Nucleophilic Reactivities of Primary and Secondary Amines in Acetonitrile†
Tanja Kanzian
Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany, Fax: +49-89-218077717
Search for more papers by this authorTobias A. Nigst
Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany, Fax: +49-89-218077717
Search for more papers by this authorAndreas Maier
Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany, Fax: +49-89-218077717
Search for more papers by this authorStefan Pichl
Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany, Fax: +49-89-218077717
Search for more papers by this authorHerbert Mayr
Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany, Fax: +49-89-218077717
Search for more papers by this authorTanja Kanzian
Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany, Fax: +49-89-218077717
Search for more papers by this authorTobias A. Nigst
Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany, Fax: +49-89-218077717
Search for more papers by this authorAndreas Maier
Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany, Fax: +49-89-218077717
Search for more papers by this authorStefan Pichl
Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany, Fax: +49-89-218077717
Search for more papers by this authorHerbert Mayr
Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany, Fax: +49-89-218077717
Search for more papers by this authorDedicated to Professor Rolf W. Saalfrank on the occasion of his 70th birthday
Graphical Abstract
The kinetics of the reactions of primary and secondary amines with benzhydrylium ions and quinone methides have been studied spectrophotometrically in acetonitrileat 20 °C. From the linear free energy relationship log k2 (20 °C) = s(N + E), the N and s parameters of these amines were determined.
Abstract
The kinetics of the reactions of primary and secondary amines with benzhydrylium ions and quinone methides in acetonitrile have been studied under pseudo-first-order conditions (high excess of amines) by UV/Vis spectrophotometry. Generally, the plots of kobs versus amine concentration were linear, in line with a second-order rate law. However, for some reactions of secondary amines with quinone methides, the plots of kobs versus amine concentration showed an upward curvature, which indicates rate-limiting deprotonation of the initially formed adduct by a second molecule of amine. From the second-order rate constants k2 for the attack on the electrophiles by the amines, the nucleophilicity parameters N and s for the amines were determined from the linear free energy relationship log k2 (20 °C) = s(N + E). The rates of the reactions of the amines with benzhydrylium ions are strongly affected by solvent polarity, in sharp contrast to the analogous reactions of other neutral nucleophiles.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
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