Lithium chloride effect

Breslow supported this suggestion by demonstrating that the cycloaddition can be further accelerated by adding anti cliaotropic salts such as lithium chloride, whereas chaotropic salts such as guanidium chloride led to a retardation " "" ". On the basis of these experiments Breslow excluded all other possible explanations for the special effect of water on the Diels-Alder reaction " . 

Dog repeUents available commercially in the 1990s have been generally unsuccessful in laboratory tests. Por example, lithium chloride treatments were usually rejected immediately with no ingestion, and bone oil treatments that contained up to 0.1% of the active ingredient were stiH consumed (93). Oleoresin capsicum [8023-77-6], the essence of red pepper, did have an extended effect on coyotes, even though the deer repeUents mentioned above were attractive to coyotes (93). Although a capsicum-base aerosol repeUent has been described as potentially harmful (94), pepper spray is commercially available in the United States to repel humans, as is Mace. 

Lithium Chloride. Of the metal haUdes, calcium bromide [7789-41-5] CaBr2, ziac chloride [7646-85-7] ZnCl2, CaCl2, and lithium chloride [7447-41-8] LiCl, (Class 1, nonregenerative) are the most effective for water removal (4). AH are available ia the form of dehquescent crystals. The hydrates of LiCl are LiCl-nH2 O, where n = 1, 2, or 3. Lithium chloride solutions are more stable ia air and less corrosive than the other metal haUdes. The high solubihty of lithium carbonate [554-13-2] Li2C02, usually eliminates scale formation problems (see LiTHlUM COMPOUNDS). 

One-electron oxidation of carboxylate ions generates acyloxy radicals, which undergo decarboxylation. Such electron-transfer reactions can be effected by strong one-electron oxidants, such as Mn(HI), Ag(II), Ce(IV), and Pb(IV) These metal ions are also capable of oxidizing the radical intermediate, so the products are those expected from carbocations. The oxidative decarboxylation by Pb(IV) in the presence of halide salts leads to alkyl halides. For example, oxidation of pentanoic acid with lead tetraacetate in the presence of lithium chloride gives 1-chlorobutane in 71% yield ... 

The bromination of 4,5-j -dihydrocortisone acetate in buffered acetic acid does not proceed very cleanly (<70%) and, in an attempt to improve this step in the cortisone synthesis, Holysz ° investigated the use of dimethylformamide (DMF) as a solvent for bromination. Improved yields were obtained (although in retrospect the homogeneity and structural assignments of some products seem questionable.) It was also observed that the combination of certain metal halides, particularly lithium chloride and bromide in hot DMF was specially effective in dehydrobromination of 4-bromodihydrocortisone acetate. Other amide solvents such as dimethylacetamide (DMA) and A-formylpiperidine can be used in place of DMF. It became apparent later that this method of dehydrobromination is also prone to produce isomeric unsaturated ketones. When applied to 2,4-dibromo-3-ketones, a substantial amount of the A -isomer is formed. 

The Diels-Alder reaction of nonyl acrylate with cyclopentadiene was used to investigate the effect of homochiral surfactant 114 (Figure 4.5) on the enantioselectivity of the reaction [77]. Performing the reaction at room temperature in aqueous medium at pH 3 and in the presence of lithium chloride, a 2.2 1 mixture of endo/exo adducts was obtained with 75% yield. Only 15% of ee was observed, which compares well with the results quoted for Diels-Alder reactions in cyclodextrins [65d]. Only the endo addition was enantioselective and the R enantiomer was prevalent. This is the first reported aqueous chiral micellar catalysis of a Diels-Alder reaction. 

Rideout and Breslow first reported [2a] the kinetic data for the accelerating effect of water, for the Diels Alder reactions of cyclopentadiene with methyl vinyl ketone and acrylonitrile and the cycloaddition of anthracene-9-carbinol with N-ethylmaleimide, giving impetus to research in this area (Table 6.1). The reaction in water is 28 to 740 times faster than in the apolar hydrocarbon isooctane. By adding lithium chloride (salting-out agent) the reaction rate increases 2.5 times further, while the presence of guanidinium chloride decreases it. The authors suggested that this exceptional effect of water is the result of a combination of two factors the polarity of the medium and the... 

