Active copper

Activated copper bronze. Commercial copper bronze does not always give satisfactory yields in the Ullmann reaction, but uniform results can... 

Place 50 g. of o-chloronitrobenzene and 75 g. of clean dry sand in a 250 ml. flask equipped with a mechanical stirrer. Heat the mixture in an oil or fusible metal bath to 215-225° and add, during 40 minutes, 50 g. of copper bronze or, better, of activated copper bronze (Section 11,50, 4) (1), Maintain the temperature at 215-225° for a further 90 minutes and stir continuously. Pour the hot mixture into a Pyrex beaker containing 125 g. of sand and stir until small lumps are formed if the reaction mixture is allowed to cool in the flask, it will set to a hard mass, which can only be removed by breaking the flask. Break up the small lumps by powdering in a mortar, and boil them for 10 minutes with two 400 ml. 

The experimental conditions for conducting the above reaction in the presence of dimethylformamide as a solvent are as follows. In a 250 ml. three-necked flask, equipped with a reflux condenser and a tantalum wire Hershberg-type stirrer, place 20 g. of o-chloronitrobenzene and 100 ml. of diinethylform-amide (dried over anhydrous calcium sulphate). Heat the solution to reflux and add 20 g. of activated copper bronze in one portion. Heat under reflux for 4 hours, add another 20 g. portion of copper powder, and continue refluxing for a second 4-hour period. Allow to cool, pour the reaction mixture into 2 litres of water, and filter with suction. Extract the solids with three 200 ml. portions of boiling ethanol alternatively, use 300 ml. of ethanol in a Soxhlet apparatus. Isolate the 2 2- dinitrodiphenyl from the alcoholic extracts as described above the 3ueld of product, m.p. 124-125°, is 11 - 5 g. 

In contrast to the situation in the absence of catalytically active Lewis acids, micelles of Cu(DS)2 induce rate enhancements up to a factor 1.8710 compared to the uncatalysed reaction in acetonitrile. These enzyme-like accelerations result from a very efficient complexation of the dienophile to the catalytically active copper ions, both species being concentrated at the micellar surface. Moreover, the higher affinity of 5.2 for Cu(DS)2 compared to SDS and CTAB (Psj = 96 versus 61 and 68, respectively) will diminish the inhibitory effect due to spatial separation of 5.1 and 5.2 as observed for SDS and CTAB. 

ProducL Sulfur, Chlorine, Active Copper strip 40° 100° Density, at Total acid Pour... 

A flow diagram for the system is shown in Figure 5. Feed gas is dried, and ammonia and sulfur compounds are removed to prevent the irreversible buildup of insoluble salts in the system. Water and soHds formed by trace ammonia and sulfur compounds are removed in the solvent maintenance section (96). The pretreated carbon monoxide feed gas enters the absorber where it is selectively absorbed by a countercurrent flow of solvent to form a carbon monoxide complex with the active copper salt. The carbon monoxide-rich solution flows from the bottom of the absorber to a flash vessel where physically absorbed gas species such as hydrogen, nitrogen, and methane are removed. The solution is then sent to the stripper where the carbon monoxide is released from the complex by heating and pressure reduction to about 0.15 MPa (1.5 atm). The solvent is stripped of residual carbon monoxide, heat-exchanged with the stripper feed, and pumped to the top of the absorber to complete the cycle. 

The reaction kinetics for the dehydrogenation of ethanol are also weU documented (309—312). The vapor-phase dehydrogenation of ethanol ia the presence of a chromium-activated copper catalyst at 280—340°C produces acetaldehyde ia a yield of 89% and a conversion of 75% per pass (313). Other catalysts used iaclude neodymium oxide and samarium hydroxide (314). 

Chlorotrifluoromethane [75-72-9] M 104.5, m -180 , b -81.5 . Main impurities were CO2, O2, and N2. The CO2 was removed by passage through saturated aqueous KOH, followed by cone H2SO4. The O2 was removed using a tower packed with activated copper on Kieselguhr at 200°, and the gas dried over P2O5. 

Dicblorodifluoromethane (Freon 12) 175-71-8] M 120.9, m -158", b -29.8"/atm, 42.5"/10atm. Passage through saturated aqueous KOH then cone H2SO4, and a tower packed with activated copper on Kielselguhr at 200° removed CO2 and O2. A trap cooled to -29° removed a trace of high boiling material. It is a non-flammable propellant. 

