Allylic chlorides, reaction with zinc-copper

Attempts were made to extend the r,(7-transfer of allyl ligand from palladium to other, metals (fdf) (magnesium, copper, zinc, cadmium, and liquid gallium). It has been found that these metals do not form their respective allyl derivatives in reaction with rr-allyl-palladium chloride. 

Nickel, palladium and copper catalysts can effect a variety of C — C bond-forming reactions P to the ester carbonyl via j8-zinc esters. These include 1,4-addition to a,jS-unsaturated carbonyl compounds (copper), arylation with aryl halides (palladium, nickel), allylation with allyl chloride (copper), and acylation with acyl chlorides (palladium, copper). " ... 

Copper derivatives, in the form of cuprates (RCu(X)Li), are usually prepared in situ from lithium, magnesium or zinc compounds, by reaction with a Cu(I) sonrce snch as CnCN. They are often used to improve conversions using, for example, an acid chloride or an allylic halide as electrophile - a number of examples appear in other sections of this book. They are also nsefnl as the organometallic partners in some crosscoupling reactions (using cobalt catalysts). ... 

CARBONIC ACID, LITHIUM SALT (554-13-2) LijCOj Aqueous solution is an organic base. Violent reaction with acids. Inconpatible with fluorine, germanium, lead diacetate, magnesium, mercurous chloride, silicon, silver nitrate, titanium. Aqueous solution incompatible with organic anhydrides, acrylates, alcohols, aldehydes, alkylene oxides, substituted allyls, cellulose nitrate, cresols, caprolactam solution, epichlorohydrin, ethylene dichloride, isocyanates, ketones, glycols, nitrates, phenols, vinyl acetate. Exothermic decomposition with maleic anhydride. Corrodes aluminum, copper, zinc in the presence of moisture. On small fires, use any extinguishing agent. 

HYDROXYLAMINE (7803-49-8) A powerful reducing agent. Aqueous solution is a base. Contact with water or steam causes decomposition to ammonium hydroxide, nitrogen, and hydrogen. Contaminants and/or elevated temperatures above certain ranges (reported at 158°F/70°C and 265°F/129°C) can cause explosive decomposition. Moisture in air or carbon dioxide may cause decomposition. Violent reaction with oxidizers, strong acids, copper(ll) sulfate, chromium trioxide, potassium dichromate, phosphorus chlorides, metals calcium, sodium, zinc. Incompatible with carbonyls, pyridine. Forms heat-sensitive explosive mixtures with calcium, zinc powder, and possibly other finely divided metals. Aqueous solution incompatible with organic anhydrides, acrylates, alcohols, aldehydes, alkylene oxides, substituted allyls. 

Joint catalysis by tin(IV) chloride and zinc chloride induces coupling of the acetal 114 with the alkyne 115 to give the propargyl ether 116. Allyl halides condense with terminal alkynes in DMF in the presence of copper(I) iodide, potassium carbonate and tetrabutylammonium chloride under phase-transfer conditions to afford eneynes, e.g. equation 19. Palladium-catalysed coupling reactions of 1-bromoallenes with terminal acetylenes have been reported for the first time thus acetylene and the allenes 117 (R R = Me or Et) in triethylamine in the presence of tetrakis(triphenylphosphine)palladium and... 

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