Lithium acetonitrile

Lithium perchlorate [7791-03-9] M 106.4, pK -2.4 to -3.1 (for HCIO4). Crystd from water or 50% aq MeOH. Rendered anhydrous by heating the trihydrate at 170-180° in an air oven. It can then be recrystd twice from acetonitrile and again dried under vacuum [Mohammad and Kosower J Am Chem Soc 93 2713 19711... 

Mobile phase Acetone — acetonitril — 0.1 mol/1 aqueous lithium chloride... 

The use of azide reagents is also important for the synthesis of cyclic sulfur(VI)-nitrogen systems. The reaction of SOCI2 with sodium azide in acetonitrile at -35°C provides a convenient preparation of the trimeric sulfanuric chloride [NS(0)C1]3 (Eq. 2.16). " Thionyl azide, SO(N3)2 is generated by the heterogeneous reaction of thionyl chloride vapour with silver azide (Eq. 2.17). This thermally unstable gas was characterized in situ by photoelectron spectroscopy. The phenyl derivative of the six-membered ring [NS(0)Ph]3 can be prepared from lithium azide and PhS(0)Cl. ... 

Whilst some organic compounds can be investigated in aqueous solution, it is frequently necessary to add an organic solvent to improve the solubility suitable water-miscible solvents include ethanol, methanol, ethane-1,2-diol, dioxan, acetonitrile and acetic (ethanoic) acid. In some cases a purely organic solvent must be used and anhydrous materials such as acetic acid, formamide and diethylamine have been employed suitable supporting electrolytes in these solvents include lithium perchlorate and tetra-alkylammonium salts R4NX (R = ethyl or butyl X = iodide or perchlorate). 

Eq. (3), with lithium diisopropylamide (LDA) to a lithiospecies and in its subsequent reaction with C02 affording via the corresponding 4-carboxylic acid its ethyl ester 59. In the alternative version perchlorate 48e is electro-chemically reduced in acetonitrile to an anionic species that was converted either to a 3 1 mixture of isomers 56 (R = f-Bu) and 60 or to 4//-thiopyran 56 (R = PhCH2) with f-BuI or PhCH2Br, respectively (90ACS524). The kinetics of the benzylation procedure was followed by cyclic voltammetry [88ACS(B)269]. 

However, even if electrolytes have sufficiently large voltage windows, their components may not be stable (at least ki-netically) with lithium metal for example, acetonitrile shows very large voltage windows with various salts, but is polymerized at deposited lithium if this reaction is not suppressed by additives, such as S02 which forms a protective ionically conductive layer on the lithium surface. Nonetheless, electrochemical stability ranges from CV experiments may be used to choose useful electrolytes. 

Similar stereochemical results were obtained from the addition of the potassium and lithium ions of ethyl acetate, /V,V-dimethylacetamide, acetonitrile, acetophenone and pinacolone to 3-(/erf-butyldimethylsilyloxy)-T-phenylsulfonyl-1-cyclohexene followed by protonation or methylation of the resulting sulfonyl carbanion intermediates7. 

Potassium or lithium derivatives of ethyl acetate, dimethyl acetamide, acetonitrile, acetophenone, pinacolone and (trimethylsilyl)acetylene are known to undergo conjugate addition to 3-(t-butyldimethylsiloxy)-1 -cyclohexenyl t-butyl sulfone 328. The resulting a-sulfonyl carbanions 329 can be trapped stereospecifically by electrophiles such as water and methyl iodide417. When the nucleophile was an sp3-hybridized primary anion (Nu = CH2Y), the resulting product was mainly 330, while in the reaction with (trimethylsilyl)acetylide anion the main product was 331. 

C. 3-Methyl-2,i-heptanedione. A dry, 500-ml., three-necked, round-bottomed flask equipped with a magnetic stirring bar, a pressureequalizing dropping funnel, a thermometer, and a condenser fitted with a nitrogen-irdet tube is charged with 17.8 g. (0.20 mole) of anhydrous lithium bromide (Note 21). Under- a nitrogen atmosphere, 34.8 g. (0.20 mole) Of -(2-oxobut-3-yl) butanethioate dissolved in 120 ml. of anhydrous acetonitrile (Note 22) is added to the flask. 

