Cupric carbonate, reaction with

The details of the cupric salt reaction with the palladium adduct are not clear. Exchange to form a cupric alkyl is one possibility or complex formation,"probably with chloride bridges between the palladium adduct and cupric chloride, may occur with subsequent anion shift from palladium to carbon or perhaps an Sn2 displacement of the complex metal group by an anion may occur. Rearrangements producing 1,3 and 1,4 substituted products from linear olefins have also been observed. For example, 1-butene produced several percent of 1,3- and 1,4-chloro acetates and diacetates under the reaction conditions used 16>. "Hydrido-palladium acetate or chloride" -complexes would seem to be likely intermediates in these arrangements. 

Furthermore we found that kasugamycin forms a chelate compound with basic cupric carbonate (7), which is stable to acid and unstable to heat and base. This evidence together with the results obtained above strongly supports the amidine structure (13) for kasugamycin. Finally the amidine compound was successfully prepared by the reaction of kasuganobiosamine with the diethyl ester of oxalimidic acid (14) and... 

In real systems (hydrocarbon-02-catalyst), various oxidation products, such as alcohols, aldehydes, ketones, bifunctional compounds, are formed in the course of oxidation. Many of them readily react with ion-oxidants in oxidative reactions. Therefore, radicals are generated via several routes in the developed oxidative process, and the ratio of rates of these processes changes with the development of the process [5], The products of hydrocarbon oxidation interact with the catalyst and change the ligand sphere around the transition metal ion. This phenomenon was studied for the decomposition of sec-decyl hydroperoxide to free radicals catalyzed by cupric stearate in the presence of alcohol, ketone, and carbon acid [70-74], The addition of all these compounds was found to lower the effective rate constant of catalytic hydroperoxide decomposition. The experimental data are in agreement with the following scheme of the parallel equilibrium reactions with the formation of Cu-hydroperoxide complexes with a lower activity. 

In any reaction where the cleavage of a carbon-hydrogen bond is important, the introduction of a metal ion into the molecule in the proper position will facilitate reaction. For example, in the elimination of the elements of a phosphoric acid monoester from the molecule below, the electrostatic attraction of the cupric ion facilitates removal of the proton on the o -carbon atom with subsequent elimination of the phosphoryl residue (8). 

A suspension of polymeric cupric dimethoxide in pyridine reacts with CO2 to yield the cupric methyl carbonate. The CO2 moiety is, however, very labile the insertion could be reversed by heating the reaction mixture at 80" under a stream of nitrogen [SO]. Another reversible carbon dioxide carrier was found in copper(I) rerr-butoxide, which was stabilized by rerr-butyl isocyanide. The rerr-butyl carbonato complex was formed during the reaction with CO2 [811. Carbon dioxide also reacts with ROCu(PPh3)2 0 produce (ROCOj)Cu(PPhj>3, Hydrolysis or thermolysis of these alkylcarbonato complexes gives the binuctear carbonato copper (I) complex (PPhj>2 CuCK Oj Cu(PPhj)2, which can be further convened into the bicarbonate complex f(HC)C02)Cu(PPh3)3] by reaction with CO2 in moist solvents [82],... 

Reaction with carbon monoxide. Cupric dimethoxide reacts with carbon monoxide in pyridine solution at 35 70° to produce dimethyl carbonate in yields as high as 84%. 

N-Acetylation of basic amino acids. The reagent reacts with an aqueous solution of the copper salt of a basic amino acid to give the N-acetyl derivative.1 The procedure is superior to the usual synthesis in which acetic anhydride is used because the reaction goes to completion. As applied to L-lysine, the method is simple and gives better yields of pure e-N-acetyl-L-lysine. Excess cupric carbonate is added to a boiling aqueous solution of L-lysine (0.1 mole) and the solution is filtered and cooled to 25° and treated with sodium bicarbonate, p-nitrophenylacetate, and a few milliliters of ethyl acetate to keep the acetate in solution. After stirring for 15 hrs the copper salt which separates is filtered, suspended in water, and freed of copper with H2S. The solution is evaporated to dryness and the N-acetyllysine crystallized from water-ethanol. 

Activated Carbon Sulfur removal from natural gas by adsorption at ambient temperature on carbon, activated with cupric oxide, is widely used. Carbon physically adsorbs sulfur compounds to its surface and the cupric oxide reacts with hydrogen sulfide. The activated carbon is typically regenerated every 30 days by passing steam through the bed at a temperature of 230°C (450°F) for 8—10 hr while air is injected. Oxygen in the air reacts with the metal sulfide to form the metal oxide and sulfur dioxide. These reactions are ... 

