Lithium methyl carbonate

In an effort to gain fundamental understanding on those key ingredients in the SEI, Xu et al. from the US Army Research Laboratory (ARL) synthesized a series of model lithium alkyl carbonate compounds to simulate the proposed chemical species on the anode surface, including lithium methyl carbonate (LMC), lithium ethyl carbonate (LEC), LEDC, and LPDC, as summarized in Scheme 5.6 [38]. 

Zhuang G. V, Yang H., Ross P. N., Xu K., low T. R. Lithium Methyl Carbonate as a Reaction Product of Metallic Lithium and Dimethyl Carbonate, Electrochem. Solid State Lett. 2006,9, A64-A68. 

Fig. 7.22 Conductivity of lithium dilithium ethylene dicarbonate (Li2EDC) > lithium methyl carbonate (LiMC) from MD simulations [91] compared to conductivity of EC/LiTESI from MD simulations [36]...

Reactions of the Hydroxyl Group. The hydroxyl proton of hydroxybenzaldehydes is acidic and reacts with alkahes to form salts. The lithium, sodium, potassium, and copper salts of sahcylaldehyde exist as chelates. The cobalt salt is the most simple oxygen-carrying synthetic chelate compound (33). The stabiUty constants of numerous sahcylaldehyde—metal ion coordination compounds have been measured (34). Both sahcylaldehyde and 4-hydroxybenzaldehyde are readily converted to the corresponding anisaldehyde by reaction with a methyl hahde, methyl sulfate (35—37), or methyl carbonate (38). The reaction shown produces -anisaldehyde [123-11-5] in 93.3% yield. Other ethers can also be made by the use of the appropriate reagent. 

A typical lithium-ion cell consists of a positive electrode composed of a thin layer of powdered metal oxide (e.g., LiCo02) mounted on aluminum foil and a negative electrode formed from a thin layer of powdered graphite, or certain other carbons, mounted on a copper foil. The two electrodes are separated by a porous plastic film soaked typically in LiPFe dissolved in a mixture of organic solvents such as ethylene carbonate (EC), ethyl methyl carbonate (EMC), or diethyl carbonate (DEC). In the charge/ discharge process, lithium ions are inserted or extracted from the interstitial space between atomic layers within the active materials. 

The reaction of lithium phenoxide with cirmamyl methyl carbonate at 50 °C gave excellent selectivities, if the reaction time was less than about 20 h. However, longer reaction times led to a fall in both regioselectivity and enantioselectivity, which indicated that the reaction is reversible. 

Distance of a methyl carbon atom of the trimethylsilyl group (Cy) to the next lithium atom of the hexamer. 

Comparison of the configuration of the stannane with the prodncts of reaction reveals that primary alkyl halides that are not benzyhc or a to a carbonyl react with inversion at the lithium-bearing carbon atom. In the piperidine series, the best data are for the 3-phenylpropyl compound, which was shown to be >99 1 er. In the pyrrolidine series, the er of the analogous compound indicates 21-22% retention and 78-79% inversion of configuration. Activated alkyl halides such as benzyl bromide and teri-butyl bromoacetate afford racemic adducts. In both the pyrrolidine and piperidine series, most carbonyl electrophiles (i.e. carbon dioxide, dimethyl carbonate, methyl chloroformate, pivaloyl chloride, cyclohexanone, acetone and benzaldehyde) react with virtually complete retention of configuration at the lithium-bearing carbon atom. The only exceptions are benzophenone, which affords racemic adduct, and pivaloyl chloride, which shows some inversion. The inversion observed with pivaloyl chloride may be due to partial racemization of the ketone product during work-up. 

Ketones of the form RCOCH3 and RCOCH2R can be carboxylated indirectly by treatment with magnesium methyl carbonate 52.613 Because formation of the chelate 53 provides the driving force of the reaction, carboxylation cannot be achieved at a disubstituted a position. The reaction has also been performed on CH3N02 and compounds of the form RCH2N02614 and on certain lactones.61s Direct carboxylation has been reported in a number of instances. Ketones have been carboxylated in the a position to give (3-keto acids.616 The base here was lithium 4-methyl-2,6-di-f-butylphenoxide. 

