Alkaline-earth preparation

Simplest examples are prepared by the cyclic oligomerization of ethylene oxide. They act as complexing agents which solubilize alkali metal ions in non-polar solvents, complex alkaline earth cations, transition metal cations and ammonium cations, e.g. 12—crown —4 is specific for the lithium cation. Used in phase-transfer chemistry. ... 

Beams of metal atoms have been prepared by many researchers tlirough thennal vaporization from a heated cmcible. An example of such a source, employed for the generation of beams of alkaline earth atoms, is described by Irvin and Dagdigian [H]. By striking an electrical discharge within this source, beams... 

Uranium can be prepared by reducing uranium halides with alkali or alkaline earth metals or by reducing uranium oxides by calcium, aluminum, or carbon at high temperatures. The metal can also be produced by electrolysis of KUF5 or UF4, dissolved in a molten mixture of CaCl2 and NaCl. High-purity uranium can be prepared by the thermal decomposition of uranium halides on a hot filament. 

Its importance depends on the nuclear property of being readily fissionable with neutrons and its availability in quantity. The world s nuclear-power reactors are now producing about 20,000 kg of plutonium/yr. By 1982 it was estimated that about 300,000 kg had accumulated. The various nuclear applications of plutonium are well known. 238Pu has been used in the Apollo lunar missions to power seismic and other equipment on the lunar surface. As with neptunium and uranium, plutonium metal can be prepared by reduction of the trifluoride with alkaline-earth metals. 

Arsenic pentafluoride can be prepared by reaction of fluorine and arsenic trifluoride or arsenic from the reaction of NF O and As (16) from the reaction of Ca(FS02)2 and H AsO (17) or by reaction of alkaH metal or alkaline-earth metal fluorides or fluorosulfonates with H AsO or H2ASO2F (18). 

Hexafluoroarsenic acid [17068-85-8] can be prepared by the reaction of arsenic acid with hydrofluoric acid or calcium fluorosulfate (29) and with alkaH or alkaline-earth metal fluorides or fluorosulfonates (18). The hexafluoroarsenates can be prepared directly from arsenates and hydrofluoric acid, or by neutrali2ation of HAsF. The reaction of 48% HF with potassium dihydrogen arsenate(V), KH2ASO4, gives potassium hydroxypentafluoroarsenate(V)... 

Difluoroethanol is prepared by the mercuric oxide cataly2ed hydrolysis of 2-bromo-l,l-difluoroethane with carboxyHc acid esters and alkaH metal hydroxides ia water (27). Its chemical reactions are similar to those of most alcohols. It can be oxidi2ed to difluoroacetic acid [381-73-7] (28) it forms alkoxides with alkaH and alkaline-earth metals (29) with alkoxides of other alcohols it forms mixed ethers such as 2,2-difluoroethyl methyl ether [461-57-4], bp 47°C, or 2,2-difluoroethyl ethyl ether [82907-09-3], bp 66°C (29). 2,2-Difluoroethyl difluoromethyl ether [32778-16-8], made from the alcohol and chlorodifluoromethane ia aqueous base, has been iavestigated as an inhalation anesthetic (30,31) as have several ethers made by addition of the alcohol to various fluoroalkenes (32,33). Methacrylate esters of the alcohol are useful as a sheathing material for polymers ia optical appHcations (34). The alcohol has also been reported to be useful as a working fluid ia heat pumps (35). The alcohol is available ia research quantities for ca 6/g (1992). 

The superoxides are ionic soHds containing the superoxide, O - A comprehensive review of the superoxides was pubHshed ia 1963 (109) they are described ia Reference 1. Superoxides of all of the alkaU metals have been prepared. Alkaline-earth metals, cadmium, and 2iac all form superoxides, but these have been observed only ia mixtures with the corresponding peroxides (110). The tendency to form superoxides ia the alkaU metal series iacreases with increasing size of the metal ion. 

