Dicationic intermediates involving protonated amides: dual modes of reactivity including the acylation of arenes.
In the Brønsted superacid CF(3)SO(3)H (triflic acid), amides are able to form reactive, dicationic electrophiles. It is shown that these dicationic intermediates participate in two distinctly different types of electrophilic reactions. The protonated amide increases the reactivity of an adjacent electrophilic group, and the protonated amide group itself shows enhanced reactivity arising from an adjacent cationic charge. In the latter case, several types of amides are even capable of reacting with benzene by Friedel-Crafts acylation. [reaction--see text]
Klumpp
Douglas A
DA
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115, USA. dklumpp@niu.edu
Rendy
Rendy
R
Zhang
Yun
Y
Gomez
Alma
A
McElrea
Aaron
A
D000215:Acylation; D000577:Amides / Q000737:chemistry*; D002412:Cations / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D015394:Molecular Structure; D011522:Protons; D013696:Temperature
D000577:Amides; D002412:Cations; D011522:Protons