Lithium perchlorate products

A remarkable effect of the addition of lithium perchlorate is found in the acetylation of 2-MN 4 with AAN in the presence of anfimony(lll) triflate (5% mol). Indeed, when acetylation is performed in nifromefhane at room temperature, or in acetonitrile or methylene chloride at 50°C without lithium perchlorate, product 20 is obtained preferentially (Table 3.7). On the other hand, a dramatic change of regioselectivity is observed when the same reaction is performed in nitromethane/lithium perchlorafe, and compound 21 is obtained in 93% yield. The 1-acetylated kinetic adduct 20 is formed in the initial stage of the reaction, and the migration from 20 to the thermodynamic 6-acetylated adduct 21 occurs during the reaction (as described in detail in Chapter 4). 

The U.S. domestic capacity of ammonium perchlorate is roughly estimated at 31,250 t/yr. The actual production varies, based on the requirements for soHd propellants. The 1994 production ran at about 11,200 t/yr, 36% of name plate capacity. Environmental effects of the decomposition products, which result from using soHd rocket motors based on ammonium perchlorate-containing propellants, are expected to keep increasing pubHc pressure until consumption is reduced and alternatives are developed. The 1995 price of ammonium perchlorate is in the range of 1.05/kg. Approximately 450 t/yr of NH ClO -equivalent cell Hquor is sold to produce magnesium and lithium perchlorate for use in the production of batteries (113). Total U.S. domestic sales and exports for sodium perchlorate are about 900 t/yr. In 1995, a solution containing 64% NaClO was priced at ca 1.00/kg dry product was also available at 1.21/kg. 

S-Substituted thiiranium ions react with secondary amines to give ring-opened products. Nitriles also react with thiiranium ions, probably via an open carbenium ion whose formation is favored by increasing the polarity of the medium by the addition of lithium perchlorate (Scheme 79) (79ACR282). An intramolecular displacement by an amide nitrogen atom on an intermediate thiiranium ion has been invoked (80JA1954). 

When the lithium perchlorate was dissolved initially in the entire 240 ml. of 1,2-dimethoxye thane and processed as above, the yield was considerably lower. The submitters report that, if less lithium perchlorate is used in the preparation of the octamethyltetraoxaquaterene, the 3neld of the product is lowered. 

The method described here gives higher yields of the macrocyclic tetraethers and allows the product from furan and cyclohexanone to be formed directly in 5-10% yield, whereas this product was previously obtained only by an indirect route. The added lithium perchlorate undoubtedly accelerates the reaction, since after short reaction times the product was isolated in 20% yield when the salt was present and in only 5% yield when the salt was absent. The lithium cation is presumably acting as a template which coordinates with the oxygen atoms of... 

Lithium hexafluoroarsenate is thermally stable [54, 55] but shows environmental risks due to possible degradation products [56-58], even though it is itself not very toxic. Its LD 50 value is similar to that of lithium perchlorate [55]. Just like lithium hexafluorophosphate, it can initiate the polymerization of cyclic ethers. Polymerization may be inhibited by tertiary amines [59], or 2-methylfuran [60], yielding highly stable electrolytes. 

Composite proplnts, which are used almost entirely in rocket propulsion, normally contain a solid phase oxidizer combined with a polymeric fuel binder with a -CH2—CH2— structure. Practically speaking AP is the only oxidizer which has achieved high volume production, although ammonium nitrate (AN) has limited special uses such as in gas generators. Other oxidizers which have been studied more or less as curiosities include hydrazinium nitrate, nitronium perchlorate, lithium perchlorate, lithium nitrate, potassium perchlorate and others. Among binders, the most used are polyurethanes, polybutadiene/acrylonitrile/acrylic acid terpolymers and hydroxy-terminated polybutadienes... 

Electrophilic additions to olefins, especially of XC1 species, can give substantial quantities of perchlorate esters as by-products if performed in the presence of lithium perchlorate. These esters are extremely explosive, and may concentrate during distillation of crude products. 

BF3.OH2).217 The use of a sulfonated phenol-formaldehyde polymer in conjunction with formic acid is also reported.208 Acids that are ineffective include phosphoric,208 trichloroacetic, dichloroacetic, and acetic acids.134 It is reported that addition of lithium perchlorate to the reaction mixture improves product... 