Orthophosphate salts are generally prepared by the partial or total neutralization of orthophosphoric acid. Phase equiUbrium diagrams are particularly usehil in identifying conditions for the preparation of particular phosphate salts. The solution properties of orthophosphate salts of monovalent cations are distincdy different from those of the polyvalent cations, the latter exhibiting incongment solubiUty in most cases. The commercial phosphates include alkah metal, alkaline-earth, heavy metal, mixed metal, and ammonium salts of phosphoric acid. Sodium phosphates are the most important, followed by calcium, ammonium, and potassium salts. 

Alkali Meta.IPhospha.tes, A significant proportion of the phosphoric acid consumed in the manufacture of industrial, food, and pharmaceutical phosphates in the United States is used for the production of sodium salts. Alkali metal orthophosphates generally exhibit congment solubility and are therefore usually manufactured by either crystallisation from solution or drying of the entire reaction mass. Alkaline-earth and other phosphate salts of polyvalent cations typically exhibit incongment solubility and are prepared either by precipitation from solution having a metal oxide/P20 ratio considerably lower than that of the product, or by drying a solution or slurry with the proper metal oxide/P20 ratio. 

Heterogeneous Catalytic Polymerization. The preparation of polymers of ethylene oxide with molecular weights greater than 100,000 was first reported in 1933. The polymer was produced by placing ethylene oxide in contact with an alkaline-earth oxide for extended periods (61). In the 1950s, the low yield and low polymerization rates of the eady work were improved upon by the use of alkaline-earth carbonates as the catalysts (62). 

Double Alkoxides. Complex double alkoxides are formed when a solution of an alkaU or alkaline earth metal alkoxide is added to a solution of an alkoxide of aluminum, titanium, or tirconium and a series of such compounds have been prepared (44). 

Tellura.tes. The water-soluble alkaU metal and alkaline-earth teUurates are prepared by chlorinating alkaline solutions of the teUurites or by heating soUd teUurites with KNO3, KCIO3, or Pb02 to form, for example, potassium teUurate [7790-58-1], K2Te03. The insoluble teUurates are made by... 

Thiosulfates. The ammonium, alkaU metal, and aLkaline-earth thiosulfates are soluble in water. Neutral or slightly alkaline solutions containing excess base or the corresponding sulfite are more stable than acid solutions. Thiosulfate solutions of other metal ions can be prepared, but their stabiUty depends on the presence of excess thiosulfate, the formation of complexes, and the prevention of insoluble sulfide precipitates. 

Other. Insoluble alkaline-earth metal and heavy metal stannates are prepared by the metathetic reaction of a soluble salt of the metal with a soluble alkah—metal stannate. They are used as additives to ceramic dielectric bodies (32). The use of bismuth stannate [12777-45-6] Bi2(Sn02)3 5H20, with barium titanate produces a ceramic capacitor body of uniform dielectric constant over a substantial temperature range (33). Ceramic and dielectric properties of individual stannates are given in Reference 34. Other typical commercially available stannates are barium stannate [12009-18-6] BaSnO calcium stannate [12013 6-6] CaSnO magnesium stannate [12032-29-0], MgSnO and strontium stannate [12143-34-9], SrSnO. ... 

Composite Oxyalkoxides. Composite oxyalkoxides can be prepared by reaction of tetraalkyl titanates and alkaline-earth metal hydroxides. These oxyalkoxides and their derivatives can be hydroly2ed and thermally decomposed to give alkaline-earth metal titanates such as barium titanate (150). 

Barium [7440-39-3] Ba, is a member of Group 2 (IIA) of the periodic table where it Hes between strontium and radium. Along with calcium and strontium, barium is classed as an alkaline earth metal, and is the densest of the three. Barium metal does not occur free in nature however, its compounds occur in small but widely distributed amounts in the earth s cmst, especially in igneous rocks, sandstone, and shale. The principal barium minerals are barytes [13462-86-7] (barium sulfate) and witherite [14941-39-0] (barium carbonate) which is also known as heavy spar. The latter mineral can be readily decomposed via calcination to form barium oxide [1304-28-5] BaO, which is the ore used commercially for the preparation of barium metal. 

