Cuprous chloride addition compounds

Application of the cuprous chloride-catalyzed conjugate Grignard addition to A -5a-3-ketones (13) gives la-methyl compounds (14) in yields up to... 

When cobaltous chloride is added instead of cuprous chloride, a 20% yield of the conjugate addition product and a 40% yield of compound 29 are obtained from 7. The isolation of some biphenyl indicates the probable presence of phenyl radicals. 

Attempts to utilize an in situ diazotization procedure (1.2 equiv. isoamyl nitrite, acetic acid, 25 °C, 30 min) [58,60-62] for DNA cleavage were made via generation of diazonium compound 17 directly from commercially available 9-aminofluorene (Fig. 18) [58]. However, addition of this solution to aqueous buffers (pH = 4-7) did not produce any DNA cleavage neither did the addition of cuprous chloride, which had been demonstrated to be successful in activating diazonium compounds for DNA cleavage [60-62]. This may be explained by ... 

It is important that the temperature should be held at 25-30° during the addition of the diazonium chloride to the cuprous chloride solution. At lower temperatures the decomposition of the unstable additive compound proceeds too slowly,... 

Another chlorinated compound which, like vinyl chloride, is used only in its polymeric form, is chloroprene (2-chloro-l,3-butadiene), which is polymerized to make neoprene, first produced in 1940. As far as is known (17) y the monomer is made commercially only from acetylene via addition of hydrochloric acid to monovinylacetylene in the presence of cuprous chloride, but syntheses from butylenes or butadiene have been described. The production of chloroprene exceeded 100,000,000 pounds per year at the wartime peak and has been somewhat lower since then, but in view of the many valuable properties of the neoprene rubber it will continue to be important. 

Fortunately, most of the palladium addition reactions with olefins can be carried out catalytically in the palladium compound so that large amounts of the expensive palladium compounds are not needed. As in the inorganic palladium salt additions, cupric chloride is a useful reoxidant. This, of course, limits the catalytic reaction to cases where olefin isomerization is not a problem. The cupric chloride is reduced to cuprous chloride during the reaction. As in the acetaldehyde synthesis, the reaction may be made catalytic in copper as well as palladium by adding oxygen and, in this case, hydrogen chloride also. 

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%). ... 

Derivation (1) From propylene oxygen and ammonia with either bismuth phosphomolybdate or a uranium-based compound as catalysts (2) addition of hydrogen cyanide to acetylene with cuprous chloride catalyst (3) dehydration of ethylene cyanohydrin. 

Compound 65a has been prepared by Rasmussen and Hassner by a different pathway, as depicted in Scheme 72 (73TL2783). Silyl ether 203 was allowed to react in the presence of a catalytic amount of cuprous chloride with carbomethoxysulfamoyl chloride (204) (63CB56) in acetonitrile. Upon anhydrous work-up, adduct 205 was obtained in addition to compound 65a. 

This reaction was first reported by Bart in 1910. It is the synthesis of arylarsenic acids from aromatic diazonium compounds with alkali arsenites in the presence of cupric salts, powdered silver, or copper. Therefore, this reaction is generally known as the Bart reaction. In addition, the reaction between aromatic diazonium and arsenious chloride in the presence of trace amounts of cuprous chloride is referred to as the Scheller modification. Besides the Scheller modification, the Sakellarios modification is the reaction between sulfanilamide and phenyldisodium arenite. ... 

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