ZIRCAT (7440-67-7) Finely divided material is spontaneously flammable in air may ignite and continue to bum under water. Violent reactions with oxidizers, alkali hydroxides, alkali metals (and their compounds), carbon tetrachloride, cupric oxide, lead, lead oxide, lead peroxide (combined material can burn explosively, and is sensitive to friction and static electricity), nitryl fluoride, oxygen difluoride, phosphoms, potassium, potassium compounds (potassium chlorate, potassium nitrate), sodium borate, sodium hydroxide. Explodes if mixed with hydrated borax when heated. Contact with lithium chromate may cause explosion above 752°F/450°C. Forms explosive mixture with potassium chlorate. Dusts of zirconium ignite and explode in a carbon dioxide atmosphere. Contact with ammonium-V-nitrosophenylhydroxylamine above 104°F/40°C forms an explosive material. Incompatible with boron, carbon, nitrogen, halogens, lead, platinum, potassium nitrate. In case of fire, use approved Class D extinguishers or smothering quantities of dry sand, crushed limestone, clay. 

The production of another important chemical and polymer intermediate, acetic acid, was revolutionized by the Wacker process that was introduced in 1960. It was a simple, high yield process for converting ethylene to acetaldehyde, which replaced the older process based on ethanol and acetylene. In the Wacker reaction, the palladium catalyst is reduced and then reoxidized. Ethylene reacts with water and palladium chloride to produce acetaldehyde and palladium metal. The palladium metal is reoxidized by reaction with cupric chloride, which is regenerated by reaction with o gen and hydrochloric acid. In 1968, BASF commercialized an acetic acid process based on the reaction of carbon monoxide and methanol, using carbonyl cobalt promoted with an iodide ion (74). Two years later, however, Monsanto scored a major success with its rhodium salt catalyst with methyl iodide promoter. Developed by James F. Roth, this new catalyst allowed operation at much milder conditions (180°C, 30-40 atm) and demonstrated high selectivity for acetic acid (75). 

Nucleophilic Displacement. PhTMS-BF3 0Et2 system has been shown to be useful in the transformation of allylic alcohols to allylic sulfides (eq IS). Preparation of unsymmetrical diaryl sulfides can be achieved by reaction of arenediazonium tetraflu-oroborates with PhSTMS (eq 19). In some cases, addition of cupric sulfide increases the yield of the diaryl sulfides. The use of (phenylthio)trimethylsilane as a coupling partner in palladium catalyzed reactions with aUyl carbonates (eq 20) and aryl iodide (eq 21) has been explored. ... 

Acid amides give a color reaction with fluorescein chloride which has already been described in the discussion on amines (p. 324). The biuret reaction is given by compounds which contain a group in which two carbonamide groups are bound to one carbon or nitrogen atom, as, for example, in malonamide (I), biuret (II), or oxamide (III) in an alkaUne medium these substances give a red-violet complex compound with cupric hydroxide. 

Cupric ion has a unique abitity to compete with oxygen for a carbon-centered free radical (compare reaction 2) ... 

Oxychlorination of Ethylene or Dichloroethane. Ethylene or dichloroethane can be chlorinated to a mixture of tetrachoroethylene and trichloroethylene in the presence of oxygen and catalysts. The reaction is carried out in a fluidized-bed reactor at 425°C and 138—207 kPa (20—30 psi). The most common catalysts ate mixtures of potassium and cupric chlorides. Conversion to chlotocatbons ranges from 85—90%, with 10—15% lost as carbon monoxide and carbon dioxide (24). Temperature control is critical. Below 425°C, tetrachloroethane becomes the dominant product, 57.3 wt % of cmde product at 330°C (30). Above 480°C, excessive burning and decomposition reactions occur. Product ratios can be controlled but less readily than in the chlorination process. Reaction vessels must be constmcted of corrosion-resistant alloys. 

Cupric chloride or copper(II) chloride [7447-39 ], CUCI2, is usually prepared by dehydration of the dihydrate at 120°C. The anhydrous product is a dehquescent, monoclinic yellow crystal that forms the blue-green orthohombic, bipyramidal dihydrate in moist air. Both products are available commercially. The dihydrate can be prepared by reaction of copper carbonate, hydroxide, or oxide and hydrochloric acid followed by crystallization. The commercial preparation uses a tower packed with copper. An aqueous solution of copper(II) chloride is circulated through the tower and chlorine gas is sparged into the bottom of the tower to effect oxidation of the copper metal. Hydrochloric acid or hydrogen chloride is used to prevent hydrolysis of the copper(II) (11,12). Copper(II) chloride is very soluble in water and soluble in methanol, ethanol, and acetone. 

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