Hthium

Thus o-hydroxyphenyl-llthium cannot be obtained from o-bromophenol and lithium but, under proper conditions, o-bromophenol reacts with n-butyl-lithium to give a good yield of the lithium salt of o-hydroxyphenyl-hthium. An interesting application is to the preparation from m-bromochlorobenzene and M-butyl-lithlum of w-chlorobenzoic acid—an expensive chemical ... 

C bol the solution of re-butyl-hthium to — 35° in a Dry Ice - acetone bath and add, whilst stirring vigorously, a solution of 48 g. of ni-chlorobromo-benzene (Section IV,62) in 75 ml. of anhydrous ether. Stir for 8-10 minutes and pour the mixture with stirring on to a large excess of sohd carbon dioxide in the form of a Dry Ice - ether slush contained in a -htre beaker. Isolate the acid as detailed above for p-Toluic acid and recrystal-lise it from hot water. The yield of ni-chlorobenzoic acid, m.p. 150-151°, is 27 g. 

Olefins add anhydrous acetic acid to give esters, usually of secondary or tertiary alcohols propjiene [115-07-1] yields isopropyl acetate [108-21-4], isobutjiene [115-11-7] gives tert-huty acetate [540-88-5]. Minute amounts of water inhibit the reaction. Unsaturated esters can be prepared by a combined oxidative esterification over a platinum group metal catalyst. Eor example, ethylene-air-acetic acid passed over a palladium—Hthium acetate catalyst yields vinyl acetate. 

Lithium Fluorobora.te, Lithium fluoroborate is used in a number of batteries (qv) as an electrolyte, for example in the hthium—sulfur battery... 

Germanium metal is also used in specially prepared Ge single crystals for y-ray detectors (54). Both the older hthium-drifted detectors and the newer intrinsic detectors, which do not have to be stored in hquid nitrogen, do an exceUent job of spectral analysis of y-radiation and are important analytical tools. Even more sensitive Ge detectors have been made using isotopicahy enriched Ge crystals. Most of these have been made from enriched Ge and have been used in neutrino studies (55—57). 

Corning 8603 lithium metasihcate, Li2OSi02 Hthium disiHcate, Li2 0-2 Si02 photochemically machinable fluid amplifiers... 

Absorption Systems. Absorption refrigeration cycles employ a secondary fluid, the absorbent, to absorb the primary fluid, refrigerant vapor, which has been vaporized in the evaporator. The two materials that serve as the refrigerant—absorbent pair must meet a number of requirements however, only two have found extensive commercial use ammonia—water and water—Hthium bromide. 

Ammonia—water systems are more complex than water—Hthium bromide systems, but can be used at temperatures down to —40° C. 

Reaction with AlCl gives lithium aluminum hydtide, which is the main apphcation of hthium hydtide. Reaction with ammonia yields hthium amide... 

Lithiation and Subsequent Transformations. Lithiation is the most geneial means of intioducing a 2-substituent on the indole hng. Three intermediates have been used most frequendy in this context. These ate 1-phenylsulfonylindole (19), l-/-butoxycarbonylindole (20), and hthium indole-l-carboxylate (21). 

Anionic polymerization of vinyl monomers can be effected with a variety of organometaUic compounds alkyllithium compounds are the most useful class (1,33—35). A variety of simple alkyllithium compounds are available commercially. Most simple alkyllithium compounds are soluble in hydrocarbon solvents such as hexane and cyclohexane and they can be prepared by reaction of the corresponding alkyl chlorides with lithium metal. Methyllithium [917-54-4] and phenyllithium [591-51-5] are available in diethyl ether and cyclohexane—ether solutions, respectively, because they are not soluble in hydrocarbon solvents vinyllithium [917-57-7] and allyllithium [3052-45-7] are also insoluble in hydrocarbon solutions and can only be prepared in ether solutions (38,39). Hydrocarbon-soluble alkyllithium initiators are used directiy to initiate polymerization of styrene and diene monomers quantitatively one unique aspect of hthium-based initiators in hydrocarbon solution is that elastomeric polydienes with high 1,4-microstmcture are obtained (1,24,33—37). Certain alkyllithium compounds can be purified by recrystallization (ethyllithium), sublimation (ethyllithium, /-butyUithium [594-19-4] isopropyllithium [2417-93-8] or distillation (j -butyUithium) (40,41). Unfortunately, / -butyUithium is noncrystaUine and too high boiling to be purified by distiUation (38). Since methyllithium and phenyllithium are crystalline soUds which are insoluble in hydrocarbon solution, they can be precipitated into these solutions and then redissolved in appropriate polar solvents (42,43). OrganometaUic compounds of other alkaU metals are insoluble in hydrocarbon solution and possess negligible vapor pressures as expected for salt-like compounds. 

