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Electrophilicities of 1,2‐Disubstituted Ethylenes
Author(s) -
Allgäuer Dominik S.,
Mayr Herbert
Publication year - 2014
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.201301779
Subject(s) - chemistry , electrophile , nucleophile , sulfonium , medicinal chemistry , pyridinium , free energy relationship , kinetics , reaction rate constant , organic chemistry , salt (chemistry) , physics , quantum mechanics , catalysis
The kinetics of the reactions of maleic anhydride, N ‐methylmaleimide, fumaronitrile, diethyl fumarate, and diethyl maleate with pyridinium and sulfonium ylides were studied in DMSO at 20 °C. All of the reactions were found to follow a second‐order rate law, and can be described by the linear free energy relationship log k 2 (20 °C) = s N ( N + E ), where N and s N are solvent‐dependent nucleophile‐specific parameters, and E is an electrophile‐specific parameter. The electrophilicity parameters E of the investigated acceptor‐substituted alkenes were derived from the linear correlations of (log k 2 )/ s N vs. N , and range from –19.8 to –11.1.