Nesmeyanov reaction

Triarylbismuthines have been synthesized by means of the Nesmeyanov reaction that employs an arenediazonium salt such as the tetrafluoroborate, a bismuth trihahde, and a reduciag agent (51). The decomposition of iodonium salts ia the preseace of bismuth trichloride and metallic bismuth also leads to the formation of triarylbismuthines, Ar Bi (52) ... 

We return now to the mercuro-de-diazoniation. Nesmeyanov s school continued the work on metallo-de-diazoniations from 1929 to 1953 (see summary by Nesmeyanov, 1972). A major discovery was made at the very beginning, namely the influence of copper powder (Nesmeyanov, 1929 b Nesmeyanov and Kahn, 1929). With this addition metallic mercury was not required instead the double salt of the diazonium chloride and mercuric chloride was used. The copper reacts stoichiometrically as an electron donor. Therefore, either arylmercuric chlorides (Scheme 10-87) or diarylmercury compounds (Scheme 10-88) can be obtained. These reactions are called Nesmeyanov reactions. Specific examples are the syntheses of di-2-naphthyl-... 

Reactions yielding compounds of the type ArwXCl3 w (X=As, Sb, or Bi) are closely related to the Nesmeyanov reaction. Bismuth has the most metallic character of that group of elements. Waters s experiments with bulk bismuth (1937, 1939) did... 

The Nesmeyanov reaction can also be used for arylarsine syntheses. Usually double salts of diazonium chlorides with zinc chloride are treated with arsenic trichloride and zinc dust in acetone (Hanby and Waters, 1946). Nesmeyanov s school used mainly double salts with ferric chloride and iron powder (Nesmeyanov and Makarova, 1950 Reutov and BundeP, 1955). 

Naphthoquinone diazides 32, 284ff., see also Quinone diazides 2,3-Naphthotriazole, formation 132 f. Negations, psycholinguistics of 215 Nesmeyanov reactions 273 ff. Nicotinamide-adenine nucleotide (NAD+) 328 f. 

Nernst-Einstein equatioon, 5 587 Nernst equation, 9 571 12 206 19 206 Nernst-Planck equation, 9 612-613 Nerol, 3 233 24 479, 501, 503-506 grades of, 24 505 hydrogenation of, 24 506 price of, 24 505 Nerolidol, 24 546-547 Neroliodyl acetate, 24 547 Nerve agents, 5 815, 818-821 Neryl, 24 479 Neryl esters, 24 505 Nesmeyanov reaction, 3 75 Nested fullerenes, 12 231 Nested situations, amount of coverage in experimental design texts compared, S 395t... 

According to Waters results,27,28 the formation of aryl-metal compounds on decomposition of arenediazonium chlorides in the presence of metals such as mercury, antimony, bismuth, lead, and tin also occurs by way of radicals, in contrast to the Nesmeyanov reaction. 

There are two main processes for direct preparation of arylmercuric salts, namely, mercuration of aromatic compounds and the so-called Nesmeyanov reaction. 

In the Nesmeyanov reaction double salts of arenediazonium salts with mercuric chloride are decomposed by copper powder in cold acetone179 or cold water 180... 

Arylarsenic compounds may also be obtained by the Nesmeyanov reaction decomposition of the double salts of arenediazonium halides and iron(m) chloride or zinc chloride in the presence of arsenic trichloride and metallic iron leads to aryldichloroarsines and diarylchloroarsines among other products 509... 

There are also the syntheses of arylantimony compounds from arenediazonium salts by the Nesmeyanov reaction, which has been very extensively investigated in just this field and shown to have manifold applications. 

Mixed arylantimony halides can also be synthesized by the Nesmeyanov reaction. Compounds of type ArAr SbCl3, for instance, are obtained by decomposition of double saltsArN2Cl Ar SbCl4 by iron powder in acetone,528... 

Table 11. The yields of symmetrical diarylmercurials obtained by Nesmeyanov reaction [137]...

The copper for performing the Nesmeyanov reaction is prepared by reaction of aqueous CUSO4 and zinc dust. 

Further important organometallics which offer ready access to the homo-coupling products are arylmercuric halides. This can be easily prepared by several ways, but the most convenienty from the corresponding aryldiazonium salts via the Nesmeyanov reaction, see Chapter 4. Arylmercuric chlorides derived from electron-rich arenes such as thiophene, which easily undergoes the direct mercuration reaction at 2-position, can be readily coupled with an equimolar amount of palladium(II) chloride in the presence of triethylamine as the base in high yield [35], Scheme 16. 

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