The absence of water in the lithium bromide is of great importance. Traces of wrater lower the yield of product by 10-20%. LiBr-2 H20 (purchased from E. Merck Company, Inc., Darmstadt or City Chemical Corporation) was dissolved three times in anhydrous acetonitrile-benzene (1 1), and the solvents removed each time on a rotary evaporator. The lithium bromide was dried under high vacuum at 100° for 1 hour, ground to a fine powder with a mortar and pestle while still warm, and again dried at 100°, as above, for 3 hours. 

In Acetonitril, Pyridin, Dimethylformamid und Bis-[2-methoxy-athyl]-ather reagieren bei 0° Aceton und verwandte aliphatische und aromatische Ketone nur in Gegenwart von Wasser, Alkoholen oder Lithium-Salzen3 5. 

Die kathodische Reduktion von N,N-Dichlor-tosylamid fiihrt zum entsprechenden Ni-tren, in Gegenwart von 1,4-Dioxan entsteht neben Tosylamid (Graphit-Kathode, max. 90% d.Th.) bis zu 32% d.Th. (Platin) 2-Tosylamino-J,4-dioxan (in Acetonitril/Lithium-perchlorat)3. 

Treatment of bis(pyridine) complexes of molybdenum and tungsten, M(f/ -allyl)Cl(CO)2(py)2 (M = Mo, W) with equimolar amounts of lithium amidinates Li[RC(NPh)2] (R = H, Me) afforded amidinato complexes of the type M(r -allyl)[RC(NPh)2](CO)2(py) (M = Mo, W). Reactions of the latter with acetonitrile, PEts, and P(OMe)3 have been investigated Free amidines react with M(r -allyl)Cl(CO)2(NCMe)2 according to Scheme 124 to give the corresponding bis(amidine) complexes. ... 

A point meriting attention is the voltage difference above. Doped polymers are rather electropositive (up to more than 4 V vs. a lithium electrode in the same solution), so much so that charging may have to be limited in order not to exceed the stability limits of the electrolyte (typically, propylene carbonate or acetonitrile as aprotic nonaqueous solvents). 

Lithium perchlorate and lithium triflate in acetonitrile catalyze intramolecular cycloaddition reactions of nitrones of allyloxybenzaldehydes and unsaturated aldehydes.154... 

Ebner, W. B. etal., Proc. 8th Power Sources Symp., 119-124, 1982 An ARC study of the thermal and pressure behaviour of actual electric batteries under various atypical conditions showed the major contributions to the exothermic behaviour as the reactions between lithium and acetonitrile, lithium and sulfur and the decomposition of lithium dithionite. The first reaction can generate enough heat to trigger other exothermic rections. The hazards associated with the various parameters are quantified. 

Another variation of this method involves the treatment of an acetonitrile solution of the aryl aldehyde, trimethylsilyl chloride, and either sodium iodide, if iodide products are desired, or lithium bromide, if bromide products are desired, with TMDO. After an appropriate reaction time (5-195 minutes) at a temperature in the range of —70° to 80°, the upper siloxane layer is removed and the benzyl iodide or bromide product is isolated from the remaining lower portion after precipitation of the inorganic salts by addition of dichloromethane. For example, p-anisaldehyde reacts to form /i-rnethoxybenzyl bromide in 84% isolated yield under these conditions (Eq. 200).314,356... 

From experiments as well as from the Gutmann donor number for acetonitrile (only 50% of that for water), it is well known that addition of water to solutions of lithium ions in acetonitrile leads to the formation of a water coordinated Li+ ion. This can be reproduced for HCN as modeled by quantum chemical calculations (RB3LYP/6-311+G ). 

Indium Iodine Acetonitrile, nitrogen dioxide, mercury(II) bromide, sulfur Acetaldehyde, acetylene, aluminum, ammonia (aqueous or anhydrous), antimony, bromine pentafluoride, carbides, cesium oxide, chlorine, ethanol, fluorine, formamide, lithium, magnesium, phosphorus, pyridine, silver azide, sulfur trioxide... 

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