Alkaline-earth hydroxides, reactions

Pentaerythritol is produced by reaction of formaldehyde [50-00-0] and acetaldehyde [75-07-0] in the presence of a basic catalyst, generally an alkah or alkaline-earth hydroxide. Reaction proceeds by aldol addition to the carbon adjacent to the hydroxyl on the acetaldehyde. The pentaerythrose [3818-32-4] so produced is converted to pentaerythritol by a crossed Cannizzaro reaction using formaldehyde. All reaction steps are reversible except the last, which allows completion of the reaction and high yield industrial production. 

The aramids are formed in the low temperature reaction, -10 to 60°C, of equimolar amounts of the diacid chloride and the diamine in an amide solvent, typically dimethyl acetamide (DMAc) or A/-meth5i-2-pyrrohdinone (NMP) and usually with a small amount of an alkaU or alkaline-earth hydroxide and a metal salt, such as LiOH [1310-65-2] LiCl, Ca(OH)2 [1305-62-0] or CaCl2 added to increase the solubiUty of the polymer and neutralize the hydrochloric acid generated in the reaction. 

Sulfur combines directly with hydrogen at 150—200°C to form hydrogen sulfide. Molten sulfur reacts with hydrogen to form hydrogen polysulfides. At red heat, sulfur and carbon unite to form carbon disulfide. This is a commercially important reaction in Europe, although natural gas is used to produce carbon disulfide in the United States. In aqueous solutions of alkaU carbonates and alkaU and alkaline-earth hydroxides, sulfur reacts to form sulfides, polysulfides, thiosulfates, and sulfites. 

The yields obtained after 10 min in a batch reactor with MgO, CaO, or SrO exceeded 92%, whereas with BaO the yield was lower (72%), probably because of its low surface area (2m /g). When alkaline earth hydroxides were used as basic catalysts, the yields were lower than for the corresponding oxides. The most active hydroxides were Sr(OH)2 8H2O and Ba(OH)2 8H2O, which gave the additional compound in yields of 75% and 70%, respectively, whereas carbonates were characterized by very poor activity. As observed for other reactions, the catalytic activity of MgO strongly depends on the pre-treatment temperature. A maximum in activity was observed when MgO was pre-treated at 673 K. At this temperature, decomposition of Mg(OH)2 to MgO is not complete, and Mg(OH)2 remains in the catalyst. It was suggested that the surface OH groups act as active sites, as for the Michael addition reactions described above. 

As the last example of C-C bond-formation reactions catalyzed by alkaline earth hydroxides, we mention the recently reported a-arylation of diethyl malonate in the presence of a palladium catalyst and a base in a separate phase 299). The arylation of carbonyl compounds is a carbon-carbon coupling reaction between an aryl halide and an enolate, which is usually catalyzed by palladium salts in the presence of an appropriate base (300,301). The arylation of diethyl malonate with bromobenzene (Scheme 48) was performed with tetrachloropalladate as the... 

Pentaerythritol is manufactured by reaction of formaldehyde and acetaldehyde in the presence of a basic catalyst, generally an alkali or alkaline-earth hydroxide. 

The salts of PH2(0)(0H) are usually prepared by boiling white phosphorus with alkali or alkaline earth hydroxide. The main reaction appears to be... 

The alkaline earth hydroxide molecules were first made in flames and studied by emission spectroscopy [15]. Metal salt solutions are aspirated into atmospheric pressure flames or the salts are placed on a loop of wire in the flame. The MOH (M is an alkaline earth metal) molecules form through a complicated set of flame reactions [18]. More recent flame work has included laser-induced fluorescence studies of CaOH [29] and SrOH [30], Some of this work is motivated by the observation that soot formation is suppressed in flames when alkaline earths salts are added [31]. 

Quinoline and isoquinoline undergo a set of reactions in which, in effect, a hydride ion is replaced by a strongly nucleophilic species. With organolithium compounds the initial adduct, on hydrolysis and mild oxidation, yields the corresponding alkyl or aryl derivative, and hydroxy or amino groups can be introduced by reaction with alkali metal (or alkaline earth) hydroxides or amides. 

