Cuprous chloride, as catalyst for

Cuprous -butylmercaptide, 42,22 Cuprous chloride as catalyst for 1,4 addition of Grignard reagents to ar,0-unsaturated esters, 41, 63 Cyanoacetic acid, tert-butyl ester, 41, 5... 

Using cuprous chloride as catalyst, hydrogen chloride adds to acetylene, giving 2-chloro-1,3-butadiene [126-99-8], chloroprene, C H Cl, the monomer for neoprene mbber. 

Allyl Chloride. Comparatively poor yields are obtained by the zinc chloride - hydrochloric acid method, but the following procedure, which employs cuprous chloride as a catalyst, gives a yield of over 90 per cent. Place 100 ml. of allyl alcohol (Section 111,140), 150 ml. of concentrated hydrochloric acid and 2 g. of freshly prepared cuprous chloride (Section II,50,i one tenth scale) in a 750 ml. round-bottomed flask equipped with a reflux condenser. Cool the flask in ice and add 50 ml. of concen trated sulphuric acid dropwise through the condenser with frequent shaking of the flask. A little hydrogen chloride may be evolved towards the end of the reaction. Allow the turbid liquid to stand for 30 minutes in order to complete the separation of the allyl chloride. Remove the upper layer, wash it with twice its volume of water, and dry over anhydrous calcium chloride. Distil the allyl chloride passes over at 46-47°. 

The cyclopropanation of alkenes, alkynes, and aromatic compounds by carbenoids generated in the metal-catalyzed decomposition of diazo ketones has found widespread use as a method for carbon-carbon bond construction for many years, and intramolecular applications of these reactions have provided a useful cyclization strategy. Historically, copper metal, cuprous chloride, cupric sulfate, and other copper salts were used most commonly as catalysts for such reactions however, the superior catalytic activity of rhodium(ll) acetate dimer has recently become well-established.3 This commercially available rhodium salt exhibits high catalytic activity for the decomposition of diazo ketones even at very low catalyst substrate ratios (< 1%) and is less capricious than the old copper catalysts. We recommend the use of rhodium(ll) acetate dimer in preference to copper catalysts in all diazo ketone decomposition reactions. The present synthesis describes a typical cyclization procedure. 

Aromatic aldehydes are prepared by passing carbon monoxide and dry hydrogen chloride through an ether or nitrobenzene solution of an aromatic hydrocarbon in the presence of a catalyst, commonly aluminum chloride with cuprous chloride as a carrier. The process is illustrated by the synthesis of p-tolualdehyde (51%). A convenient procedure for obtaining an equimolar mixture of anhydrous hydrogen chloride and carbon monoxide consists in dropping chlorosulfonic acid on formic acid, viz.,... 

In an improved process for the synthesis of tropilidene (5) by E. Muller, a solution of diazomethane in benzene is added gradually to refluxing benzene containing cuprous bromide as catalyst. Benzene is used in large excess, and the product is isolated most easily by filtering the solution from the catalyst and adding it to a solution of phosphorus pentachloride in carbon tetrachloride. The tropylium chloride which separates is dissolved in water and treated with perchloric acid to afford tropylium perchlorate in 85% yield. The success of the method is attributed to formation of the intermediate (3), a deactivated electrophilic carbon metal complex. Tropilidene... 

The following mechanism of the Sandmeyer reaction has been proposed as a result of a kinetic study, and incidentally accounts for the formation of the azu compounds as by-products. The catalyst is the CuCl ion produced in the dissolution of cuprous chloride in the chloride solution ... 

For reaction with hydrogen haUdes, the substitution reaction with haUde ion easily occurs when a cuprous or cupric compound is used as the catalyst (23) and yields a halogenated aHyl compound. With a cuprous compound as the catalyst at 18 °C, the reaction is completed in 6 h. Zinc chloride is also a good catalyst (24), but a by-product, diaHyl ether, is formed. 

The Ullman reaction has long been known as a method for the synthesis of aromatic ethers by the reaction of a phenol with an aromatic halide in the presence of a copper compound as a catalyst. It is a variation on the nucleophilic substitution reaction since a phenolic salt reacts with the halide. Nonactivated aromatic halides can be used in the synthesis of poly(arylene edier)s, dius providing a way of obtaining structures not available by the conventional nucleophilic route. The ease of halogen displacement was found to be the reverse of that observed for activated nucleophilic substitution reaction, that is, I > Br > Cl F. The polymerizations are conducted in benzophenone with a cuprous chloride-pyridine complex as a catalyst. Bromine compounds are the favored reactants.53,124 127 Poly(arylene ether)s have been prepared by Ullman coupling of bisphenols and... 

To manufacture aniline from chlorobenzene and ammonia, cuprous oxide or diamino cuprous chloride has been used as the catalyst and the reaction is usually carried out in the liquid phase under pressure (7). There are few reports on the reaction in gas phase. Jones (8) found that CuX was active for aniline formation while ZnX led to the formation of dichlorobenzenes. The reaction of benzaldehyde with ammonia over zeolite has never been reported. 

