2013
DOI: 10.1002/ejoc.201300265
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Quantification of the Nucleophilic Reactivities of Ethyl Arylacetate Anions

Abstract: The kinetics of the reactions of substituted ethyl arylacetates with quinone methides and structurally related diethyl benzylidenemalonates have been studied in DMSO. The second‐order rate constants (lg k2) correlated linearly with the electrophilicities E according to the linear free‐energy relationship lg k2 = sN(N + E), allowing us to determine the nucleophilicity parameters N and sN for these anions. The nucleophilic reactivities of the carbanions vary from N = 27.5 for the parent compound to N = 20.0 for … Show more

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Cited by 25 publications
(12 citation statements)
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“…Thus, the second‐order rate constants ( k 1 ) were calculated from the slope of the linear plots. The results are summarized in Table , which also includes the calculated rate constants using the E values evaluated in this work and the previously published parameters N and s N for anion 11 in DMSO …”
Section: Resultsmentioning
confidence: 99%
“…Thus, the second‐order rate constants ( k 1 ) were calculated from the slope of the linear plots. The results are summarized in Table , which also includes the calculated rate constants using the E values evaluated in this work and the previously published parameters N and s N for anion 11 in DMSO …”
Section: Resultsmentioning
confidence: 99%
“…Reactions of carbanions with alkyl halides, Michael acceptors, or carbonyl groups are among the most important methods for the formation of carbon–carbon bonds 1. In previous work, we studied the nucleophilic reactivities of different types of carbanions2 and found that p K aH values are not a reliable measure for their relative reactivities 2b,d,f,g. Since these investigations were mostly performed in DMSO solution at low ion concentrations, ion pairing was neglected.…”
Section: Introductionmentioning
confidence: 99%
“…[a] p K aH in DMSO solution. From reference 4; [b] the nucleophilic reactivities of the anions 2‐CO 2 Et and 2‐NO 2 were reported in references 2b and 2g; [c] λ max from reference 2g; [d] 2‐COPh = 1‐Ph .…”
Section: Introductionmentioning
confidence: 99%
“…Because the adducts of the reactions of 1X – 4X with 5 j ‐BF 4 − were isolated with relatively high yields (59–93 %, Table ), the contribution of undesired side reactions to the observed kinetics cannot play a significant role. Moreover, the addition of a stoichiometric amount of 18‐crown‐6 did not change the reaction kinetics, indicating that potassium cation does not exert a noticeable effect on the observed rate constants (see the Supporting Information for details) . N and s N parameters were derived from log k vs. E plots (Figure ) according to the free energy relationship of Equation (1) …”
Section: Figurementioning
confidence: 99%
“…Moreover, the addition of a stoichiometric amount of 18‐crown‐6 did not change the reaction kinetics, indicating that potassium cation does not exert a noticeable effect on the observed rate constants (see the Supporting Information for details) . N and s N parameters were derived from log k vs. E plots (Figure ) according to the free energy relationship of Equation (1) …”
Section: Figurementioning
confidence: 99%