Lithium containing sodium

The course of the reaction is greatly influenced by the nature of the halide and the solvent used. Also, the ease with which it occurs depends appreciably on the sodium content of the lithium 37 direct synthesis of vinyllithium, for instance, is impossible unless the lithium contains sodium (Na content about 2%).38... 

Greases may contain soaps of lithium, calcium, sodium, aluminium, etc., or they may be non-soap greases. 

All the cations of Group I produce a characteristic colour in a flame (lithium, red sodium, yellow potassium, violet rubidium, dark red caesium, blue). The test may be applied quantitatively by atomising an aqueous solution containing Group I cations into a flame and determining the intensities of emission over the visible spectrum with a spectrophotometer Jlame photometry). 

Lithium containing 0.5-1% of sodium should be used the very pure metal reacts sluggishly and gives lower yields. 

Great Salt Lake, Utah, is the largest terminal lake in the United States. From its brine, salt, elemental magnesium, magnesium chloride, sodium sulfate, and potassium sulfate ate produced. Other well-known terminal lakes ate Qinghai Lake in China, Tu2 Golu in Turkey, the Caspian Sea and Atal skoje in the states of the former Soviet Union, and Urmia in Iran. There ate thousands of small terminal lakes spread across most countries of the world. Most of these lakes contain sodium chloride, but many contain ions of magnesium, calcium, potassium, boron, lithium, sulfates, carbonates, and nitrates. 

Calcium hypochlorite is the principal commercial soHd hypochlorite it is produced on a large scale and marketed as a 65—70% product containing sodium chloride and water as the main diluents. A product with a significantly higher available chlorine, av CI2, (75—80%) has been introduced by Olin. Calcium hypochlorite is also manufactured to a smaller extent as a hemibasic compound (- 60% av Cl ) and to a lesser extent in the form of bleaching powder (- 35% av CI2). Lithium hypochlorite is produced on a small scale and is sold as a 35% assay product for specialty appHcations. Small amounts of NaOCl ate employed in the manufacture of crystalline chlorinated ttisodium phosphate [56802-99-4]. 

Linder an atmosphere of argon, a solution of n-butyl bromide (137 g, 1 moll in anhydrous ether (500 ml) is added with stirring to small chips of lithium containing 1-2% of sodium (15.5 g, 2.2 g-atom) in ether (150 mL). The... 

A remarkable feature of the Birch reduction of estradiol 3-methyl ether derivatives, as well as of other metal-ammonia reductions, is the extreme rapidity of reaction. Sodium and -butyl alcohol, a metal-alcohol combination having a comparatively slow rate of reduction, effects the reduction of estradiol 3-methyl ether to the extent of 96% in 5 minutes at —33° lithium also effects complete reduction under the same conditions as is to be expected. Shorter reaction times were not studied. At —70°, reduction with sodium occurs to the extent of 56 % in 5 minutes, although reduction with lithium is virtually complete (96%) in the same time. (The slow rates of reduction of compounds of the 5-methoxytetralin type is exemplified by 5-methoxy-tetralin itself with sodium and f-butyl alcohol reduction occurs to the extent of only 50% in 6 hours vs. 99+% with lithium.) The iron catalyzed reaction of sodium with alcohols must be very fast since it competes so well with the rapid Birch reduction. One cannot compensate for the presence of iron in a Birch reduction mixture containing sodium by adding additional metal to extend the reaction time. The iron catalyzed sodium-alcohol reaction is sufficiently rapid that the aromatic steroid still remains largely unreduced. 

While keeping the collected deuterioammonia at dry ice-isopropyl alcohol temperature, lithium wire (10 mg) is added, followed by a solution of 3/3-hydroxy-5a-cholest-7-en-6-one (161 50 mg) in anhydrous tetrahydrofuran (4 ml). The reaction mixture is stirred for 20 min, the cooling bath is then removed and the ammonia is allowed to boil under reflux for 40 min. A saturated solution of ammonium chloride in tetrahydrofuran is added dropwise until the deep blue color disappears and then the ammonia is allowed to evaporate. The residue is extracted with ether and the organic layer washed with dilute hydrochloric acid and sodium bicarbonate solution and then with water. Drying and evaporation of the solvent gives a semicrystalline residue which is dissolved in acetone and oxidized with 8 N chromic acid solution. After the usual workup the residue is dissolved in methanol containing sodium hydroxide (0.2 g) and heated under reflux for 1 hr to remove any deuterium introduced at C-5 or C-7. (For workup, see section II-B). 

Compounds of the same stoichiometry type usually have the same type crystal structure within the row of alkali metals K - Rb - Cs rarely the same type structure with sodium-containing analogues and never ciystallize similarly with lithium-containing compounds. The crystal structure analysis of different fluoride and oxyfluoride compounds clearly indicates that the steric similarity between all cations and tantalum or niobium must be taken into account when calculating the X Me ratio. 

Table 55 presents the results discussed above. Fluoride melts containing tantalum contain two types of complex ions, namely TaF6 and TaF72 . The equilibrium between the complexes depends on the concentration of fluoride ions in the system, but mostly upon the nature of the outer-sphere cations. The complex ionic structure of the melts can be adjusted by adding cations with a certain polarization potential. For instance, the presence of low polarization potential cations, such as cesium, leads primarily to the formation of TaF72 complexes, while the addition of cations with relatively high polarization potentials, such as lithium or sodium, shifts the equilibrium towards the formation of TaF6 ions. 

