Alkaline earth metals reactions with alcohols

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). 

Reaction of tetraisopropyl titanate with an alkali or alkaline earth metal hydroxide in alcohol solution to form a soluble intermediate ... 

The speed of the reaction depends both on the metal and on the alcohol, increasing as electropositivity iacreases and decreasiag with length and branching of the chain. Thus sodium reacts strongly with ethanol, but slowly with tertiary butyl alcohol. The reaction with alkaU metals is sometimes carried out ia ether, ben2ene, or xylene. Some processes use the metal amalgam or hydride iastead of the free metal. Alkaline earth metals and aluminum are often covered with an oxide film which hinders the reaction. 

Explosive reactions can occur between oxygen and a wide range of chemicals including organic compounds (such as acetone, acetylene, secondary alcohols, hydrocarbons), alkali and alkaline earth metals, ammonia, biological specimens previously anaesthetized with ether, hydrogen and foam rubber. 

The Guerbet reaction is an important industrial process for increasing the carbon numbers of alcohols. Thus, a primary or secondary alcohol reacts with itself or another alcohol to produce a higher alcohol (Scheme 23). Alkaline earth metal oxides have been used as catalysts for the condensation of alcohols. Ueda et al. (158,159) reported the condensation of methanol with other primary or secondary alcohols having a methyl or methylene group at the )S-position they used MgO, CaO, and ZnO as catalysts. The reactions were performed with gas-phase reactants at 635 K only MgO was found to be both active and selective (>80%). 

By this approach, esters such as di(2-ethylhexyl) adipate and an oligomeric ester of neopentyl glycol have been synthesized recently by alcoholysis of dimethyl adipate ester and the corresponding alcohols, with alkaline earth metal compounds as the catalysts (171) (Scheme 30). These types of esters find application as lubricants, and it is suggested that they can be used as environment-friendly substitutes for petroleum-derived lubricants. The reactions were carried out with isooctane as a... 

The crystal structures of alkaline earth metal complexes of several (1 + 1) and (2 + 2) Schiff base macrocycles have been reported. These macrocycles are formed by the metal template-controlled condensation of the required heterocyclic dicarbonyl derivative and a, co functional diamine in alcoholic solution. (1 +1) complexes arise from the condensation reaction of one dicarbonyl with one diamine and (2 + 2) complexes from the condensation of two dicarbonyls with two diamines. 

In summary, the reaction between an alkali metal alkoxide and a poly-hydroxy compound in hot alcoholic media produces an alcoholate and, possibly, a small proportion of alkoxide adduct however, the conditions governing the ratio of alcoholate to adduct have not yet been well defined. Reactions with alkali metal hydroxides and cyanides produce mixtures (of alcoholate and adduct) that consist mainly of alcoholate. Occurrence of reactions between alkaline-earth metal hydroxides and polyhydroxy compounds in anhydrous alcoholic media has not been reported. 

IV. Alcoholates from Reactions, in Liquid Ammonia, of Carbohydrates with Alkali Metals, Alkaline-earth Metals, and Alkali Metal Amides... 

Methylene Chloride tdichtaromethane). CAS 75-09-2. As with the other members of the methyl series of chlorinated hydrocarbons, methylene chloride can he produced hy direct chlorination of methane. The usual procedure involves a modification of the simple methane process. The product from Ihe first chlorination passes through aqueous zinc chloride, contacting methanol at about 100 C. Thus. HCl from chlorination is used to displace the alcohol group, producing additional methyl chloride. This is further chlorinated to methylene chloride. Methylene chloride reacts violently in the presence of alkali or alkaline earth metals and will hydrolyze to formaldehyde in the presence of an aqueous base. Alkvlalion reactions occur at both functions, thus di-suhstiiulioiis result. For example. 