The cubic 2inc blende form of boron nitride is usually prepared from the hexagonal or rhombohedral form at high (4—6 GPa (40—60 kbar)) pressures and temperatures (1400—1700°C). The reaction is accelerated by lithium or alkaline-earth nitrides or amides, which are the best catalysts, and form intermediate Hquid compounds with BN, which are molten under synthesis conditions (11,16). Many other substances can aid the transformation. At higher pressures (6—13 GPa) the cubic or wurt2itic forms are obtained without catalysts (17). 

Main Group Element Carborane Derivatives. Main group element carborane derivatives have been reviewed (231). Only a few alkaline-earth element metaHacarborane derivatives have been characterized. The icosahedral beryUacarborane, /(9j (9-3-[(CH3)3N]-3,l,2-BeC2B H, shown in Figure 24a, has been prepared via the reaction of nido-1 and Be(CH3)2 [0(C2H3)2]2 followed by reaction of the diethyletherate product and... 

Other Bromides. Alkali and alkaline earth bromides can be prepared by neutralizing a solution of the corresponding hydroxide or carbonate with hydrobromic acid. Alternatively, bromine and a reducing agent such as ammonia are used in the van der Meulen process (13) ... 

Hypobromites, the salts of hypobromous acid, do not keep well because they gradually disproportionate to bromide and bromate. Solutions are best prepared as needed from bromine and alkafl with cooling. Because disproportionation is catalyzed by cobalt, nickel, and copper (70), these impurities should be avoided. SoHd alkaline earth hypobromites, or more properly, bromide hypobromites such as calcium bromide hypobromite [67530-61 CaBr(OBr), have been known for many years, but the pure crystalline hydrates sodium hypobromite pentahydrate [13824-96-9] NaOBr 5H20, and potassium hypobromite tribydrate [13824-97-0], KOBr 3H20, were not described until 1952 (71). Hypobromites are strong bleaching agents, similar to hypochlorites. 

No attempt should be made to purify perchlorates, except for ammonium, alkali metal and alkaline earth salts which, in water or aqueous alcoholic solutions are insensitive to heat or shock. Note that perchlorates react relatively slowly in aqueous organic solvents, but as the water is removed there is an increased possibility of an explosion. Perchlorates, often used in non-aqueous solvents, are explosive in the presence of even small amounts of organic compounds when heated. Hence stringent care should be taken when purifying perchlorates, and direct flame and infrared lamps should be avoided. Tetra-alkylammonium perchlorates should be dried below 50° under vacuum (and protection). Only very small amounts of such materials should be prepared, and stored, at any one time. 

The in-out bicyclic amines prepared by Simmons and Park bear a remarkable semblance to the cryptands but lack the binding sites in the bridges. As a result, these molecules interact with electrophiles in a fashion similar to other tertiary amines and generally do not exhibit strong interactions with alkali or alkaline earth metal ions. The in-out bicyclic amines are prepared by reaction of the appropriate acid chlorides and amines in two stages to yield the macrobicyclic amine after reduction of the amidic linkages. A typical amine is shown above as compound 18. 

We have not attempted to cover all or even most aspects of crown chemistry and some may say that the inclusions are eclectic. We felt that anyone approaching the field would need an appreciation for the jargon currently abounding and for the so-called template effect since the latter has a considerable bearing on the synthetic methodology. We have, therefore, included brief discussions of these topics in the first two chapters. In chapters 3—8, we have tried to present an overview of the macrocyclic polyethers which have been prepared. We have taken a decidedly organic tack in this attempting to be comprehensive in our inclusion of alkali and alkaline earth cation binders rather than the compounds of use in transition metal chemistry. Nevertheless, many of the latter are included in concert with their overall importance. 

Hydrogen can be prepared by the reaction of water or dilute acids on electropositive metals such as the alkali metals, alkaline earth metals, the metals of Groups 3, 4 and the lanthanoids. The reaction can be explosively violent. Convenient laboratory methods employ sodium amalgam or calcium with water, or zinc with hydrochloric acid. The reaction of aluminium or ferrosilicon with aqueous sodium hydroxide has also been used. For small-scale preparations the hydrolysis of metal hydrides is convenient, and this generates twice the amount of hydrogen as contained in the hydride, e.g. ... 

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