Diazonium salts from aryl amines

Another, especially historically important copper-mediated radical aryl-aryl bond forming reaction is the Pschorr reaction (Gomberg-Bachmann reaction), which has been first described in 1896 for the preparation of phenanthrene and its derivatives [85]. Later, in 1924, Gomberg and Bachmann described an intermolecular version of this reaction and prepared several biphenyl derivatives in moderate yield [86]. The reaction is initiated by formation of diazonium salts from aromatic amines, which release nitrogen upon reaction with copper salts. The intermediary formed aryl radial then undergoes the desired coupling reaction and allows the isolation of biaryl compounds. An example of such a reaction is outlined in Scheme 12.23 [87],... 

This is most practically carried out via the use of aryl diazonium salts (Ar-N2 Cl ) which are derived from aryl amines(Ar-NH2) which are themselves produced by the catalytic reduction of aryl nitro compounds (Ar-N02). Thus, we would seem to need to put a nitro group para to the original hydroxyl group. We must be aware of phenol s immense reactivity and the subsequent danger of polynitration. To avoid this danger, we treat phenol with dilute nitric acid instead of with concentrated nitric acid and with concentrated sulfuric acid as the catalyst. 

The reaction of an aryl diazonium salt with potassium iodide is the standard method for the preparation of aryl iodides The diazonium salt is prepared from a primary aro matic amine m the usual way a solution of potassium iodide is then added and the reac tion mixture is brought to room temperature or heated to accelerate the reaction... 

Addition of Vinyl and Aryl Groups. The reaction of aromatic radicals, generated by decomposition of diazonium salts, with iminium salts in the presence of TiCE in aqueous media produces secondary amines (Eq. 11.53).91 The iminium salts are formed in situ from aromatic amines and aldehydes. 

These types of switchable electrode surfaces have been used to selectively pattern two different cell populations onto a surface [151] and additionally these surfaces can selectively release different cells at different applied potentials [152]. However, it is important to recognize that electrochemically switching a surface from inactive to conjugation and active to conjugation has been well explored with nitro-terminated aryl diazonium salts. In such studies, the application where very anodic potential resulted in a six-electron reduction to an amine [139], to which proteins could be attached [153-155]. The key difference is that the interaction of the biological medium with the surface is controlled by the presence of the antifouling layer. In many ways these electrode surfaces developed by Mrksich and coworkers [150-152, 156] are very similar to the antifouling surfaces with molecular wires discussed in Section 1.4.2 [131, 132, 138, 142]. In both cases the electrode is... 

Although it is possible to prepare aryl chlorides and aryl bromides by electrophilic aromatic substitution, it is often necessary to prepare these compounds from an aromatic amine. The amine is converted to the corresponding diazonium salt and then treated with copper(I) chloride or copper(I) bromide as appropriate. 

An alternate entry to the narciclasine class of alkaloids has provided access to compounds related to isonarciclasine (263) (Scheme 24). In the event, the aryla-tion of p-benzoquinone with diazonium salts derived from the aryl amines 250 and 251 yielded the aryl-substituted benzoquinones 252 and 253, respectively (146). The selective hydroxylation of 252 and 253 with osmium tetraoxide provided the corresponding m-diols 254 and 255. Catalytic hydrogenation of 254 and 255 using Pd/C or Raney Ni and subsequent lactonization gave the triols 256 and 257 together with small amounts of the C-2 a-epimers 258 and 259. Aminolysis of 256 and 257 afforded the corresponding racemic tetrahydrophen-anthridones 260 and 261, whereas similar treatment of the a-epimers 258 and 259 led to the formation of ( )-isolycoricidine (262) and ( )-isonarciclasine (263), respectively. 

This route is particularly valuable for substituents that cannot easily be added by electrophilic substitution such as OH or CN. Table 2.2 gives you a selection of reagents. For the addition of CN, Cl or Br, copper (I) derivatives usually give the best results. So the aryl nitrile 46 might come from amine 47 via a diazonium salt and routine disconnections lead us back to toluene. 

Support-bound triazenes, which can be prepared from resin-bound secondary, aliphatic amines and aromatic diazonium salts [37], undergo cleavage upon treatment with acids, whereby the aromatic diazonium salts are regenerated. In cross-linked polystyrene these diazonium salts decompose to yield nitrogen and, preferentially, aryl radicals. If the acid-olysis of polystyrene-bound triazenes is conducted in the presence of hydrogen-atom donors... 

Aryl amines, 403 4-Aryl-2-aminothiazoles, 178-182 mercuration of, 81 nitration of, 72 reduction of, 86 Schiff bases from, 99 Aryl diazonium salts, reaction with, rho-danine, 419... 

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. ... 

Incidentally, 34 contributes more to the hybrid than 35, as shown by bond-distance measurements. In benzenediazonium chloride, the C—N distance is 1.42 A, and the N—N distance 1.08 A, which values fit more closely to a single and a triple bond than to two double bonds (see Table 1.5). Even aromatic diazonium salts are stable only at low temperatures, usually only < 5°C, although more stable ones, such as the diazonium salt obtained from sulfanilic acid, are stable up to 10 or 15°C. Diazonium salts are usually prepared in aqueous solution and used without iso-lation, although it is possible to prepare solid diazonium salts if desired (see 13-23). The stability of aryl diazonium salts can be increased by crown ether complexion. For aromatic amines, the reaction is very general. Halogen, nitro, alkyl, aldehyde, sulfonic acid, and so on, groups do not interfere. Since aliphatic amines do not react with... 

The isolation of the diazonium salt is not always necessary. Several procedures allow the preparation of aryl chlorides from aromatic amines in one step. " ... 

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