Copper recrystallization

Additions of cadmium (0.05—1.3%) to copper raise the recrystallization temperature and improve the mechanical properties, especially in cold-worked conditions, with relatively Htde reduction in conductivity. Copper containing 0.07% cadmium is used in automotive cooling fins, heavy-duty radiators, motor commutators, and electric terminals. 

Effect of Thermal History. Many of the impurities present in commercial copper are in concentrations above the soHd solubihty at low (eg, 300°C) temperatures. Other impurities oxidize in oxygen-bearing copper to form stable oxides at lower temperatures. Hence, because the recrystallization kinetics are influenced primarily by solute atoms in the crystal lattice, the recrystallization temperature is extremely dependent on the thermal treatment prior to cold deformation. 

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°. 

Copper(II) also forms stable complexes with O-donor ligands. In addition to the hexaaquo ion, the square planar /3-diketonates such as [Cu(acac)2l (which can be precipitated from aqueous solution and recrystallized from non-aqueous solvents) are well known, and tartrate complexes are used in Fehling s test (p. 1181). 

Meyers has also reported the use of chiral oxazolines in asymmetric copper-catalyzed Ullmann coupling reactions. For example, treatment of bromooxazoline 50 with activated copper powder in refluxing DMF afforded binaphthyl oxazoline 51 as a 93 7 mixture of atropisomers diastereomerically pure material was obtained in 57% yield after a single recrystallization. Reductive cleavage of the oxazoline groups as described above afforded diol 52 in 88% yield. This methodology has also been applied to the synthesis of biaryl derivatives. 

A stirred suspension of a 2-ehlorobenzoic acid (1 mol), benzene-1,2-diamine (108 g, 1 mol) and finely powdered copper (63.5 g, 1 g-atom) in chlorobenzene (3 L) was refluxed for 8 li in an apparatus fitted with a Dean-Stark separator. The hot mixture was rapidly filtered and the filtrate was concentrated to 1 L under reduced pressure. The product, which separated on cooling, was recrystallized (MeOH or dioxane). 

The pentafluorophenylcopper tetramer is usually analytically pure as isolated and melts at 200° with decomposition. If any significant decomposition occurs during the final drying, the product can be purified by dissolution in ether, filtration to remove copper metal, and precipitation by addition of hexane. It can also be recrystallized from benzene. When kept in a sealed container under nitrogen at room temperature, pentafluorophenyl copper tetramer appears to be stable for reasonable periods. It can be stored indefinitely at -78° under an atmosphere of carbon dioxide. 

DBpD was prepared by slowly heating a mixture of o-chlorophenol (480 mmoles), potassium carbonate (240 mmoles), and purified copper powder (50 mmoles) in a 500-ml Erlenmeyer flask to 160°-180°C and maintaining this temperature for 6 hours. DBpD, which sublimed to the walls of the flask as it was formed, was recovered by scraping and was recrystallized from absolute ethanol (14% yield white needles, mp 119°-120°C reported 120°-122°C (7) elemental analyses—calcd. C = 78.26, H = 4.34, found C = 77.98, H = 4.48). 

Tetrachlorodiben2o- >-dioxin. Purified 2,4,5-trichlorophenol (50 grams, 0.26 mole) was converted to its potassium salt and dissolved in 100 ml of bEEE. After addition of the copper catalyst and ethylene diacetate, the mixture was transferred to the bottom of a 300-ml sub-limer with chloroform. Sublimation (200°C/2 mm) yielded 14 grams (39% yield) of 2,3,7,8-tetrachlorodibenzo-p-dioxin. Mass spectral analysis revealed trace quantities of pentachlorodibenzo-p-dioxin, tetrachloro-dibenzofuran, and several unidentified substances of similar molecular weight. The combined impurity peaks were estimated to be <1% of the total integrated GLC area. The product was further purified by recrystallizations from o-dichlorobenzene and anisole. The final product had an estimated 260 ppm of trichlorodibenzo-p-dioxin as the only detected impurity. 

Galena, tetrahedrite-tennantite, mawsonite and native silver occur in the copper rich ores but not in ordinary pyritic ores and copper rich ores most commonly occur as offshoots, tongues and veins in the deformed deposits. This suggests that these minor minerals formed during the metamorphic deformation stage accompanied by recrystallization. 

General Considerations. The following chemicals were commercially available and used as received 3,3,3-Triphenylpropionic acid (Acros), 1.0 M LiAlH4 in tetrahydrofuran (THF) (Aldrich), pyridinium dichromate (Acros), 2,6 di-tert-butylpyridine (Acros), dichlorodimethylsilane (Acros), tetraethyl orthosilicate (Aldrich), 3-aminopropyltrimethoxy silane (Aldrich), hexamethyldisilazane (Aldrich), tetrakis (diethylamino) titanium (Aldrich), trimethyl silyl chloride (Aldrich), terephthaloyl chloride (Acros), anhydrous toluene (Acros), and n-butyllithium in hexanes (Aldrich). Anhydrous ether, anhydrous THF, anhydrous dichloromethane, and anhydrous hexanes were obtained from a packed bed solvent purification system utilizing columns of copper oxide catalyst and alumina (ether, hexanes) or dual alumina columns (tetrahydrofuran, dichloromethane) (9). Tetramethylcyclopentadiene (Aldrich) was distilled over sodium metal prior to use. p-Aminophenyltrimethoxysilane (Gelest) was purified by recrystallization from methanol. Anhydrous methanol (Acros) was... 