Robertson et al.261 measured rates of bromination of some aromatic hydrocarbons in acetic acid containing sodium acetate (to eliminate protonation of the aromatic by liberated hydrogen bromide) and lithium bromide (to reduce the rate to a measurable velocity ) at 25 °C, the second-order rate coefficients for 3-nitro-N,N-dimethylaniline and anisole being 14.2 and 0.016 respectively the former compound was thus stated to be about 1012 times as reactive as benzene (though no measurement of the latter rate coefficient, inferred to be 1.33 xlO-11, could be found in the literature) and this large rate spread gives one further indication of the unreactive nature of the electrophile. Other rates relative to benzene were ... 

The agreement is also satisfactory for lithium and sodium sulfide. The oxide was used in calculating the lithium radius, 0.60 A., for in this compound it is safe to assume that the anions are not in mutual contact. It is further highly pleasing to note that even in zirconium and cerium oxide, containing quadrivalent cations, our theoretical radii are substantiated by the experimental inter-atomic distances for this makes it probable that even in these crystals the ions are not greatly deformed. 

The reductive removal of halogen can be accomplished with lithium or sodium. Tetrahydrofuran containing /-butanol is a useful reaction medium. Good results have also been achieved with polyhalogenated compounds by using sodium in ethanol. 

The synthetic importance of non-nucleophilic strong bases such as lithium diisopro-pylamide (LDA) is well known but its synthesis involves the use of a transient butyl lithium species. In order to shorten the preparation and make it economically valuable for larger scale experiments an alternate method of synthesis has been developed which also involves a reaction cascade (Scheme 3.14) [92]. The direct reaction of lithium with diisopropylamine does not occur, even with sonication. An electron transfer agent is necessary, and one of the best in this case is isoprene. Styrene is used in the commercial preparation of LDA, but it is inconvenient in that it is transformed to ethylbenzene which is not easily removed. It can also lead to undesired reactions in the presence of some substrates. The advantages of isoprene are essentially that it is a lighter compound (R.M.M. = 68 instead of 104 for styrene) and it is transformed to the less reactive 2-methylbutene, an easily eliminated volatile compound. In the absence of ultrasound, attempts to use this electron carrier proved to be unsatisfactory. In this preparation lithium containing 2 % sodium is necessary, as pure lithium reacts much more slowly. 

A detailed study of the conversion of 3,4-dichloro-l,2,5-thiadiazole into 3,4-diamino-l,2,5-thia-diazole has been carried out <76JHC13>. Reaction with lithium or sodium amide produces only 4% of the diamine together with cyano-containing by-products, a consequence of direct attack on sulfur. Use of a less powerful nucleophile, ammonia or potassium phthalimide, resulted in an increased attack on carbon and produced the diamine in 24% and 66% yields, respectively. Secondary amines, e.g. morpholine <76JOC3l2l> and dimethylamine <72JMC315>, produce the normal displacement products. The reaction of dichlorothiadiazole with potassium fluoride in sulfolane gives a mixture of 3-chloro-4-fluoro and 3,4-difluoro-l,2,5-thiadiazole <82CB2135>. 

The solubility of sodium chloride in aq. acetone at 20° falls to 27"18 with 10 c.c. of acetone per 100 c.c. of solvent to 0 25 with 90 c.c. of acetone per 100 c.c. of solvent at 0°, 100 grms. of acetone dissolve 4"6 grms. of lithium chloride, and at 58°, 214 grms., so that the solubility is diminished by a rise of temp. The solubility of potassium in aq. soln. of acetone increases from almost zero with 100 per cent, acetone at 20° to 8"46 with 50 per cent, acetone and to 21 "38 with 20 per cent, acetone. At 30°, 100 grms. of a soln. with 696 per cent, acetone carries 23 42 per cent, potassium chloride and the remainder is water 8"06 per cent, of this salt is present in a soln. with 45 98 per cent, acetone and 0-13 per cent, of this salt in a soln. with 89"88 per cent, of acetone. At 40°, a soln. with 15"75 per cent, acetone carries 21 "28 per cent, of potassium chloride and with 79"34 per cent, of acetone there is 0"58 per cent, of potassium chloride. At 40°, therefore, for cone, of acetone between 20 and 80 per cent., the sat. soln. separates into two layers the upper layer has 55 2 per cent, water, 31 "82 acetone, and 12"99 KC1, when the lower layer has 28"14 per cent, water, 69 42 acetone, and 2"44 KC1. Similarly, when the upper layer has water, acetone, and potassium chloride in the respective ratio 46 49, 45"34, and 8 17 the lower layer has 38 68, 56"17, and 5 25. The separation into two layers with sat. soln. of potassium chloride containing 26 per cent, acetone, occurs at 46"5° and the temp, of separation with other proportions of acetone is indicated in Fig. 22. C. E. Linebarger (1892) and J. E. Snell (1898) 34 found the phenomenon also occurs with the chlorides of lithium, ammonium, sodium, rubidium, calcium, strontium, cobalt, and many other radicles also with bromides, sulphates, cyanides, and numerous other salts with aq. acetone,... 

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