The contamination with water of the cathodic ACN-Et(4)NBF(4)solution gave us the opportunity to investigate alkyl isocyanate reactivity toward electrogenerated anions. The cathodic reduction of a ACN-Et(4)NBF(4)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.
Scarano, V., Bortolami, M., Pandolfi, F., Petrucci, R., Rocco, D., Zollo, G., et al. (2020). Reaction of Electrogenerated Cyanomethyl Anion with Cyclohexylisocyanate: Synthesis of N-(cyclohexylcarbamoyl)acetamide. An Unexpected Product. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 167(15) [10.1149/1945-7111/abb8f4].
Reaction of Electrogenerated Cyanomethyl Anion with Cyclohexylisocyanate: Synthesis of N-(cyclohexylcarbamoyl)acetamide. An Unexpected Product
Rocco, Daniele;
2020-01-01
Abstract
The contamination with water of the cathodic ACN-Et(4)NBF(4)solution gave us the opportunity to investigate alkyl isocyanate reactivity toward electrogenerated anions. The cathodic reduction of a ACN-Et(4)NBF(4)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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