A solution of 24 g of 4-(N,N-dimethylaminoethoxy)bromobenzene was added dropwise over 45 min to magnesium in 90 ml of anhydrous tetrahydrofuran. 2 ml of 1,2-dibromoethane were added as catalyst. After the addition, the mixture was stirred at 25°C for one hour to obtain a solution of 0.7 M of 4-(N,N-dimethylaminoethoxy)-benzene magnesium bromide which was then added to a solution of 6.16 g of dimethylsulfide-cuprous bromide complex in 20 ml of tetrahydrofuran. The mixture was stirred at room temperature for 20 min and a solution of 3.7 g of 3,3-[l,2-(ethanediyl-bisoxy)]-5a,10a-epoxy-17a-prop-l-ynyl-8(9(1 L))-estrene-17p-ol in 50 ml of tetrahydrofuran was added thereto dropwise over a few minutes. The mixture was stirred under an inert atmosphere for one hour and was then poured into a solution of 15 g of ammonium chloride in 20 ml of iced water. The mixture was extracted with ether and the organic phase was washed with aqueous saturated sodium chloride solution, was dried and evaporated to dryness under reduced pressure. The 18.3 g of oil were chromatographed over silica gel and eluted with chloroform to obtain 4.5 g of 3,3-[l,2-ethanediyl-bisoxy]-lip-[4-(N,N-dimethylaminoethoxy)phenyl]-17a-(prop-l-ynyl)-89-estrene-5a,17p-diol with a specific rotation of [a]D20 =-44(+/-)1.5° (c = 1% in chloroform). 

Acetylene is condensed to vinylacetylene and divinylacetylene by cuprous chloride and ammonium chloride. Similar additions of other compounds containing an active hydrogen atom occur in the presence of various catalysts. Mercury salts ate most effective in the vapor-phase reaction of acetylene with hydrogen chloride to give vinyl chloride (100%). Basic catalysts such as potassium hydroxide, potassium ethoxide, or zinc oxide are used for the vinylation of alcohols, glycols, amines, and acids. Most of these reactions involve the use of acetylene under pressure, and few have been described as simple laboratory procedures. Chloroacetic acid, however, reacts with acetylene at atmospheric pressure in the presence of mercuric oxide to yield vinyl chloro-acetate (49%). ... 

Example 3 was also repeated using from 5 to 10 mole % of cuprous oxide, cuprous chloride, cuprous iodide and copper dust, as the catalyst for conversion of the iodovanillin to hydroxyvanillin. Recovery of 5-hydroxyvanillin was 80-85% (remainder vanillin) with copper dust, from 70-80% with the copper oxide or salts. 

In both cases the catalyst cannot be reduced to a lower degree of oxidation since trouble will arise due to precipitation of cuprous chloride. Even the palladium salt concentration which can be kept in solution depends on the degree of oxidation of the catalyst. At lower degrees of oxidation the concentration decreases due to removal from the catalyst as metallic palladium. Due to the high corrosive ability of the catalyst solution, titanium is used as construction material for all catalyst-contaning equipment. The reactor for the single-stage process is usually resin-(or ceramic)-lined. 

In the early sixties, a redox catalyst system for the addition of halogenated hydrocarbons to olefins was discovered at Dow (3). The addition was carried out in the presence of a mixture of cuprous chloride and an amine such as piperidine or cyclohexylamine (Scheme II). Essentially quantitative yields of the one-to-one adducts could be obtained and the new catalyst system worked as well with carbon tetrachloride as bromotrichloromethane. Independently, M. Asscher and D. Vofsi (4) found a similar catalyst system. 

Cuprous chloride supported on a Y-type zeolite by high-temperature anhydrous reaction gave a DMC productivity as good as the active carbon supported catalyst. Addition of tetraalkyl ammonium chlorides to copper chlorides on zeolites or alumina increased the DMC productivity and the catalyst life. In any case, active carbons are the most preferred supports for this reaction, compared to zeolites or alumina, because of higher DMC productivity when working with copper(II) chlorides. 

Ethanol is produced from ethylene and liquid water under high pressure and at temperatures of 200° to 300° C. in the presence of dissolved or suspended salts such as silver nitrate, cuprous chloride, and mercuric chloride which have an affinity for ethylene. Bomb experiments only are described. For instance, by operating with 20 cc. of water in a 150 cc. bomb and 40 atmospheres of ethylene cold, and by heating to 300° C. for six hours without a catalyst only one per cent conversion of ethylene to ethanol is obtained. However, by using water saturated with mercuric chloride under otherwise the same conditions, a 10 per cent ethylene conversion is obtained.81... 

Most of the absorbers for CO involve reduced copper salts, and cuprous chloride generally is used This can be in acid, which is the case here, or in base. The only difference is in the order that you take out the gases. Cuprous sulfate can be used as an absorber for CO, but it absorbs slowly unless beta naphthol is added to it to act as a catalyst. The capacity of acid cuprous chloride for CO is generally pretty high. One mL wilt absorb 18 mL of CO gas. 

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