Radiolytically formed carbenium ions, such as sec-C3H7+, sec-C4H9+, and t-C4H9+, react in the gas phase with model aliphatic and aromatic nitriles yielding the corresponding nitrilium ions. The latter undergo efficient condensation with water that eventually leads to the formation of the corresponding N-alkylamides. The mechanism is analogous to the Ritter reaction in solution. The reactivity and selectivity of the gas-phase electrophilic attack on nitriles has been deduced from competition experiments under conditions that largely exclude the effects of solvation, ion pairing, etc., which complicate the interpretation of solution-chemistry measurements.
Alkylation of nitriles with gaseous carbenium ions. The Ritter reaction in the dilute gas state / Cacace, Fulvio; Giovanna, Ciranni; Giacomello, Pierluigi. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - STAMPA. - 104:8(1982), pp. 2258-2261. [10.1021/ja00372a025]
Alkylation of nitriles with gaseous carbenium ions. The Ritter reaction in the dilute gas state.
CACACE, Fulvio;GIACOMELLO, Pierluigi
1982
Abstract
Radiolytically formed carbenium ions, such as sec-C3H7+, sec-C4H9+, and t-C4H9+, react in the gas phase with model aliphatic and aromatic nitriles yielding the corresponding nitrilium ions. The latter undergo efficient condensation with water that eventually leads to the formation of the corresponding N-alkylamides. The mechanism is analogous to the Ritter reaction in solution. The reactivity and selectivity of the gas-phase electrophilic attack on nitriles has been deduced from competition experiments under conditions that largely exclude the effects of solvation, ion pairing, etc., which complicate the interpretation of solution-chemistry measurements.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.