Turanose Phenylosotriazole. A solution of 15 g. of turanose phenylosazone in 300 cc. of hot water was placed on the steam-bath and a solution of 22 g. of copper siilfate pentahydrate in 150 cc. of hot water was added. The mixture turned a deep cherry-red at once and in a short time (fifteen min.) a red precipitate had formed and the solution had become green. After thirty minutes from the time of addition of the copper solution, the solution was cooled, filtered, and the copper removed as sulfide. The clear light yellow filtrate was neutralized with 45 g. of barium carbonate and the insoluble material removed by filtration. The filtrate was extracted with five 50-cc. portions of ether to remove the aniline, and the aqueous portion was concentrated in vacuo to a thick sirup. The sirup was dissolved in 60 cc. of warm alcohol, filtered to remove a slight turbidity and diluted with 65 cc. of ether. Upon cooling and scratching, the product crystallized as large prisms yield 8.9 g. (72%). The phenylosotriazole was recrystallized from 10 parts of alcohol and when pure showed the melting point 193-194° and rotated [a Jj" + 74.5° in aqueous solution (c, 0.90). 

Polymers Polyacrylamide and hydrolyzed polyacrylamide were prepared by the American Cyanamid Company specifically for this project, starting with l C labelled monomer. The radioactivity level of the monomer was kept below 0.20 mC /g in order to avoid significant spontaneous polymerization, utilizing a copper inhibitor. The homopolymer was synthesized by free radical solution polymerization in water at 40°C, using monomer recrystallized from chloroform, an ammonium persulfate-sodium metabisulfite catalyst system, and isopropanol as a chain transfer agent. Sodium... 

The syntheses of 1 utilized the Ullmann ether synthesis.13 Reaction of 2 mol of 1-bromonaphthalene with 4,4-(hexafluoroisopropylidiene)diphenol afforded the desired product 1. The reaction was carried out in DM Ac at 160°C in the presence of potassium carbonate as the base and copper (I) iodine as the reaction catalyst to yield 1, as depicted in Scheme 1. The reaction proceeded slowly but in good yield with easy isolation of the desired compound. Acylation of 1 with 4-fluorobenzoyl chloride to prepare 2 was carried out under modified Friedel-Crafts reaction conditions14 using dimethyl-sulfone as catalyst moderator. Both 1 and 2 were easily recrystallized to yield high-purity monomers suitable for polymerizations. 

A version of P.R.202 in a platelet form is obtainable by recrystallizing of the crude pigment from a polar solvent such as DMF in the presence of a thiol compound and sodium methoxide. The new form affords, for instance in PVC, the appearance of a lustrous copper bronze tone [27]. 

Recrystallization of the crude copper complex from boiling 20% ammonium chloride (/>H 4) affords lustrous brick red needles. Analytically pure material is obtained on a second recrystallization from O.OOIA hydrochloric acid followed by drying over phosphorous pentoxide. 

As an additional example of high practical significance, we refer here to copper depKJsits when used in microelectronics, mirrors, and other optical applications. Those deposits have been observed to soften in time even when stored at room temperature for only 4 to 6 weeks. Also, mirrors and other precision objects made of copper will undergo surface deformation after a few months. This type of degradation can be counterbalanced by a suitable metal overcoating. Another, not always practical way is heat treatment to about 300°C. These phenomena are the direct results of microstructural instabilities, often referred to as recrystallization in the copper. It is worth stressing that recrystallization is not limited to copper (5). 

N,a-DMT. JMC, 9, 343 (1966). Mix 5.5 g of indole, 15 ml of cyclohexane, and 0.5 g of clean copper. Bring this mixture to a reflux and add 2.9 g of diazoacetone dropwise. After some time, the reaction goes very rapidly and forms two layers. Filter, evaporate in vacuo to get 2 h. g of 3-indoyl-acetone. 3.3 g of 3-idoyl-acetone in 100 ml of ethanol is then reduced in the presence of an excess of methylamine (3 g), or analog, over palladium carbon catalyst (see the reductions chapter). After 2 hours the catalyst is filtered off and the solution is concentrated, acidified, extracted with ether, and the aqueous layer is made alkaline. The title product precipitated is a tan solid (2.2 g) with a melting point of 93-94° and can be recrystallized with a mixture of THF-hexane. 

Methoxy-2-Naphthol. A mixture of 10 g of 6-bromo-2-methoxynaphalene, 0.5 g of copper bronze, 8.5 g of NaOH, and 175 cc of water are shaken in a suitable high pressure vessel at 200° for 75 minute. Cool, dilute with a little water, filter copper off, and acidify with coned HCl acid. Collect the resulting product, wash with water and dry in air. Recrystallize the resulting crude product with dilute ethanol to get a little over 5 g. 

Commercial copper bromide or its dimethyl sulfide complex contains impurities that are deleterious to the reaction. Therefore, the copper(l) bromide-dimethyl sulfide complex is prepared according to the method of House from copper(l) bromide generated by reduction of copper(ll) bromide (Aldrich Chemical Company, Inc., 99%) with sodium sulfite. Best results ctre obtained using copper(l) bromide-dimethyl sulfide complex freshly recrystallized according to the following procedure. 

The metallic arsenic is obtained primarily from its mineral, arsenopyrite. The mineral is smelted at 650 to 700°C in the absence of air. However, the most common method of production of the metal involves reduction of arsenic trioxide, AsOs with charcoal. Arsenic trioxide is produced by oxidation of arsenic present in the lead and copper concentrates during smelting of such concentrates. The trioxide so formed, readily volatilizes and is collected in a dust flue system where further treatment and roasting can upgrade the trioxide content. The trioxide vapors are then condensed and further purified by pressure leaching and recrystallization techniques. It is then reduced with charcoal to give metallic arsenic. 

Silver nitrate is prepared by dissolving silver metal in dilute nitric acid. The solution is evaporated and residue is heated to dull red heat with concentrated nitric acid to decompose impurities such as copper nitrate. Residue then is dissolved in water, filtered, and recrystallized to obtain pure silver nitrate. 

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