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Updated: Jul 2, 2026

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Nucleophilic reactivities of benzenesulfonyl-substituted carbanions
Florian Seeliger1, Herbert Mayr
1Department Chemie und Biochemie, Ludwig-Maximilians-Universität, Butenandtstr. 5-13 (Haus F), 81377 München, Germany.
Abstract:
Kinetics of the reactions of four benzenesulfonyl-stabilized carbanions (1a-d)- with reference electrophiles (quinone methides 2 and diarylcarbenium ions 3) have been determined in dimethyl sulfoxide solution at 20 degrees C in order to derive the reactivity parameters N and s according to the linear free-energy relationship logk(20 degrees C) = s(N + E) (eqn (1)). The additions of (1a-d)- to ordinary Michael acceptors (e.g., benzylidene Meldrum's acid 4a, benzylidenebarbituric acids 5a-c, and benzylidene-indan-1,3-diones 6a-d) were also studied kinetically and found to be 5-24 times slower than predicted by eqn (1).
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