Diazonium salts reaction with cuprous halides

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. 

Introduction. The diazo group, N2X, is easily replaced by a number of other functional groups, such as OH, Cl, Br, I and CN. This affords a convenient method for the preparation of such derivatives as cannot be obtained by other methods except with great difficulty. The replacement of N2X by a halogen group is accomplished by heating the solution of diazonium salt with cuprous halide (Sandmeyer reaction) or with finely divided copper (Gatterman reaction). In the preparation of iodides the catalytic effect of copper is not required it is necessary only to pour the diazonium salt into a solution of potassium iodide and then to acidify the solution ... 

Another common transformation of diazonium salts is their conversion to aryl halides by reaction with cuprous salts (CuX), in what is known as the Sandmeyer reaction, named after Traugott Sandmeyer (Switzerland 1854-1922). This means that the Ar-NH2 ArX conversion is possible, where Ar = an aryl group. When 132 is treated with cuprous bromide (CuBr), the product is bromobenzene (18). The reaction works with many other cuprous salts as well, including cuprous chloride (CuCl). A variation of this reaction treats the diazonirun salt with cuprous cyanide (CuCN) to give a nitrile. In this manner, 4-methylanihne (24) is treated with HCI and NaN02 and then with CuCN to give 4-methyl-l-cyanobenzene (134). 

Aryl Halides from Diazonium Ion Intermediates. Replacement of diazonium groups by halides is a valuable alternative to direct halogenation for the preparation of aryl halides. Aryl bromides and chlorides are usually prepared by a reaction using the appropriate Cu(I) salt, which is known as the Sandmeyer reaction. Under the classic conditions, the diazonium salt is added to a hot acidic solution of the cuprous halide.99 The Sandmeyer reaction occurs by an oxidative addition reaction of the diazonium ion with Cu(I) and halide transfer from a Cu(III) intermediate. 

Answer Procedure Xli-7 which requires a diazonium salt, and the Roscnumd-von Braun reaction in which an aromatic halide is treated with cuprous cyanide as shown below. 

For the preparation of chlorides or bromides, the diazonium salt is decomposed with a solution of cuprous chloride or bromide in the corresponding halogen acid (Sandmeyer reaction). It is possible to prepare the aryl bromide from the diazonium chloride or sulfate. A variation Involves the use of copper powder and a mineral acid for the decomposition step (Gattermann reaction). Both procedures are illustrated by the syntheses of the isomeric bromotoluenes and chlorotoluenes. The usual conditions of the Sandmeyer reaction fail in the preparation of the chloro- and bromo-phenanthrenes. However, these compounds can be successfully obtained by the interaction of the diazonium compound with mercuric and potassium halides (Schwechten procedure). Another procedure for formation of aryl bromides involves treatment of the amine hydrobromide with nitrogen trioxide in the presence of excess 40% hydro-bromic acid. The Intermediate diazonium perbromide is then decomposed by heat. ... 

Treatment of diazonium salts with cuprous, Cu(I), salts generates aryl halides. When 398 reacts with CuCl (cuprous chloride) or CuBr (cuprous bromide), the products are chlorobenzene or bromobenzene via what is probably a radical reaction.29l jhis conversion is known as the Sandmeyer reaction. 2 The use of copper powder rather than cuprous salts for this transformation is often called the Gattermann reaction. 93,292b,c Aryl iodides are also produced from diazonium salts by reaction with potassium iodide (KI) but the actual reactive species may be l3-.294,295 Treatment of aniline derivative 403 with sodium nitrite and HCl followed by treatment with KI, for example, gave a 89% yield of 404.Aryl nitriles are generated under Sandmeyer conditions using cuprous cyanide (CuCN), as in the conversion of 405 to benzonitrile derivative 407 via diazonium chloride, 406. 

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. 

Aryl bromides and iodides are usually prepared from diazonium salts by a copper-catalyzed process, a reaction commonly known as the Sandmeyer reaction. Under the classic conditions of the Sandmeyer reaction, the diazonium salt is added to a hot acidic solution of the cuprous halide.It is also possible to convert anilines to aryl halides by generating the diazonium ion in situ. Reaction of anilines with alkyl nitrites and cuprous halides in acetonitrile gives good yields of aryl bromides by a copper-mediated process which is mechanistically similar to that occurring under the usual Sandmeyer conditions. Diazonium salts can also be converted to... 

Meenvein reaction [1, 166, before references]. The arylation of olefinic com pounds by diazonium halides with copper salt catalysis was discovered by Meerweit (1939).8 Cupric chloride has been usually employed. Cleland,9 however, prefers cuprous bromide (MCB reagent grade) and recommends that the salt (light green) be washed with acetone until the washings are colorless and then with benzene and then with hexane. The resulting solid is dried at 120° and is only faintly colored. He... 

---