The nitro anomaly and Brønsted βnuc values in SN2 reactions on chlorine

Linoam Eliad; Shmaryahu Hoz

doi:10.1002/poc.482

The nitro anomaly and Brønsted β_nuc values in S_N2 reactions on chlorine

Linoam Eliad, Shmaryahu Hoz

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

Abstract

The kinetics of chlorine transfer reactions between N-chlorosuccinimide (NCS) and four carbon nucleophiles (the conjugated bases of phenyldinitromethane, Meldrum's acid, phenylmalononitrile and phenylnitro-methane) in water were determined. A plot of log k for the S_N2 reactions vs the pK_a of the first three conjugated acids of the nucleophiles gave a straight line with a slope (β_nuc) of 1.8. The data point for the mononitro derivative, phenylnitromethane, deviates negatively from the line by 6.7 log units. This deviation is typical of proton transfer reactions and was recently shown to occur also in S_N2 reactions on bromine.

Original language	English
Pages (from-to)	540-543
Number of pages	4
Journal	Journal of Physical Organic Chemistry
Volume	15
Issue number	8
DOIs	https://doi.org/10.1002/poc.482
State	Published - Aug 2002

Keywords

Halophilic reactions
Nitro anomaly
S2 on chlorine

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10.1002/poc.482

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abstract = "The kinetics of chlorine transfer reactions between N-chlorosuccinimide (NCS) and four carbon nucleophiles (the conjugated bases of phenyldinitromethane, Meldrum's acid, phenylmalononitrile and phenylnitro-methane) in water were determined. A plot of log k for the SN2 reactions vs the pKa of the first three conjugated acids of the nucleophiles gave a straight line with a slope (βnuc) of 1.8. The data point for the mononitro derivative, phenylnitromethane, deviates negatively from the line by 6.7 log units. This deviation is typical of proton transfer reactions and was recently shown to occur also in SN2 reactions on bromine.",

keywords = "Halophilic reactions, Nitro anomaly, S2 on chlorine",

author = "Linoam Eliad and Shmaryahu Hoz",

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N2 - The kinetics of chlorine transfer reactions between N-chlorosuccinimide (NCS) and four carbon nucleophiles (the conjugated bases of phenyldinitromethane, Meldrum's acid, phenylmalononitrile and phenylnitro-methane) in water were determined. A plot of log k for the SN2 reactions vs the pKa of the first three conjugated acids of the nucleophiles gave a straight line with a slope (βnuc) of 1.8. The data point for the mononitro derivative, phenylnitromethane, deviates negatively from the line by 6.7 log units. This deviation is typical of proton transfer reactions and was recently shown to occur also in SN2 reactions on bromine.

AB - The kinetics of chlorine transfer reactions between N-chlorosuccinimide (NCS) and four carbon nucleophiles (the conjugated bases of phenyldinitromethane, Meldrum's acid, phenylmalononitrile and phenylnitro-methane) in water were determined. A plot of log k for the SN2 reactions vs the pKa of the first three conjugated acids of the nucleophiles gave a straight line with a slope (βnuc) of 1.8. The data point for the mononitro derivative, phenylnitromethane, deviates negatively from the line by 6.7 log units. This deviation is typical of proton transfer reactions and was recently shown to occur also in SN2 reactions on bromine.

KW - Halophilic reactions

KW - Nitro anomaly

KW - S2 on chlorine

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The nitro anomaly and Brønsted β_nuc values in S_N2 reactions on chlorine

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