Lithium halide

Lithium Halides. Lithium haHde stabiHty decreases with increasing atomic weight of the halogen atom. Hence, the solubiHty increases from the sparingly soluble Hthium fluoride to the very soluble bromide and iodide salts. The low melting points of Hthium haHdes are advantageous for fluxes in many appHcations. 

N-Alkylations, especially of oxo-di- and tetra-hydro derivatives, e.g. (28)->(29), have been carried out readily using a variety of reagents such as (usual) alkyl halide/alkali, alkyl sulfate/alkali, alkyl halide, tosylate or sulfate/NaH, trialkyloxonium fluoroborate and other Meerwein-type reagents, alcohols/DCCI, diazoalkanes, alkyl carbonates, oxalates or malon-ates, oxosulfonium ylides, DMF dimethyl acetal, and triethyl orthoformate/AcjO. Also used have been alkyl halide/lithium diisopropylamide and in one case benzyl chloride on the thallium derivative. In neutral conditions 8-alkylation is observed and preparation of some 8-nucleosides has also been reported (78JOC828, 77JOC997, 72JOC3975, 72JOC3980). 

Alkyl halide Lithium Anion radical Lithium cation... 

Studies of alkyl halide-lithium alkyl reactions have been almost wholly concerned with proton polarization. The one exception to date is an investigation of polarization in the reaction of n-butyl lithium with p-fluorobenzyl chloride giving p,p -difluorobibenzyl (A/E multi-plet) and l-fluoro-4-pentylbenzene (E/A) (Rakshys, 1970). Surprisingly H-polarization is not observed. 

In densely packed solids without obvious open channels, the transport number depends upon the defects present, a feature well illustrated by the mostly ionic halides. Lithium halides are characterized by small mobile Li+ ions that usually migrate via vacancies due to Schottky defects and have tc for Li+ close to 1. Similarly, silver halides with Frenkel defects on the cation sublattice have lc for Ag+ close to 1. Barium and lead halides, with very large cations and that contain... 

Chlorohydrins epoxides. Chloromethyllithium is thermally unstable, but can be obtained by reaction of lithium wire with bromochloromethane. The halide-lithium exchange is markedly accelerated by sonication [(( ], which also promotes a subsequent reaction of the chloromethyllithium with an aldehyde or a ketone to form epoxides via chlorohydrins.1 Overall yields are 70-90%. 

Because the free energy of the aryl halide/lithium exchange equilibrium is essentially equal to the enthalpy change of the reaction, we consider other reactions from the same source of the general type (equation 11),... 

Ammino-lithium Halides.—Lithium halides absorb gaseous ammonia in the dry state. The chloride forms four compounds depending on the temperature at which absorption takes place. Below 13° C. tetrammino-lithium chloride, [Li(NH3)4]Cl, is produced. Triam-mino-lithium chloride, [Li(NH3)3]Cl, is formed between 20° and 60° C. diammino-lithium chloride, [Li(NH3)2]Cl, between 60° and 85° C. and at 85° C. the monmnmine, [Li(NH3)]Cl, is produced. These are white unstable substances.1... 

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. 

SAMPLE SOLUTION (a) In the preparation of organolithium compounds from organic halides, lithium becomes bonded to the carbon that bore the halogen. Therefore, isopropenyllithium must arise from isopropenyl bromide. 

Tributyltin hydride, 316 Zinc iodide, 280 From alkyl halides Lithium aluminum hydride-Ceri-um(III) chloride, 159 Palladium catalysts, 230 Sodium cyanoborohydride-Tin(II) chloride, 280 From alkyl sulfonates Lithium triethylborohydride, 153 From thiols... 

Formylation of an alkyllithium (1, 280).1 Formylation of an alkyllithium or a Grignard reagent with DMF (Bouveault reaction) is generally unsatisfactory because of side reactions. However, sonication of the mixture of an alkyl or aryl halide, lithium, and DMF substantially improves the rate and the yield. The method is applicable to primary, secondary, and tertiary bromides or chlorides. Typical yields are in the range 65-85%. 

CLAISEN REARRANGEMENT Alkylaluminum halides. Lithium diisopropylamide. Potassium hydride. Sodium dithionite. Titanium(TV) chloride. Trifluoroacetic acid. Trimethylaluminum. 

Like the other halides, lithium iodide forms double salts with other metallic iodides, such as those of mercury 5 and lead.6... 

RiZn. Dialkylzinc reagents can be prepared from an organic halide, lithium wire, and zinc bromide at 0° in toluene-THF by sonication in a cell-disruptor generator. Yields are essentially quantitative. Diarylzinc reagents and dimethylzinc can be prepared by sonication in an ultrasonic laboratory cleaner. 

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... 

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