Lithium carbon dioxide, effect

Carbon dioxide has been proposed as an additive to improve the performance of lithium batteries [60]. Aurbach et al. [61] studied the film formed on lithium in electrolytes saturated with C02, and using in situ FTIR found that Li2C03 is a major surface species. This means that the formation of a stable Li2C03 film on the lithium surface may improve cyclability [62], Osaka and co-workers [63] also studied the dependence of the lithium efficiency on the plating substrate in LiC104-PC. The addition of C02 resulted in an increase in the efficiency when the substrate was Ni or Ti, but no effect was observed with Ag or Cu substrates. 

Salt effects of lithium chloride and calcium chloride on the solubility of carbon dioxide in a mixture of methanol and water were observed at 25°C and 1 atm. Experimental results can be correlated by the Setschenow equation for a fixed solvent composition of salt-free basis. The salting-out parameter is not linear with solvent composition, which is opposite to the results obtained when a mixed salt is used. 

In the present investigation, the salt effects of lithium chloride and calcium chloride on the solubility of carbon dioxide in the mixed solvents of methanol and water were experimentally studied at 25°C and 1 atm. 

C-Carboxylation of enolates.1 Carboxylation of potassium enolates generated from silyl enol ethers is not regioselective because of extensive enolate equilibration. Regiospecific C-carboxylation of lithium enolates is possible with carbonyl sulfide in place of carbon dioxide. The product is isolated as the thiol methyl ester. If simple esters are desired, transesterification can be effected with Hg(OAc)2 (8, 444). Carboxylation of ketones in this way in the presence of NaH and DMSO is not satisfactory because of competing alkylation of the enolate.2 Example ... 

The procedure described here is based on the observation that amine monohydroxo complexes of cobalt(III), rhodium(IIl), and iridium(III) react directly with carbon dioxide to form the corresponding carbonato complexes,2 3 without effect on the configuration of the amine ligands.4 The amine monoaqua complex is allowed to react with lithium carbonate or carbon dioxide gas at room temperature at pH 8.0 for a few minutes, and the carbonato complex is isolated by adding alcohol. The procedure has been used to prepare salts of the following cations pentaammine(carbonato)-cobalt(III),2 ds-ammine(carbonato)bis(ethylenediamine)cobalt(III),5 trans-... 

The combined action of lithium in liquid ammonia and carbon dioxide upon androst-4-en-3-one led to a synthesis of the /3-keto-ester (189), after esterification of the intermediate acid the reaction is one of reductive methoxycarbonyla-tion.82 Alkylation of the keto-ester (189) afforded a separable mixture of the 4/3-methyl steroid (190) as the major product (55%) and the corresponding 4a-methyl epimer. Reduction of the steroid (190) led to 4a-hydroxymethyl-4/3-methyl-5a-androstan-3/3-ol. Finally in this section, it has been noted that vinyl-magnesium bromide effects 1,4-addition to the a(3-unsaturated ketone 17/3-hydroxy-5a-androst-l-en-3-one to yield la-vinyl-5a-androstan-3-on-17/3-ol, which could be further reduced to the la-ethyl-3-ketone.83... 

Anhydrous diethyl ether, freshly obtained from a commercial supplier, is preferred for the reactions involving lithium hydro-aluminaie. The ether must be peroxide-free. Carbon dioxide must be rigorously excluded from these reaction systems. Explosions have been observed during evaporation of solutions of aluminum hydride and related compounds when carbon dioxide is present as an impurity.If it is necessary to concentrate ether solutions of lithium hydroaluminate by distillation, the following precautions must be observed. A large fluid volume must be maintained in the distillation flask such solutions should never be concentrated so far that very little ether remains in the reaction flask. Distillations must be effected in a protective atmosphere. Cyclic ethers, and especially tetrahydropyran solutions of lithium hydroaluminate, present a far greater explosion risk than diethyl ether solutions. 

The ruthenium-cobalt bimetallic complex system catalyzes the homologation of methanol with carbon dioxide and hydrogen in the presence of iodide salts. A synergistic effect is found between these two metals. The yield of ethanol is also affected by the Lewis acidity of the iodide salt, lithium iodide being most effective. The reaction profile shows that methanol is homologated with CO formed by the hydrogenation of CO2. 

The first half of the 20th century brought further attempts to use drugs and other therapies to treat mental illness. For example, tests were conducted on the effectiveness of giving amphetamines to depressed and narcoleptic patients, and carbon dioxide inhalation procedures were used in the treatment of illnesses referred to as psychoses and neuroses. Also used in the treatment of psychoses were antihistamines, insulin shock, and psychosurgery. Electroshock therapy was used to treat severe depression (a procedure still used today). Finally, in 1949 an Australian physician named John Cade discovered that the alkali metal lithuim successfully moderated manic conditions, although concerns about toxic reactions to it prevented its approval for use in the United States until 1970. Lithium remains a mainstay in the treatment of bipolar illnesses today. 

Anhydrous lithium hydroxide is white, granular, and free flowing. It readily absorbs both carbon dioxide and water from the atmosphere. Both the hydroxide and the monoxide have a marked irritating effect on the skin. The hydroxide has a density of 2.54 g./cc. 

One of the most effective A-substituents for C-2 lithiation of indoles and pyrroles is the t-butylcarbamoyl group, the lithiated derivatives of which react with a wide range of electrophiles such as trimethylsilyl chloride, A,7V-dimethylbenzamide, and carbon dioxide, to give the substituted products in 45-95% yield <9isi079>. Removal of the Af-group can be effected by treatment with lithium hydroxide in methanolic THF (Scheme 39). 1-Methoxyindole also can be lithiated selectively at C-2 and converted to substituted products hydrogenolysis removes the methoxy group <91H(32)22i>. Even 7V-phenylpyrrole can be selectively monolithiated at the pyrrole C-2 position. 

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