Diazotization-cyanation of aromatic amines with crosslinked poly(4-vinylpyridine)-supported cyanide ions

• Published in: Journal of applied polymer science 2012-08, Vol.125 (3), p.2163-2169
• Main Authors: Karimi Zarchi, Mohammad Ali, Ebrahimi, Nahid
• Format: Article
• Language: English
• Subjects: Acetonitrile; Amines; Applied sciences; Aromatic compounds; Chemical modifications; Chemical reactions and properties; Chemistry; Crosslinking; Cyanides; Exact sciences and technology; functionalization of polymers; macroporous polymers; Materials science; modification; networks; Nitriles; Noncondensed benzenic compounds; Organic chemistry; Organic polymers; Physicochemistry of polymers; Polymers; Preparations and properties; Reproduction; Sodium nitrite; supports
• ISSN: 0021-8995; 1097-4628
• DOI: 10.1002/app.36394

A simple, mild, and efficient method for the cyanation of stable arenediazonium salts was developed with polymer‐supported cyanide. Arenediazonium hydrogen sulfate (ArN2+HSO4−) was obtained by the reaction between a primary aryl amine and sodium nitrite in the presence of concentrated sulfuric acid (H2SO4) at low temperature (0–5°C). By an ion‐exchange reaction between ArN2+HSO4− and NaBF4, the stable arenediazonium tetrafluoroborate, ArN2+BF4−, was prepared. ArN2+BF4− was then converted to aryl nitrile with crosslinked poly(4‐vinylpyridine) supported cyanide ion in acetonitrile at room temperature. The spent polymeric reagent was regenerated and reused several times without any loss in its activity. This procedure offered advantages, including a higher isolated yield, shorter reaction time, and simple reaction workup. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012