Sandmeyer reaction cyanation

Hanson, P., Rowell, S. C., Taylor, A. B., Walton, P. H., Timms, A. W. Sandmeyer reactions. Part 6.1 A mechanistic investigation into the reduction and ligand transfer steps of Sandmeyer cyanation. J. Chem. Soc., Perkin Trans. 2 2002, 1126-1134. 

Salcomine, 360 Salicylaldehyde, 96, 217, 457 Sandmeyer reaction, 87 o-Santalene, 291 Schiff bases, 66, 249 Selenium dioxide, 93, 360-362 Selenium dioxide-Hydrogen peroxide, 362 Semicarbazide, 98 Semicarbazones, 65 Sensitizers, 285-286 L-Serine, 143 Serini reaction, 459, 460 Silica gels, 453 Silver acetate, 233, 362-363 Silver benzoate, 103 Silver carbonate, 363 Silver chlorate, 363-364 Silver cyanate, 224 Silver fluoride, 364-365 Silver fluoroborate, 365-366 Silver nitrate, 224, 240, 363, 366-368, 369, 371... 

The Dainippon Pharmaceutical Company has utilized a Sandmeyer reaction in the preparation of antibacterial pyridonecarboxylic acids. The diazonaphthyridone (39) was either chlorinated or cyanated under Sandmeyer conditions to provide the desired products (40 and 41 respectively) in good yield. These products were eventually processed to the active pharmaceutical agents (42). 

These major routes to quinoxalmecarbonitriles have been covered already by primary synthesis (Chapter 1), by cyanalysis of halogenoquinoxalines (Section 3.2.5), by deoxidative cyanation of quinoxaline N-oxides (Section 4.6.2.2), by cyanolysis of nitroquinoxalines (Section 6.1.2.2), from primary quinoxalina-mines by a Sandmeyer-type reaction (Section 6.3.2.3), from quaternary ammonio-quinoxalines with cyanide ion (Section 6.3.2.4), and by dehydration of quinoxalinecarboxamides (Section 7.4.2). Those remaining preparative routes that have been used recently are illustrated in the following examples. 

In contrast to traditional methods for preparing nitriles such as the Sandmeyer [12] and Rosenmund-von Braun [13] reactions, the Pd-catalyzed cyanation provides an opportunity to convert an aryl halide or pseudohalide to a nitrile under relatively mild conditions. 

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