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

Abstract

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

Diazotization–azidation of amines in water by using crosslinked poly(4‐vinylpyridine)‐supported azide ion

“…But when aniline was subjected to this novel diazotization–azidation even after 100 min, no azido product was separated and a few byproducts are formed that are not identified (Table I, entry 1). This result is in agreement with previously reported diazotization–iodination of aniline 58. Also there is no reported result in some other methods for conversion of aryl amines into aryl azides, from anilines,47, 53, 59 and conversion of aryl boronic acids into aryl azides 51.…”

Recent trends in the chemistry of Sandmeyer reaction: a review

“…Aromatic diazonium salts, discovered by Griefs in 1858 [1], have wide spread applications in organic synthesis as well as at industrial level. They are frequently used for the preparation of organic nanocompounds and grafted a variety of organic molecules on metallic surfaces [2]. Furthermore, Meerwein arylation [3,4], Balz-Schiemann [5,6] and various metal-catalyzed reactions [7,8] involve diazonium salts as starting precursors for the production of various halides, phenols, cyanides, azides and alkenes [9] which serve as effective intermediates for the synthesis of important molecules [10][11][12][13].…”