Magnesium coupling

Negative values of ° (such as a Na = —2.71 V) indicate that the reduced form of the couple will react with protons to form hydrogen gas, as in Equation (7.35). The more negative the value of e, the more potent the reducing power of the redox state, so for the magnesium couple is —2.36 V, and F K = —2.93. 

DoM-Derived Cross-Coupling Reactions. Synthetic Comparison of Boron, Zinc, and Magnesium Coupling Partners... 

Recently, the coupling of halosilanes with lithium (40) or magnesium (41, 42) in tetrahydrofuran (THF) has been carried out. While the magnesium coupling reaction is useful for the production of functional... 

Baboian, R., Final Report on the ASTM Study Atmospheric Galvanic Corrosion of Magnesium Coupled to Other Metals, ... 

Baboian, R., Final Report on the ASTM Study Atmospheric Galvanic Corrosion of Magnesium Coupled to Other Metals, Atmospheric Factors Affecting the Corrosion of Engineering Metals, ASTM STP 646, S. Cobum, Ed., 1978, ASTM International, West Conshohocken, PA, pp. 17-29. 

In 1992 Belzner prepared the cyclotrisilane 77 by magnesium coupling of the pentaco-ordinate dichlorosilane 78 (equation 121). 77 reacted with silylene trapping agents under truly mild conditions, at 50°C, to give three equivalents of trapping products . The reactions with benzil and diphenylacetylene" are shown as examples in equations 122 and 123. 

JX Jia, A Atrens, G Song, T Muster, Simulation of galvanic corrosion of magnesium coupled to a steel fastener in NaCl solution. Materials and Corrosion, 2005, 56, 468-174. 

JX Jia, G Song, A Atrens, Experimental measurement and computer simmulation of galvanic corrosion of magnesium coupled to steel. Advanced Engineering Materials, 2007, 9, 65-74. 

MetaUic ions are precipitated as their hydroxides from aqueous caustic solutions. The reactions of importance in chlor—alkali operations are removal of magnesium as Mg(OH)2 during primary purification and of other impurities for pollution control. Organic acids react with NaOH to form soluble salts. Saponification of esters to form the organic acid salt and an alcohol and internal coupling reactions involve NaOH, as exemplified by reaction with triglycerides to form soap and glycerol,... 

Electroreductive coupling of ben2otrifluorides with sacrificial aluminum or magnesium anodes in the presence of acetone, carbon dioxide, or /V, /V-dimethylformamide provides a novel route to ArCF2-derivatives (310). 

Detergents are metal salts of organic acids used primarily in crankcase lubricants. Alkylbenzenesulfonic acids, alkylphenols, sulfur- and methjiene-coupled alkyl phenols, carboxyUc acids, and alkylphosphonic acids are commonly used as their calcium, sodium, and magnesium salts. Calcium sulfonates, overbased with excess calcium hydroxide or calcium carbonate to neutralize acidic combustion and oxidation products, constitute 65% of the total detergent market. These are followed by calcium phenates at 31% (22). 

Table 8 indicates the compatibiUty of magnesium with a variety of chemicals and common substances. Because the presence of even small amounts of impurities in a chemical substance may result in significantly altered performance, a positive response in the table only means that tests under the actual service conditions are warranted (132). Other factors which may significantly alter magnesium compatibiUty include the presence of galvanic couples, variations in operating temperatures, alloy composition, or humidity levels. 

Some tests indicate that magnesium alloys are resistant to loam sod. However, in the presence of chlorides, corrosive attack may be serious particularly if galvanic couples are present as a result of coupling to iron stmctures. 

Sodium and magnesium do not react with tetrachlorosilane at room temperature, but do so at elevated temperatures and ia the presence of polar aprotic solvents at moderately elevated temperatures. The Wurtz-Fittig coupling of organosilanes to form disilanes (168) and polysdanes (169) is usually accomphshed usiag molten sodium ia toluene or xylene. 

Benzyl chloride readily forms a Grignard compound by reaction with magnesium in ether with the concomitant formation of substantial coupling product, 1,2-diphenylethane [103-29-7]. Benzyl chloride is oxidized first to benzaldehyde [100-52-7] and then to benzoic acid. Nitric acid oxidizes directly to benzoic acid [65-85-0]. Reaction with ethylene oxide produces the benzyl chlorohydrin ether, CgH CH20CH2CH2Cl (18). Benzylphosphonic acid [10542-07-1] is formed from the reaction of benzyl chloride and triethyl phosphite followed by hydrolysis (19). 

The transmetallation of lithio derivatives with either magnesium bromide or zinc chloride has been employed to increase further their range of synthetic application. While the reaction of l-methyl-2-pyrrolyllithium with iodobenzene in the presence of a palladium catalyst gives only a poor yield (29%) of coupled product, the yield can be dramatically improved (to 96%) by first converting the lithium compound into a magnesium or zinc derivative (Scheme 83) (81TL5319). 

A mixture consisting of 0.69 g (10.5 mmoles) of zinc-copper couple, 12 ml of dry ether, and a small crystal of iodine, is stirred with a magnetic stirrer and 2.34 g (0.7 ml, 8.75 mmoles) of methylene iodide is added. The mixture is warmed with an infrared lamp to initiate the reaction which is allowed to proceed for 30 min in a water bath at 35°. A solution of 0.97 g (2.5 mmoles) of cholest-4-en-3/ -ol in 7 ml of dry ether is added over a period of 20 min, and the mixture is stirred for an additional hr at 40°. The reaction mixture is cooled with an ice bath and diluted with a saturated solution of magnesium chloride. The supernatant is decanted from the precipitate, and the precipitate is washed twice with ether. The combined ether extracts are washed with saturated sodium chloride solution and dried over anhydrous sodium sulfate. The solvent is removed under reduced pressure and the residue is chromatographed immediately on 50 g of alumina (activity III). Elution with benzene gives 0.62 g (62%) of crystalline 4/5,5/5-methylene-5 -cholestan-3/5-ol. Recrystallization from acetone gives material of mp 94-95° Hd -10°. 

In addition to sodium, other metals have found application for the Wurtz coupling reaction, e.g. zinc, iron, copper, lithium, magnesium. The use of ultrasound can have positive effect on reactivity as well as rate and yield of this two-phase reaction aryl halides can then even undergo an aryl-aryl coupling reaction to yield biaryls. ... 

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