarboxylic acids (58-60) or of the thiazoleacetic adds. The Cannizzaro reaction of 4-thiazolealdehyde gives 4-(hydroxymethyl)-thiazole (53). The main reactions of hydroxyalkyl thiazoles are the synthesis of halogenated derivatives by the action of hydrobroraic acid (55, 61-63), thionyl chloride (44, 45, 63-66), phosphoryl chloride (52, 62, 67), phosphorus penta-chloride (58), tribromide (38, 68), esterification (58, 68-71), and elimination that leads to the alkenylthiazoles (49, 72). 

Thiazole acids may undergo many different types of reduction. Chemical reduction of thiazolecarboxy lic acids and of their derivatives to yield the corresponding alcohols can be accomplished with lithium aluminium hydride in ether solution (53). 

Reduction with sodium in alcohol was unsuccessful (54). The introduction of lithium aluminium hydride has provided an elegant method for the reduction of thiazole esters to hydroxythiazoles for example, ethyl 2-methyl-4-thiazolecarboxylate (11 with lithium aluminium hydride in diethyl ether gives 2-methyl-4-(hydroxymethyl)thiazole (12) in 66 to 69% yield (Scheme 7) (53),... 

Reductions carried out with lithium aluminium hydride are not always so successful. As noted by Sprague (46) the esters of 2-aminothiazole carboxylic acids behave somewhat differently with AlLiH4 (55). 

Most classical reducing agents leave the pyrimidine nucleus unaffected, as does sodium borohydride lithium aluminium hydride usually gives a di- or tetra-hydro derivative, according to substituent(s) present (70HC(16-S1)322). 

Magnesium sulfate, potassium carbonate, sodium sulfate. Calcium chloride, c cium sulfate, magnesium sulfate, sodium, lithium aluminium hydride. 

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. 

The purification of diethyl ether (see Chapter 4) is typical of liquid ethers. The most common contaminants are the alcohols or hydroxy compounds from which the ethers are prepared, their oxidation products (e.g. aldehydes), peroxides and water. Peroxides, aldehydes and alcohols can be removed by shaking with alkaline potassium permanganate solution for several hours, followed by washing with water, concentrated sulfuric acid [CARE], then water. After drying with calcium chloride, the ether is distilled. It is then dried with sodium or with lithium aluminium hydride, redistilled and given a final fractional distillation. The drying process should be repeated if necessary. 

Lithium aluminium hydride [16853-85-3] M 37.9, m 125 (dec). Extracted with EI2O, and, after filtering, the solvent was removed under vacuum. The residue was dried at 60 for 3h, under high vacuum [Ruff J Am Chem Soc 83 1788 1961], IGNITES in the presence of a small amount of water and reacts EXPLOSIVELY. 

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