Figure 8. Isotherms of l and Mc in (Li, Cs)Cl at 973 K. (Reprinted from I. Okada and H. Horinouchi, The Chemla Effect in the Mobilities in the Molten Binary System of Lithium Chloride and Caesum Chloride, J. Electroanal. Chem 396 547, Fig. 4, Copyright 1995 with permission of Elsevier Science.)...

An alternative procedure for effecting the condensation of phosphonoacetates is to carry out the reaction in the presence of lithium chloride and an amine such as diiso-propylethylamine. The lithium chelate of the substituted phosphonate is sufficiently acidic to be deprotonated by the amine.262... 

Decarboxylation of 16 using the previously described NMP, lithium chloride method provided the dione 32. Selective reduction of the least hindered carbonyl was readily effected using sodium borohydride providing 33. Hydroxymethylenation followed by O-alkylation of the butenolide unit by standard procedures provided the A-B-D-ring analog 34a,b (racemic mixture of epimers). 

As the battery produces electricity, lithium chloride is formed on the cathode, and eventually the battery is no longer effective. Lithium batteries have long life and give high current-to-weight ratio, so they are widely used in digital cameras, watches, pacemakers, and so forth. 

Taylor and Zeitlin [43] described an X-ray fluorescence procedure for the determination of total sulfur in seawater. They studied the matrix effects of sodium chloride, sodium tetraborate, and lithium chloride and show that the X-ray fluorescence of sulfur in seawater experiences an enhancement by chloride and a suppression by sodium that fortuitously almost cancel out. The use of soft scattered radiation as an internal standard is ineffective in compensating for matrix effects but does diminish the effects of instrument variations and sample inhomogeneity. 

See also Lithium compounds Lithium chlorate, 6 117 Lithium chloride, 15 131, 139 corrosive effect on iron, 7 806 dessicant, 8 360 solvent for cotton, 8 21 Lithium chromate, 15 142... 

The most recent addition to Shine s extensive study of the benzidine-type rearrangements41 involved remeasuring the nitrogen and the carbon-13 and carbon-14 kinetic isotope effects at the 4- and at the 4- and 4 -carbons as well as determining the carbon-13 and carbon-14 isotope effects at the 1- and at the 1- and l -carbons in the benzidine rearrangement of hydrazobenzene (equation 30). The reaction, which was carried out in 75% aqueous ethanol that was 0.1 M in hydrochloric acid and 0.3 M in lithium chloride at 0°C, gave an 86% yield of benzidine (11) and a 14% yield of diphenyline (12). The kinetic isotope effects found for the formation of benzidine and diphenyline under these reaction conditions are presented in Table 5. 

TABLE 5. The nitrogen, carbon-13 and carbon-14 kinetic isotope effects found for the acid-catalyzed benzidine rearrangement of hydrazobenzene in 75% aqueous ethanol that was 0.1 M in hydrochloric acid and 0.3 M in lithium chloride at 0°C... 

When the reaction with substituted benzaldehydes is conducted in the presence of ammonia, the a-amino carboxylic acids are formed [11], The corresponding reaction involving bromoform is less effective and, for optimum yields, the addition of lithium chloride, which enhances the activity of the carbonyl group, is required. In its absence, the overall yields are halved. The reaction of dichlorocarbene with ketones or aryl aldehydes in the presence of secondary amines produces a-aminoacetamides [12, 13] (see Section 7.6). 

Al-Sahhaf, T. and Kapetanovic, E. Salt effects of lithium chloride, sodium bromide, or potassium iodide on liquid-liquid equilibrium in the system water + 1-butanol, J. Chem. Eng. Data, 42(l) 74-77, 1997. 

Kollig, H.P., Ellington, J.J., Weber, E.J., and Wolfe, N.L. Environmental research brief - Pathway analysis of chemical hydrolysis for 14 RCRA chemicals. Office of Research and Development. U.S. EPA Report 600/M-89/009, 1990, 6 p. Kolthoff, I.M. and Chantooni, M.K., Jr. Crown ether complexed alkali metal picrate ion pairs in water-saturated dichloro-methane as studied by electrolytic conductance and by partitioning into water. Effect of lithium chloride on partitioning, J. Chem. Eng. Data, 42(l) 49-53, 1997. 

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