The contamination with water of the cathodic ACN-Et4NBF4 solution gave us the opportunity to investigate alkyl isocyanate reactivity toward electrogenerated anions. The cathodic reduction of a ACN-Et4NBF4 solution led to the formation of both hydroxide and cyanomethyl anions. The reaction of the catholyte with cyclohexylisocyanate led to the exclusive formation of acetamidated product, with no traces of cyanomethylated one. On the contrary, when reacting with benzaldehyde only the cyanomethylated was isolated. Considering that the acetamidated product of benzaldehyde is reported to be unstable (thus its formation cannot be excluded), various experiments were carried out in order to understand the anomalous reactivity of cyclohexylisocyanate. Moreover, computational analysis allowed to state the higher stability of acetamidated product with respect to the cyanomethylated one. The possibility of a concerted reaction, instead of acetamide anion formation prior to the reaction, is still an open question.

Reaction of Electrogenerated Cyanomethyl Anion with Cyclohexylisocyanate: Synthesis of N-(cyclohexylcarbamoyl) acetamide. An Unexpected Product / Scarano, Vincenzo; Bortolami, Martina; Pandolfi, Fabiana; Petrucci, Rita; Rocco, Daniele; Zollo, Giuseppe; Feroci, Marta. - In: JOURNAL OF THE ELECTROCHEMICAL SOCIETY. - ISSN 0013-4651. - 167:(2020), p. 155514. [10.1149/1945-7111/abb8f4]

Reaction of Electrogenerated Cyanomethyl Anion with Cyclohexylisocyanate: Synthesis of N-(cyclohexylcarbamoyl) acetamide. An Unexpected Product

Vincenzo Scarano;Martina Bortolami;Fabiana Pandolfi;Rita Petrucci;Daniele Rocco;Giuseppe Zollo;Marta Feroci
2020

Abstract

The contamination with water of the cathodic ACN-Et4NBF4 solution gave us the opportunity to investigate alkyl isocyanate reactivity toward electrogenerated anions. The cathodic reduction of a ACN-Et4NBF4 solution led to the formation of both hydroxide and cyanomethyl anions. The reaction of the catholyte with cyclohexylisocyanate led to the exclusive formation of acetamidated product, with no traces of cyanomethylated one. On the contrary, when reacting with benzaldehyde only the cyanomethylated was isolated. Considering that the acetamidated product of benzaldehyde is reported to be unstable (thus its formation cannot be excluded), various experiments were carried out in order to understand the anomalous reactivity of cyclohexylisocyanate. Moreover, computational analysis allowed to state the higher stability of acetamidated product with respect to the cyanomethylated one. The possibility of a concerted reaction, instead of acetamide anion formation prior to the reaction, is still an open question.
2020
electrochemistry, Cyanomethyl anion, Density Functional Theory
01 Pubblicazione su rivista::01a Articolo in rivista
Reaction of Electrogenerated Cyanomethyl Anion with Cyclohexylisocyanate: Synthesis of N-(cyclohexylcarbamoyl) acetamide. An Unexpected Product / Scarano, Vincenzo; Bortolami, Martina; Pandolfi, Fabiana; Petrucci, Rita; Rocco, Daniele; Zollo, Giuseppe; Feroci, Marta. - In: JOURNAL OF THE ELECTROCHEMICAL SOCIETY. - ISSN 0013-4651. - 167:(2020), p. 155514. [10.1149/1945-7111/abb8f4]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/1444502
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