Clays and Other Sources. Sedimentary deposits, especially hthium-bearing clays found in the western United States, offer an additional source of lithium. These clays contain lithium-hearing trioctahedral smectites, of which hectorite [12173-47-6] NaQ23(Mg,Li)2Si402Q(F,0H)2, is one mineral. 

An emerging electrochemical appHcation of lithium compounds is in molten carbonate fuel ceUs (qv) for high efficiency, low poUuting electrical power generation. The electrolyte for these fuel ceUs is a potassium carbonate—hthium carbonate eutectic contained within a lithium aluminate matrix. The cathode is a Hthiated metal oxide such as lithium nickel oxide. 

Lithium Carbonate. Lithium carbonate [554-13-2], Li2C02, is produced in industrial processes from the reaction of sodium carbonate and Hthium sulfate or Hthium chloride solutions. The reaction is usually performed at higher temperatures because aqueous Hthium carbonate solubiHty decreases with increasing temperatures. The solubiHty (wt %) is 1.52% at 0°C, 1.31% at 20°C, 1.16% at 40°C, 1.00% at 60°C, 0.84% at 80°C, and 0.71% at 100°C. Lithium carbonate is the starting material for reactions to produce many other Hthium salts, including the hydroxide. Decomposition of the carbonate occurs above the 726°C melting point. 

Lithium carbonate addition to HaH-Heroult aluminum ceU electrolyte lowers the melting point of the eutectic electrolyte. The lower operating temperatures decrease the solubiHty of elemental metals in the melt, allowing higher current efficiencies and lower energy consumption (55). The presence of Hthium also decreases the vapor pressure of fluoride salts. 

Lithium carbonate is used to prepare Hthium aluminosiHcate glass ceramics which have low thermal coefficients of expansion, allowing use over a wide temperature range. It also finds uses in specialty glasses and enamels. 

The molten carbonate fuel ceU uses eutectic blends of Hthium and potassium carbonates as the electrolyte. A special grade of Hthium carbonate is used in treatment of affective mental (mood) disorders, including clinical depression and bipolar disorders. Lithium has also been evaluated in treatment of schizophrenia, schizoaffective disorders, alcoholism, and periodic aggressive behavior (56). 

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. 

Lithium Chloride. Lithium chloride [7447- 1-8], LiCl, is produced from the reaction of Hthium carbonate or hydroxide with hydrochloric acid. The salt melts at 608°C and bods at 1382°C. The 41-mol % LiCl—59-mol % KCl eutectic (melting point, 352°C) is employed as the electrolyte in the molten salt electrolysis production of Hthium metal. It is also used, often with other alkaH haHdes, in brazing flux eutectics and other molten salt appHcations such as electrolytes for high temperature Hthium batteries. 

A simple and economical route involving the reaction of Hthium metal and organic haHdes was developed in 1930 to prepare organ oHthium compounds such as / -butyUithium (76) ... 

This property has been exploited in syntheses of /V-nitrosamine derivatives by the reaction of electrophiles (E) with a-Hthiated intermediates. These intermediates are prepared by hydrogen—Hthium exchange using Hthium dusopropylamide [4111-54-0] (LDA) (76,77). 

A fused-salt electrolysis process has been demonstrated (30). Carbon dioxide is introduced to the cathode area of a melt of 60 wt % LiCl—40 wt % Li2C02 at 550°C. The carbon dioxide reacts with hthium oxide which is produced by electrolysis. Oxygen is released at the anode and carbon plates onto the cathode. The reaction requites a potential of 4.5 V. The reactions ate as follows ... 

Deuterium is abundant in and easily separated from water. There is enough deuterium on earth to provide power for geological time scales. In contrast, tritium is not available in nature, but can be produced from n+ lithium reactions (see Lithium and lithium compounds). Natural Hthium is exhaustible, but sufficient tritium can be provided from it until fusion energy production is efficient enough to involve only D-D reactions ... 

Other agents are also used for the treatment of manic-depressive disorders based on preliminary clinical results (177). The antiepileptic carbamazepine [298-46-4] has been reported in some clinical studies to be therapeutically beneficial in mild-to-moderate manic depression. Carbamazepine treatment is used especially in bipolar patients intolerant to lithium or nonresponders. A majority of Hthium-resistant, rapidly cycling manic-depressive patients were reported in one study to improve on carbamazepine (178). Carbamazepine blocks noradrenaline reuptake and inhibits noradrenaline exocytosis. The main adverse events are those found commonly with antiepileptics, ie, vigilance problems, nystagmus, ataxia, and anemia, in addition to nausea, diarrhea, or constipation. Carbamazepine can be used in combination with lithium. Several clinical studies report that the calcium channel blocker verapamil [52-53-9] registered for angina pectoris and supraventricular arrhythmias, may also be effective in the treatment of acute mania. Its use as a mood stabilizer may be unrelated to its calcium-blocking properties. Verapamil also decreases the activity of several neurotransmitters. Severe manic depression is often treated with antipsychotics or benzodiazepine anxiolytics. 

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