Amines oxidations, copper bromide

COPPER BROMIDE (7789-45-9) BFjCu Aqueous solution is an acid. Incompatible with bases, inducing amines, amides, and inorganic hydroxides strong oxidizers, including chlorine, fluorine, peroxides and hydroperoxides potassium. 

Suitable catalysts are copper(I) salts [e.g., Cu(I) chloride, bromide, and sulfate] in combination with amines to form oxidation sensitive phenolates. The amine/copper salt ratio must be made as large as possible, to minimize the formation of diphenylquinone and to give a high molecular weight. 

The reaction with ammonia or amines, which undoubtedly proceeds by the SNAr mechanism, is catalyzed by copper8" and nickel105 salts, though these are normally used only with rather unreactive halides.106 This reaction, with phase transfer catalysis, has been used to synthesize triarylamines.107 Copper ion catalysts (especially cuprous oxide or iodide) also permit the Gabriel synthesis (0-58) to be applied to aromatic substrates. Aryl bromides or iodides are refluxed with potassium phthalimide and Cu 0 or Cul in dimethylacetamide to give N-aryl phthalimides, which can be hydrolyzed to primary aryl amines.108... 

Compounds with a terminal acetylenic function, RCsCH, react with 1-bromoalkynes, R CsCBr in the presence of an aliphatic amine and a catalytic amount of a copper salt to give the coupling products RCsCCsCR. This useful reaction, discovered by Cadiot and Chodkiewicz [195], gives a ready access to a number of poly-unsaturated systems. The usual procedure involves dropwise addition of the bromoacetylene R GsCBr to a mixture of the acetylene RCsCH, ethylamine, ethanol or methanol, a catalytic amount of copper chloride or bromide and a small amount of hydroxylamine.HCl. This reducing agent prevents the oxidation to copper ). The reaction is usually very fast at temperatures in the region of 30 C. Since much heat is evolved, the reaction can be monitored easily by temperature observation. 

In addition to reactions initiated with copper metal, reactions have been conducted with copper salts, such as copper oxides, alloys and coordination complexes. Reactions with many bases in several polar solvents have also been explored. Diphenylamine and o-bromonitrobenzene couple with stoichiometric amounts of copper(I) oxide and copper(I) bromide in DMA (equation 59)234. The synthesis of triaryl amines from aryl iodides and arylamines in one-pot proceeds in the presence of Cul and potassium tart-butoxide at 135 °C235. The highest yields were obtained with aryl iodides and electron-rich arylamines. 

MERCURIC BROMIDE (7789-47-1) HgBfj Noncombustible solid. Light and heat cause decomposition keep out of sunlight. Violent reaction with strong oxidizers, including chlorine trifluoride. Aqueous solution is acidic. Incompatible with acetylene, ammonia, azides (may form mercury azide, a heat- and shock-sensitive explosive), bases, caustics, amines, amides, inorganic hydroxides calcium (forms amalgam) carbide, chlorine dioxide, copper and its alloys hydrazines, indium (violent at 662°F/350°C), lithiiun, potassium, rabidium, sodium. Note Be especially careful not to allow this compound to accumulate in sink traps with many of the above incompatible... 

The various aspects of oxidative polymerization of phenols have been thoroughly reviewed. Most commonly PPEs are produced by the self-con-densation of a monovalent phenol in the presence of oxygen and a metal-amine-complex catalyst. Manganese, copper and cobalt can be used as the metal in the catalyst. Cu+ is most commonly utilized. For example, the preparation of the catalyst can be achieved by stirring cuprous bromide and di-n-butyl amine in toluene. ... 

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