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Ionic‐Liquid Controlled Nitration of Double Bond: Highly Selective Synthesis of Nitrostyrenes and Benzonitriles
Author(s) -
Casiello Michele,
Caputo Daniela,
Fusco Caterina,
Cotugno Pietro,
Rizzi Vito,
Dell'Anna Maria Michela,
D'Accolti Lucia,
Nacci Angelo
Publication year - 2020
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202001027
Subject(s) - chemistry , ionic liquid , nitration , selectivity , aryl , organic chemistry , green chemistry , solvent , substrate (aquarium) , combinatorial chemistry , medicinal chemistry , catalysis , alkyl , oceanography , geology
Unprecedented in literature, the conversion of aryl alkenes into β‐nitrostyrenes ( 2 ) or benzonitriles ( 3 ) with sodium nitrite can be governed by an appropriate choice of ionic liquid (IL) medium. A general trend was found for the selectivity of these processes, which depends on the nature of IL, with imidazolium‐based ILs, such as [Bmim]Cl, that favor the C–H nitration leading to β‐nitrostyrenes, while tetraalkylammonium‐based ILs, such as TBAA, privilege the C=C bond cleavage affording benzonitriles. Besides a substrate scope, mechanistic hypotheses were provided on the origin of the different selectivity in the two kinds of ILs, based on their own tunable properties such as polarity, viscosity, and solvent cage effects.