The reactivity profiles of the boronate complexes are also diverse.43 For example, the lithium methyl-trialkylboronates (75) are inert, but the more reactive copper(I) methyltrialkylboronates (76) afford conjugate adducts with acrylonitrile and ethyl acrylate (Scheme 16).44 In contrast, the lithium alkynylboronates (77) are alkylated by powerful acceptors, such as alkylideneacetoacetates, alkylidene-malonates and a-nitroethylene, to afford the intermediate vinylboranes (78) to (80), which on oxidation (peracids) or protonolysis yield the corresponding ketones or alkenes, respectively (Scheme 17).45a Similarly, titanium tetrachloride-catalyzed alkynylboronate (77) additions to methyl vinyl ketone afford 1,5-diketones (81).4Sb Mechanistically, the alkynylboronate additions proceed by initial 3-attack of the electrophile and simultaneous alkyl migration from boron to the a-carbon. 

A number of conflicting reports exist on the stereochemical course of halogenolysis of carbon-lithium and carbon-tin bonds when the carbon atom undergoing substitution is part of an alicyclic ring. Halogenolysis of optically active 1-methyl-... 

Magnesium methyl carbonate, 310 Malic acid, 135 Malyngolide, 224, 316 Manganese(II) chloride-lithium aluminum hydride, 310 Manganese dioxide, 311 Manicone, 121... 

The intercalation process on the anode side takes place in stages as more and more lithium enters the crystal lattice. A typical electrolyte in lithium-ion cells contains ethylene carbonate and a mixture of aliphatic carbonates such as methyl carbonate, and ethyl methyl carbonate, along with 1M LiPF6 salt. The propylene carbonate containing electrolyte, used in primary lithium cells, could... 

Wilkes launched the field of air- and moisture-stable ionic liquids by introducing five new materials, each containing the Tethyl-3-methylimidazolium cation [EMIMJ+ with one of five anions nitrate [NC>3], nitrite [NO2]-, sulfate [SC>4]2, methyl carbonate [CH3CO2]- and tetrafluoroborate [BF [47]. Only the last two materials had melting points lower than room temperature, and the reactive nature of the methyl carbonate would make it unsuitable for many applications. This led to the early adoption of [EMIM][BF4] as a favored ionic liquid, which has since been the subject of over 350 scientific publications. One of the first appeared in 1997 [50], reporting the investigation of [EMIM][BF4] as the electrolyte system for a number of processes, including the electrodeposition of lithium (intended for use in lithium ion batteries). 

In case of the direct reaction of the natural oil or lower alkyl ester of natural fatty acid and the amine the reaction method for producing the amide derivatives is as follows That is, about 1 mol of the said oils and 1 to 100 equivalent mols of the said amines are mixed in the absence or presence of solvents such alcohols as methanol, ethanol or the like, such aromatic hydrocarbons as benzene, toluene, xylene or the like, such halogenoalkanes as methylene chloride, chloroform, carbon tetrachloride or the like, and such alkenes or alkanes as petroleum ether, benzene, gasoline, ligroin or cyclohexane, such ethers as tetrahyrofuran, dioxane and the like, or a mixture thereof, and the mixture is subjected to the reaction in the absence or presence of catalyst amount or equimolar amount to the amine of an auxiliary agent of condensation, such as alkoholate of alkali metal, i.e. lithium, methylate, lithium ethylate, sodium methylate, sodium ethylate, potassium-t-butylate and the like, or acidic auxiliary agents, i.e. p-toluenesulfonic acid and the like, thereby to yield the amide derivatives. In this reaction, a formal alcohol may be removed from the reaction system. 

Esters 106 (R = Me, Et or Pr = Et, Pr, r-Bu or PhCHi) of aliphatic carboxylic acids react with lithium acetylides 107 (R = H, C5 Hi i or Ph) in the presence of boron trifluoride etherate in THE to give acetylenic ketones 108 (equation 18). Palladium-[tetrakis(triphenylphosphine)]-copper(I) iodide catalyses the oxidative addition-decarboxylation of propargyl methyl carbonates, e.g. 109, with terminal alkynes to yield 1,2-dien-4-ynes (allenylacetylenes) 110. The regiochemistry of the palladium-catalyzed addition of phenylacetylene to the allenic ester 111 depends on the nature of the catalyst used palladium(III) acetate-triphenylphosphine yields a 81 19 mixture of adducts 112 and 113, while in the presence of tetrakis(carbomethoxy)palladacyclopentadiene-tris(2,4,6-trimethoxyphenyl)phosphine the ratio is reversed to 9 91 k... 

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