Cuprous azide chloride

Singh published details of the preparation of cuprous azide from cuprous chloride dissolved in saturated aqueous sodium chloride in presence of a small amount of potassium bisulfite and acidified by acetic acid. The cuprous azide was precipitated by addition of aqueous sodium azide [76,110]. Another way of preparing CuNs is based on the reaction of freshly prepared cuprous oxide (from cupric hydroxide and... 

As with other metals, cupric and cuprous halides can detonate in contact with potassium. In addition, the action of cuprous chloride on lithium azide gives rise to a very violent reaction. 

Examples of the three mechanistic types are, respectively (a) hydrolysis of diazonium salts to phenols89 (b) reaction with azide ion to form aryl azides90 and (c) reaction with cuprous halides to form aryl chlorides or bromides.91 In the paragraphs that follow, these and other synthetically useful reactions of diazonium intermediates are considered. The reactions are organized on the basis of the group that is introduced, rather than on the mechanism involved. It will be seen that the reactions that are discussed fall into one of the three general mechanistic types. 

The addition of copper to a boiling solution of benzenesulphonyl azide in methanol gave benzenesulphonamide 18 (80%) as the major product together with minor amounts of methylenebis(benzenesulphon-amide) 22 and 1,3,5-tris (benzenesulphonyl) hexahydro-s-triazine 23, resulting from condensation of 18 with the formaldehyde formed in the reaction 33>. Cuprous chloride was even more effective, but cuprous... 

Chloro-3-methoxycarbonyl-5,6-diphenylpyrazine refluxed with sodium methoxide gave 2-carboxy-3-methoxy-5,6-diphenylpyrazine (371) and the attempted Schmidt reaction of 2,5-dimethoxycarbonylpyrazine, in concentrated sulfuric acid with trichloroacetic acid at 60° with subsequent addition of sodium azide, gave 2,5-dicarboxypyrazine (1176). 2-Methoxy-3-methoxycarbonyl-5,6-diphenylpyrazine, when refluxed with cuprous chloride in dry dimethylformamide, gave 2-carboxy-3-methoxy-5,6-diphenylpyrazine (10%) 2-hydroxy-3-methoxycarbonyl-5,6-diphenyl-pyrazine similarly treated gave 5-hydroxy-2,3-diphenylpyrazine (30%) (837). 

Acetylene additions Hexafluoro-2-butyne. Iodine azide. 1-Iodoheptafluoropropane. Acetylenic coupling n-Butyllithium. Cuprous chloride. 

Examples of the three mechansims are, respectively (a) hydrolysis of aryl diazonium salts to phenols (b) reaction of aryl diazonium ions with Ns to give the aryl azides " and (c) the Sandmeyer reaction, involving cuprous chloride or bromide for synthesis of aryl halides. Specific synthetically important substitution processes are considered in the succeeding sections. 

If a methanol solution of sodium azide is added to a chloroform solution of cuprous chloride and triphenylphosphine, the dimer which is obtained contains a bridging azide group (8.112). 

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