It is found that only alkali and alkaline earth hydroxides can promote the reaction that is, acidic and amphoteric oxides are inactive for the production of acrylonitrile. The best performances are obtained with silica-supported hydroxides of Cs, Rb, and K. The activity for the formation of acrylonitrile decreases in the order of Cs = Rb = K > Na > Li, and Ba > Ca Mg. This indicates that the activity is related to the electronegativity (basic property) of metal ions corresponding to the hydroxides supported on silica. 

The alkaline earth hydroxides are not very soluble and are used only when the solubility factor is not important. In fact, the low solubility of these bases can sometimes be an advantage. For example, many antacids are suspensions of metal hydroxides, such as aluminum hydroxide and magnesium hydroxide. The low solubility of these compounds prevents a large hydroxide ion concentration that would harm the tissues of the mouth, esophagus, and stomach. Yet these suspensions furnish plenty of hydroxide ion to react with the stomach acid, since the salts dissolve as this reaction proceeds. 

In reaction 1, a large negative salt effect is observed when an alkaline-earth hydroxide or thaUous hydroxide is used (a decrease of 11% in rate at F = 0.05 mole 1 for Ca(OH)2) and this has been... 

The formation of methylene bridges is slow for the first group, faster for group 2. The following mechanism can be written for the reaction between a phenolic compound and methanal in the presence of alkaline and alkaline earth hydroxides (Scheme 5) [56,73]. 

Reaction Mechanism of the Sodium Hydroxide Catalyzed Reaction between Phenol and Methanal. This Mechanism also Occurs in the Presence of other Alkaline and Alkaline Earth Hydroxides, (source ref [73])... 

Catalysts for aldol condensation may be either acidic or basic, but basic catalysts are much more common. The most common catalyst is Ba(OH)2. Besides Ba(OH)2, alkali and alkaline earth hydroxides or phosphates, and anion exchange resins are examples of solid base catalysts for the reactions. 

Alkali and Alkaline-earth Hydroxides. In the field of fonnaldehyde diemistiy, alkalies are chiefly of importance as reaction catalysts. Since the utility of alkalies in this connection has already been pointed out, the subject need only be revieAved biiefly in this place. When pure formaldehyde, paraformaldehyde, alpha-polyoxymethyiene, or any of the polyoxA methylene glycols are treated with alkalies in aqueous systems the foUoAA ing reactions ai e catalyjsed ... 

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). 

Basic oxides of metals such as Co, Mn, Fe, and Cu catalyze the decomposition of chlorate by lowering the decomposition temperature. Consequendy, less fuel is needed and the reaction continues at a lower temperature. Cobalt metal, which forms the basic oxide in situ, lowers the decomposition of pure sodium chlorate from 478 to 280°C while serving as fuel (6,7). Composition of a cobalt-fueled system, compared with an iron-fueled system, is 90 wt % NaClO, 4 wt % Co, and 6 wt % glass fiber vs 86% NaClO, 4% Fe, 6% glass fiber, and 4% BaO. Initiation of the former is at 270°C, compared to 370°C for the iron-fueled candle. Cobalt hydroxide produces a more pronounced lowering of the decomposition temperature than the metal alone, although the water produced by decomposition of the hydroxide to form the oxide is thought to increase chlorine contaminate levels. Alkaline earths and transition-metal ferrates also have catalytic activity and improve chlorine retention (8). 

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). 

The quality and yield of carbon black depends on the quaUty of the feedstock, reactor design, and input variables. The stmcture is controlled by the addition of alkaU metals to the reaction or mixing 2ones. Usual practice is to use aqueous solutions of alkaU metal salts such as potassium chloride or potassium hydroxide sprayed into the combustion chamber or added to the make oil in the oil injector. Alkaline-earth compounds such as calcium acetate that increase the specific surface area are introduced in a similar manner. 

A number of basic materials such as hydroxides, hydrides and amides of alkaline and alkaline earth metals and metal oxides such as zinc oxide and antimony oxide are useful catalysts for the reaction. Acid ester-exchange catalysts such as boric acid, p-toluene sulphonic acid and zinc chloride are less... 

---