Water reaction with lithium

The in situ generation of the carbon dioxide adduct of an indole provides sufficient protection and activation of an indole for metalation at C-2 with r-butyl-lithium. The lithium reagent can be quenched with an electrophile, and quenching of the reaction with water releases the carbon dioxide. ... 

Passivating films may change their chemical composition after their formation due to reactions with water or carbon dioxide lithium alkylcarbonates react with traces of water to yield lithium carbonate (see Table 8). 

Practically all metals can be passivated. Even lithium, which is a highly active alkali metal, can be passivated in concentrated LiOH solution this is the reason for its greatly reduced rate of reaction with water. 

Lithium has a moderate reaction with water when cold, but extremely violent when hot. The violent release of hydrogen along with a high temperature rise of the lithium particles sometimes provokes the gas to combust. With powdered lithium, an explosion will occur. 

The finely divided hydride produced by pyrolysis is pyrophoric in air, while synthesis from the elements produces a substantially air-stable product [1]. That prepared by reduction of butylmagnesium bromide with lithium tetrahydroalumi-nate is pyrophoric and reacts violently with water and other protic compounds [2], The hydride produced from magnesium anthracene has a very large specific surface area and is pyrophoric [3], In the context of use of the hydride for energy storage purposes, ignition and combustion behaviour of 100-400 g portions were studied, as well as the reaction with water [4],... 

For over 15 years we have conducted research utilizing metal atoms in low temperature spectroscopic and synthetic studies at Rice University.8 Our synthetic work was started in the late 1960s with the work of Krishnan, on lithium atom reactions with carbon monoxide, extended by Meier- in his studies of lithium atom reactions with water and ammonia and expanded over the next several years to include metal atom interactions with HF, H2O, H3N, H4C, and their hundreds of organic analogs—RF, R2O, ROH, R3N,. . . H3N, R4C, R3CH, etc. A most exciting aspect of... 

Any reaction in solution may be considered to result from both EPD-EPA and ED-EA interactions. The sequence of functions follows the functional principle a chemical interaction is initiated when the reacting entity exhibits one of the four functions, while the other reactant exhibits the reverse correlated function. The reaction is completed when the resulting electronic changes are compensated for by the reverse non-correlated functions. This may be illustrated by the reaction of lithium metal with water 3, 5). 

Assume that you wanted to prepare a small volume of pure hydrogen by reaction of lithium metal with water. How many grams of lithium would you need to prepare 455 mL of H2 if the density of hydrogen is 0.0893 g/L ... 

Note. (1) Reaction of lithium borohydride with water may be rapid and violent do not expose to high humidity and avoid contact with eyes, skin and clothing (contact with cellulosic material may cause combustion). It should be handled with the same caution as is afforded to lithium aluminium hydride (Section 4.2.49, p. 445). 

Unless otherwise known, the toxicides of lithium organometallic compounds should be regarded as those of lithium compounds and of organometallic compounds in general. The latter were discussed in Section 12.4. Lithium oxide and hydroxide are caustic bases, and they may be formed by the combustion of lithium organometallic compounds or by their reaction with water. 

Besides its use as a mechanistic probe, deuteriation of anions under kinetically controlled conditions is a potentially promising way to access deuteriated molecules in a regio- and stereo- controlled manner, in opposition to the thermodynamic equilibration in the presence of an excess of deuterium donor. Thus, treatment of the lithium anion of 2-methyltetralone (p E = 7.31, pfsfEa = 10.8, pKkr = 18.1 in water)335, by one equivalent of a solution of deuterium chloride in deuterium oxide, generates the intermediate O-deuteriated enol whose reaction with water or with an excess of deuterium chloride in deuterium oxide conducts to, respectively, the tetralone or the deuteriated tetralone (Scheme 69)336. 

Caution The following reactions can proceed explosively Calculate the number of moles of hydrogen that can be produced by reaction with water of (a) 0.600 g of lithium and (b) 0.600 g of barium, (c) Explain the difference. 

SAFETY PROFILE Poison by ingestion and skin contact. Moderately toxic by inhalation and intraperitoneal routes. A corrosive irritant to skin, eyes, and mucous membranes. Questionable carcinogen with experimental neoplastigenic data. Mutation data reported. A flammable liquid and very dangerous fire hazard when exposed to heat or flame. Violent reaction with water or hexafluoroisopropylideneamino lithium. A... 

Secondary aromatic phosphines can be prepared from tertiary phosphines by cleavage with sodium in liquid ammonia, and the detailed preparation of diphenylphosphine by this method has been reported. Diphenylphosphine has also been prepared by the reaction of chlorodiphenylphosphine with alkali metals or with lithium tetrahydroaluminate. This phosphine has been also obtained from diphenyltrichlorophosphorane or tetraphenyldiphosphine-disulfide with lithium aluminum hydride. A faster and easier method of preparation, which gives equally high yields, consists in the cleavage of tri-phenylphosphine with lithium metal in tetrahydrofuran, followed by hydrolysis of lithium diphenylphosphide with water to generate the phosphine. ... 

Summary l-[2,6-bis(dimethylaminomethyl)phenyl]silenes (2a-d) were prepared by treatment of the (dichloromethyl)oligosilanes R (Me3Si)2Si-CHCl2 la-d (a R = Me b R=tert-Bu c R=Ph d R = Me3Si) with 2,6-bis(dimethylaminomethyl)phenyl-lithium and were characterized by NMR studies and (in part) by X-ray stmctural analyses as well as by their reactions with water to give silanols. Treatment of 2a-d with benzaldehyde produced 2,2-bis(trimethylsilyl)styrene (4) and a silanone polymer as the expected products. For the reaction of 2a and 2c with benzaldehyde, an interesting side reaction was observed leading to the 2-oxa-l-sila-l,2,3,4-tetrahydro-naphthalenes 6a and 6c, respectively. 

The high reactivities of the alkali metals are illustrated by their vigorous reactions with water. Lithium reacts readily sodium reacts so vigorously that the hydrogen gas it forms may ignite and potassium, rubidium, and cesium cause the H2 to burst into flames when... 

Reactions with Water-Sensitive Reagents such as Grignard Reagents, Lithium Alkyls, or Zinc Oiganyls [375] on Solid Phases... 

Regarding the well-known disappearance of lithium or sodium in reaction with water, it must be demonstrated that the gas hydrogen is formed and new white substances - hydroxides of the metals, appear after the water has been evaporated from the alkaline solutions (see E3.7). So the metals are reacting... 

In 1947 Wittig and Wetterling 162> examined the reaction between tetra-methylammonium bromide and phenyllithium in ether in an effort to prepare tetramethylammonium phenyl. None of the desired product was obtained, but benzene was formed along with an insoluble material which was characterized as the lithium bromide complex of the ylid on the basis of its reactions with water, iodine, methyl iodide, and benzophenone. 

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