Lithium aluminum hydride alkyl halides

Alkyl azides prepared by nucleophilic substitution of alkyl halides by sodium azide as shown m the first entry of Table 22 3 are reduced to alkylammes by a variety of reagents including lithium aluminum hydride... 

Alkyl azides prepared by nucleophilic substitution by azide ion in primary or secondary alkyl halides are reduced to primary alkylamines by lithium aluminum hydride or by catalytic hydrogenation... 

Lithium aluminum hydride (LiAlH4) is the most powerful of the hydride reagents. It reduces acid chlorides, esters, lactones, acids, anhydrides, aldehydes, ketones and epoxides to alcohols amides, nitriles, imines and oximes to amines primary and secondary alkyl halides and toluenesulfonates to... 

A thio-substituted, quaternary ammonium salt can be synthesized by the Michael addition of an alkyl thiol to acrylamide in the presence of benzyl trimethyl ammonium hydroxide as a catalyst [793-795]. The reaction leads to the crystallization of the adducts in essentially quantitative yield. Reduction of the amides by lithium aluminum hydride in tetrahydrofuran solution produces the desired amines, which are converted to desired halide by reaction of the methyl iodide with the amines. The inhibitor is useful in controlling corrosion such as that caused by CO2 and H2S. 

Tin alkyl hydrides can be prepared from the halides by the reaction with lithium aluminum hydride. 

Protodehalogenation.1 This hydride is the reagent of choice for hydrogenolysis of alkyl halides. Lithium aluminum hydride is somewhat less powerful, particularly for reduction of alkyl chlorides. 

Tetra-p,3-carbonyldodecacarbonylhexa-rhodium, 288 of alkyl halides to alkanes Chromium(II) chloride, 84 Lithium aluminum hydride-Ceri-um(III) chloride, 159... 

The use of acyl azides in the preparation of amines by the Curtius rearrangement has been discussed previously (Section 23-12E). Alkyl azides can be reduced readily by lithium aluminum hydride to amines and, if a pure primary amine is desired, the sequence halide — azide — amine may give as good or better results than does the Gabriel synthesis (Section 23-9D). 

Both the alkyl halide and the alkoxide ion are prepared from alcohols. The problem then becomes one of preparing the appropriate alcohol (or alcohols) from the starting ester. This is readily done using lithium aluminum hydride. 

Primary and secondary alkyl bromides, iodides, and sulfonates can be reduced to the corresponding alkanes with LiBHEt3 (superhydride) or with lithium aluminum hydride (LiAlH4, other names lithium tetrahydridoaluminate or lithium alanate). If such a reaction occurs at a stereocenter, the reaction proceeds with substantial or often even complete stereoselectivity via backside attack by the hydride transfer reagent. The reduction of alkyl chlorides to alkanes is much easier with superhydride than with LiAlH4. The same is true for sterically hindered halides and sulfonates ... 

Formation and Reduction of Nitriles Like the azide ion, cyanide ion (- C=N ) is a good Sn2 nucleophile it displaces leaving groups from unhindered primary and secondary alkyl halides and tosylates. The product is a nitrile (R—C=N), which has no tendency to react further. Nitriles are reduced to primary amines by lithium aluminum hydride or by catalytic hydrogenation. 

Reductive dehalogeuation of alkyl halides. Lithium aluminum hydride has commonly been used only for reductive dchalogenation of reactive substrates organotin hydrides, for example tri- -btityltin hydride (I. 1192-1193 2, 424 3, 294), have been used for reduction of inert halides. Recently JeflToid ei al. have reported that supposedly inert halides are reducible by lithium aluminum hydride. Thus the vinyl halide (I) is reduced to (2, endb-2-phenylbicyclo[3.2. l]octene-3) by lithium aluminum hydride in refluxing ether (24 hr.). 3-Bromobicyclo[3.2.l]octene-2 is reduced to the parent... 

Lithium aluminum hydride (LAH) reacts with pyridines and their analogs in aprotic solvents to give dihydro- and tetrahydro-pyridines. In the absence of proton sources dihydropyridines normally predominate, solutions of pyridine and LAH form lithium complexes (32 Scheme 7), which likely consist of both 1,2- and 1,4-dihydropyridlnes. This intermediate has been used as a reducing agent for ketones, and reaction with alkyl halides generates 3-substituted pyridines (33) in good yield. 

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