Hydrogenation of the carbon-carbon double bond occurs without alteration of the ester function when citronellyl acetate is treated with 2.5 equivalents of trifluoroacetic acid and two equivalents of triethylsilane in 2-nitropropane.205 The reduced product is obtained in 90% yield after 22 hours at room temperature in the presence of one equivalent of added lithium perchlorate (Eq. 82). The yields are lower in the absence of this added salt. Similar reduction of an unsaturated phenolic chroman derivative occurs to give an 85% yield of product with only the carbon-carbon double bond reduced (Eq. 83).205... 

Lithium oxide(s), 15 134, 141 Lithium perchlorate, 3 417 15 141-142 dessicant, 3 360 in lithium cells, 3 459 Lithium peroxide, 15 142 18 393 Lithium phosphate, 15 142 Lithium-polymer cells, 3 551 in development, 3 43 It Lithium primary cells, 3 459-466 Lithium production, 9 640 Lithium products, sales of, 15 121 Lithium salts, 15 135-136, 142 Lithium secondary cells, 3 549-551 ambient temperature, 3 541-549 economic aspects, 3 551-552 high temperature, 3 549-551 Lithium silicate glass-ceramics, 12 631-632... 

The lithium perchlorate-catalysed aminolysis of styrene oxide has been investigated. Amines of low nucleophilicity, such as aromatic amines, give almost exclusively products of type 30, sterically hindered amines (diisopropylamine, dicyclohexylamine etc.) give... 

Electron-rich aromatic compounds, such as phenol, anisole and A,./V-dimethylaniline, add to bis(2-trichloroethyl) azodicarboxylate under the influence of lithium perchlorate, boron trifluoride etherate or zinc chloride to yield para-substituted products 74, which are transformed into the anilines 75 by means of zinc and acetic acid86. Triflic acid (trifluoromethanesulphonic acid) catalyses the reactions of phenyl azide with benzene, toluene, chlorobenzene and naphthalene, to give TV-arylanilines (equation 34)87. 

Rhee and Shine39 used an impressive combination of nitrogen and carbon kinetic isotope effects to demonstrate that a quinonoidal-type intermediate is formed in the rate-determining step of the acid-catalyzed disproportionation reaction of 4,4 -dichlorohydrazobenzene (equation 26). When the reaction was carried out at 0°C in 60% aqueous dioxane that was 0.5 M in perchloric acid and 0.5 M in lithium perchlorate, extensive product analyses indicated that the major pathway was the disproportionation reaction. In fact, the disproportionation reaction accounted for approximately 72% of the product (compounds 6 and 7) while approximately 13% went to the ortho-semidine (8) and approximately 15% was consumed in the para-semidine (9) rearrangement. 

TABLE 4. The nitrogen, carbon-13 and carbon-14 kinetic isotope effects found for the acid-catalyzed formation of the disproportionation product, the ortho-semidine and the para-semidine at 0°C in 60% aqueous dioxane that was 0.5 M in perchloric acid and 0.5 M in lithium perchlorate... 

For this section, yield of the head-to-head product is relevant. In DMF with 0.1 M of tetra-butylammonium perchlorate, electrolysis of acetophenone at the potential of the first one-electron wave produces this dimer in 30% yield. This is in accord with the earlier-mentioned prediction that all the three directions of this dimerization are equally probable. If lithium perchlorate is the supporting electrolyte in the same solution, the head-to-head dimer yield rises to 70% (GuTtyai et al. 1987a). Hence, head-to-head coupling becomes the main route of dimerization. 

M.F, Muiphy, Two Explosives Generating Condensible Products", NOLTR 63-12(1963) [Mixts studied were Lithium Perchlorate Trihydrate (3 moles) Aluminum (8 moles) and amorphous Al powd with aq hydrogen peroxide (90%)]... 

Indoles can be alkylated by alkyl alcohols in the presence of lithium perchlorate and acetic acid for example, products such as the precursor (86) to the anti-fertility alkaloid yuehchukene can be produced (Equation 3) (93CC510). 

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