Nitroalkanols are intermediate compounds of /1-amino alcohols that are used extensively in many important syntheses. They are obtained by Henry s reaction through the condensation of nitroalkanes with aldehydes. Different nitro compounds have been reacted with carbonyl compounds in reactions catalysed by alkaline earth metal oxides and hydroxides/621 Among the catalysts examined, MgO, CaO, Ba(OH)2, and Sr(OH)2, exhibited high activity for the reaction of nitromethane with propionaldehyde. The yields were between 60 % (for MgO) and 26 % [for Sr(OH)2] at 313 K after 1 h in a batch reactor. The study of the influence of the pretreatment temperature of the solid showed that for MgO and CaO a... 

Calcium bis[tetrahydroborate(l-)] may be prepared from sodium tetra-hydroborate( 1 -) and calcium dichloride by cation exchange11 in a suitable solvent such as dimethylformamide,12 an amine13,14 or an alcohol.13,14 A particularly good preparation of very pure Ca[BH4]2 involves the reaction of calcium dihydride with the triethylamine-borane adduct.15,16 This method may also be used for the preparation of other tetrahydroborates of alkali and alkaline earth metals. The triethylamine-borane adduct17 may be synthesized in a variety of ways, e.g., from triethylamine, sodium tetrahydro-borate(l —), and trichloroborane 18 from a trialkoxyborane, aluminum metal, and hydrogen in the presence of triethylamine 19 or by hydrogenation under pressure of a mixture of triethylborane and triethylamine.20 The triethylamine-borane adduct is a colorless liquid (mp — 2°). It is stable to air and moisture at room temperature and it is easily purified by vacuum distillation (bp 95-96°/12 torr). 

Pentafluoropropan-l-ol (1) can also be prepared by interacting tetrafluoroethene with an alkali metal fluoride or an alkaline earth metal fluoride, followed by reaction with formaldehyde, and Anally by hydrolysis of the metal alcoholate with water. ... 

For reductions carried out in the absence of an added proton donor the usual solvents are liquid NH3, usually with an ethereal cosolvent, or less commonly an ether (THF, DME or diethyl ether). TTie reducing agent is usually one of the common alkali metals (Li, Na, K), although Rb, Cs and alkaline earth metals have also been used. " At least in the case of camphor both types of solvent systems give similar ratios of epimeric alcohols however, product ratios may vaiy as a function of the metal used as reducing agent. In reductions carried out in ethereal solvents the use of ultrasound increases the rate of the reaction, but does not affect the product distribution. ... 

All the arsinic acids dealt with in the following pages arc crystalline solids. Some of tlie primary acids, when heated above their melting-points, eliminate water and form anliydrides. The acids are very stable but may be reduced by amalgamated zinc dust and hydrochloric acid, or by electrolysis in aqueous alcoholic hydrochloric acid, to arylarsines, RAsIIs- An exception to tlie above-mentioned stability is the case of benzylarsinic acid, which is decomposed by mineral adds, and differs from all other members of this series in its reactions. The salts formed with alkali and alkaline earth metals show that the acids are dibasic. Esters may be formed by heating the silver salts of tlie acids in ethereal solution under reflux with the calculated amount of alkyl iodide, but excess of the latter must be avoided or alkyi-arylarsenites are formed ... 

Syntheses that exploit the solubility of the alkaline-earth metals in liquid ammonia have proven practical for alkoxide work, as they generate high yields, reaction rates, and purity (Table 8, Equation (3)). In a refinement of this approach, Caulton and co-workers have used dissolved ammonia in an ethereal solvent, usually THF, to effect the production of a number of alkoxides of barium, and this method has also been examined with calcium and strontium (Table 8, Equations (4a) to (4c)). Displacement reactions using alkali metal alkoxides and alkaline-earth dihalides (Table 8, Equation (5)), and between alkaline-earth hydrides or amides and alcohols (Table 8, Equations (6) and (7)), have been examined, but alkali-metal halide impurities, incomplete reactions, and unexpected equilibria and byproducts can affect the usefulness of these approaches. 

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