Magnesium isolation

Group II hydrogencarbonates have insufficient thermal stability for them to be isolated as solids. However, in areas where natural deposits of calcium and magnesium carbonates are found a reaction between the carbonate, water and carbon dioxide occurs ... 

Prepare a Grignard reagent from 24 -5 g. of magnesium turnings, 179 g. (157 ml.) of n-heptyl bromide (Section 111,37), and 300 ml. of di-n-butyl ether (1). Cool the solution to 0° and, with vigorous stirring, add an excess of ethylene oxide. Maintain the temperature at 0° for 1 hour after the ethylene oxide has been introduced, then allow the temperature to rise to 40° and maintain the mixture at this temperature for 1 hour. Finally heat the mixture on a water bath for 2 hours. Decompose the addition product and isolate the alcohol according to the procedure for n-hexyl alcohol (Section 111,18) the addition of benzene is unnecessary. Collect the n-nonyl alcohol at 95-100°/12 mm. The yield is 95 g. 

Method 1. Arrange the flask containing the reaction mixture for steam distillation as in Fig. II, 40, 1. Proceed with the steam distillation until crystals of p-dibromobenzene appear in the condenser. Change the receiver and continue with the distillation until all the p-dibromobenzeiie has passed over from time to time run out the water from the condenser so that the crystals melt and run down into the receiver. Reject the residue in the flask. Transfer the first distillate to a separatory funnel, wash it with a httle water, and dry the lower layer with a little anhydrous magnesium sulphate or anhydrous calcium chloride filter. Distil slowly from a small distilling flask use a wire gauze or an air bath (Fig. II, 5, 3). Collect the fraction which passes over at 150-170° pour the residue (R), while it is still hot, into a small beaker or porcelain basin for the isolation of p-dibromobenzene. Redistil the fraction of b.p. 150-170° and collect the bromobenzene at 154-157° (3). The yield is 60 g. 

Method 2. Into a 500 ml. round-bottomed flask place 120 ml. of dry A.R. benzene, and 35 g. (29 ml.) of redistilled benzoyl chloride. Weigh out 30 g. of finely-powdered, anhydrous aluminium chloride into a dry corked test-tube, and add the solid, with frequent shaking, during 10 minutes to the contents of the flask. Fit a reflux condenser to the flask, and heat on a water bath for 3 hours or until hydrogen chloride is no longer evolved. Pour the contents of the flask wliile still warm into a mixture of 200 g. of crushed ice and 100 ml. of concentrated hydrochloric acid. Separate the upper benzene layer (filter first, if necessary), wash it with 50 ml. of 5 per cent, sodium hydroxide solution, then with water, and dry with anhydrous magnesium sulphate. Isolate the benzophenone as in Method 1. The yield is 30 g. 

In an alternative method of preparation, benzophenone is used. Prepare the Grignard reagent from 13 -5 g. of magnesium turnings as above, cool in cold water, and add a solution of 91 g. of benzophenone (Section IV,139) in 200 ml. of dry benzene at such a rate that the mixture refluxes gently. Reflux the mixture for 60 minutes, and isolate the triphenylcarbinol in the manner described above. The yield is of the same order. 

A 20% excess of ethylmagnesium bromide was prepared from magnesium (6.5 g) in ether (80 ml) by adding ethyl bromide (30 g) in ether (30 ml). Indole (25.8 g) in benzene (50 ml) was then added slowly with stirring and stirring was continued for 20 min after addition was complete. A solution of allyl bromide (29.2 g) in benzene (20 ml) was then added slowly. The mixture was stirred overnight and then diluted with ether and the product isolated and purified by distillation (22.7 g, 70% yield). 

Thioformamide is prepared in situ at 25 to 30°C. as described previously, and in the presence of magnesium carbonate (492. 512. 578). The mixture is then mildly heated on a water bath, and when temperature reaches 70°C, a-haloaldehyde is added in small quantities. At the end of this addition the reaction mixture is stirred for 2 hr at 100°C. Thiazoles were isolated in the usual manner by a double steam distillation. 

The base-catalyzed reaction of acetaldehyde with excess formaldehyde [50-00-0] is the commercial route to pentaerythritol [115-77-5]. The aldol condensation of three moles of formaldehyde with one mole of acetaldehyde is foUowed by a crossed Cannizzaro reaction between pentaerythrose, the intermediate product, and formaldehyde to give pentaerythritol (57). The process proceeds to completion without isolation of the intermediate. Pentaerythrose [3818-32-4] has also been made by condensing acetaldehyde and formaldehyde at 45°C using magnesium oxide as a catalyst (58). The vapor-phase reaction of acetaldehyde and formaldehyde at 475°C over a catalyst composed of lanthanum oxide on siHca gel gives acrolein [107-02-8] (59). 

Anhydrous magnesium nitrate [10377-60-3] Mg(N02)2, is very difficult to isolate. The commercial product is the deUquescent hexahydrate [13446-18-9] Mg(N02)2 6H20. As illustrated in the solubiUty curve in Figure 7, the hexahydrate is the stable soHd phase between —18 and 55—56°C. Properties are given in Table 17 (1 4). The unit ceU contains two formula units and the calculated density is 1.643 g/cm. ... 