Aryl bromides were also perfluoroethylated under these conditions [205] The key to improved yields was the azeotropic removal of water from the sodium perfluoroalkylcarboxylate [205] Partial success was achieved with sodium hepta-fluorobutyrate [204] Related work with halonaphthalene and anthracenes has been reported [206 207] The main limitation of this sodium perfluoroalkylcarboxylate methodology is the need for 2 to 4 equivalents of the salt to achieve reasonable yields A trifluoromethylcopper solution can be prepared by the reaction of bis(tri-fluoromethyl)mercury with copper powder in /V-methylpyrrolidone (NMP) at 140 °C [208] (equation 138) or by the reaction of N-trifluoromethyl-A-nitro-sotnfluoromethane sulfonamide with activated copper in dipolar aprotic solvents [209] This trifluoromethylcopper solution can be used to trifluoromethylate aro matic [209], benzylic [209], and heterocyclic halides [209]... 

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. 

The axially chiral natural product mastigophorene A (70) was synthesized via a copper-catalyzed asymmetric homocoupling of bromooxazoline 68. Treatment of 68 with activated copper in DMF afforded 69 in 85% yield as a 3 1 mixture of atropisomers. The major atropisomer was converted into mastigophorene A (70) the minor regioisomer was transformed into the atropisomeric natural product mastigophorene... 

To a mixture of naphthyloxazoline 71 (4.31 g, 12.97 mmol) in pyridine (4 mL) was added activated copper (1.99 g). The mixture was heated to reflux for 24 h then was cooled to rt, diluted with CH2CI2 and washed with aqueous ammonia until the copper had been completely removed. The organic phase was washed with water then dried over anhydrous magnesium sulfate, filtered, and concentrated to afford the title compound as a tan solid. This material was used without further purification. 

A low-pressure process has been developed by ICl operating at about 50 atm (700 psi) using a new active copper-based catalyst at 240°C. The synthesis reaction occurs over a bed of heterogeneous catalyst arranged in either sequential adiabatic beds or placed within heat transfer tubes. The reaction is limited by equilibrium, and methanol concentration at the converter s exit rarely exceeds 7%. The converter effluent is cooled to 40°C to condense product methanol, and the unreacted gases are recycled. Crude methanol from the separator contains water and low levels of by-products, which are removed using a two-column distillation system. Figure 5-5 shows the ICl methanol synthesis process. 

There are many ways to produce acetaldehyde. Historically, it was produced either hy the silver-catalyzed oxidation or hy the chromium activated copper-catalyzed dehydrogenation of ethanol. Currently, acetaldehyde is obtained from ethylene hy using a homogeneous catalyst (Wacker catalyst). The catalyst allows the reaction to occur at much lower temperatures (typically 130°) than those used for the oxidation or the dehydrogenation of ethanol (approximately 500°C for the oxidation and 250°C for the dehydrogenation). 

The advanced all-metallic catalysts are believed to be formed by bonding active copper-nickel alloys onto stainless steel wires. Under the scanning electron microscope, it appears that the surface area may be more than twenty times the geometric surface area (42) ... 

Vinylic halides can be coupled to give 1,3-butadienes by treatment with activated copper powder in a reaction analogous to the Ullmann reaction (13-14). " This reaction is stereospecific, with retention of configuration at both carbons. 

Byproducts, such as methyltrichlorosilane (Mj), trimethylchlorosilane (M3), methyldichlorosilane (MH), and some residuals (R) having a boiling point above 70 C are also produced. One of the most efficient ways to prepare the active copper-silicon alloy is by the uniform mixing of CuCl and silicon particles. The following reaction takes place when the mixture is heated to the reaction temperature ... 

In this reaction, the more active zinc replaces the less active copper from solution. The reaction is evident because the blue color of the copper sulfate solution slowly turns colorless and a deposit of copper can be seen to form on the strip of zinc. 

When you place a piece of zinc metal into a solution of CuS04, you expect a chemical reaction because the more active zinc displaces the less active copper from its compound (Sec. 7.3). We learned in Chap. 13 that this is an oxidation-reduction reaction, involving transfer of electrons from the zinc to the copper. 

Structural Understanding of ATRP Active Copper Complexes. 227... 

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