Butyrolactone (41) and a moderate excess of ammonia are passed through a reactor at ca 250°C and 8—9 MPa (80—90 atm). Yields of 90—95% have been reported (77). The reaction proceeds in two steps, but the intermediate 4-hydroxybutyramide (42) is not ordinarily isolated. Improved yields are obtained if the reaction is carried out in the gas phase on a magnesium siUcate catalyst (250—290°C, 0.4—1.4 MPa), owing to supression of the undeskable by-product 4-(A/-2-pyrrohdonyl)butyramide (78). 

Fast Color Salts. In order to simplify the work of the dyer, diazonium salts, in the form of stable dry powders, were introduced under the name of fast color salts. When dissolved in water they react like ordinary diazo compounds. These diazonium salts, derived from amines, free from solubilizing groups, are prepared by the usual method and are salted out from the solutions as the sulfates, the metallic double salts, or the aromatic sulfonates. The isolated diazonium salt is sold in admixture with anhydrous salts such as sodium sulfate or magnesium sulfate. 

The main metals in brines throughout the world are sodium, magnesium, calcium, and potassium. Other metals, such as lithium and boron, are found in lesser amounts. The main nonmetals ate chloride, sulfate, and carbonate, with nitrate occurring in a few isolated areas. A significant fraction of sodium nitrate and potassium nitrate comes from these isolated deposits. Other nonmetals produced from brine ate bromine and iodine. 

Seawater. Salt extraction from seawater is done by most countries having coastlines and weather conducive to evaporation. Seawater is evaporated in a series of concentration ponds until it is saturated with sodium chloride. At this point over 90% of the water has been removed, and some impurities, CaSO and CaCO, have been crystallized. This brine, now saturated in NaCl, is transferred to crystallizer ponds where salt precipitates on the floor of the pond as more water evaporates. Brine left over from the salt crystallizers is called bitterns because of its bitter taste. Bitterns is high in MgCl2, MgSO, and KCl. In some isolated cases, eg, India and China, magnesium and potassium compounds have been commercially extracted, but these represent only a small fraction of total world production. 

A competing side reaction is chlorate formation, 3 CIO — 2 Cl + CIO3, which decreases the yields of dibasic magnesium hypochlorite [11073-21-5] and of evolved chlorine. The difficult to filter slurries can be dried with Httle loss to a white, powdery soHd with av CI2 in the range of 52—59%. The yields of isolated product and recovered chlorine are typically about 40% each, while product solubiUty loss and chlorate formation amount to about 10% each. 

Solutions in contact with polyvinyl chloride can become contaminated with trace amounts of lead, titanium, tin, zinc, iron, magnesium or cadmium from additives used in the manufacture and moulding of PVC. V-Phenyl-2-naphthylamine is a contaminant of solvents and biological materials that have been in contact with black rubber or neoprene (in which it is used as an antioxidant). Although it was only an artefact of the separation procedure it has been isolated as an apparent component of vitamin K preparations, extracts of plant lipids, algae, livers, butter, eye tissue and kidney tissue [Brown Chem Br 3 524 1967]. 

Cathodic protection with magnesium anodes can be just as economical as impressed current anode assemblies for pipelines only a few kilometers in length and with protection current densities below 10 xA m" e.g., in isolated stretches of new pipeline in old networks and steel distribution or service pipes. In this case, several anodes would be connected to the pipeline in a group at test points. The distance from the pipeline is about 1 to 3 m. The measurement of the off potential... 

Magnesium anodes are usually built into the object to be protected through isolating sockets or holes (see Fig. 20-6) and joined to them with cables. They must be readily accessible and easily exchangeable for convenient control [4]. The directions for use have to indicate the necessity for an inspection after 2 years of operation. During operation, control can be exercised by electrical measurements (current, resistance). In addition, acoustic and optical methods exist to determine the amount of anode consumption [4]. The life of the anodes is usually more than 5 years (see Section 6.6). 

The epimeric 17 -methylandrost-5-ene-3, 17a-diol could be isolated as a by-product from larger scale experiments. Reaction of (49) with ethyl-magnesium halide affords the corresponding 17a-ethyl compound. In this... 

In this reaction only 5% of the expected 12a-methyl steroid (19) can be isolated from the mother liquors after ketal cleavage. Rearrangement is undoubtedly due to magnesium halides in solution, since dimethylmagnesium smoothly effects the transformation of (17) to (19). A 41 % overall yield of (19) is obtained in this experiment. ... 

Dimethylindole magnesium iodide reacts with chloroacetonitrile in ether to give 3-cyanomethyl-2,3-dimethylindolenine (234). Majima and Hoshino obtained 3-(2-cyanoethyl)lndole (235) by the action of -chloropropionitrile on indole magnesium iodide. The reaction was slower with -chloropropionitrilc than with chloro-aoetonitrile. 3-(3-Cyano-w-propyl)indole (236), required as an intermediate in the synthesis of 3-indolyl-y-w-butyric acid, was prepared, but not isolated, by the action of y-chloro-w-butyronitrile on indole magnesium iodide. ... 

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