Nucleophilic Reactivity. Part II. Kinetics of Reactions of Methyl Perchlorate with Nucleophiles in Water.

Koskikallio, Jouko; Norris, Kjeld; Clauson-Kaas, Niels; Svanholt, Karen; Olsen, Gert E.; Jansen, Gert; Lamm, Bo; Samuelsson, Benny

doi:10.3891/acta.chem.scand.23-1477

Cited by 37 publications

(29 citation statements)

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“…The positive ⌬S value obtained in 2-propanol is an indication of a greater disorder in the transition state, caused by disruption of the alcohol-phenoxide hydrogen bonds in the reacting solvent-separated ion-pair. Similar observations had been made before, in a kinetic study of the nucleophilic (HO Ϫ , MeO Ϫ ) displacements of iodomethane in protic solvents [28].…”

supporting

confidence: 63%

Kinetics of methylation of a solvatochromic vinylogous ?-pyridone in different solvents

1999

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supporting

confidence: 63%

Kinetics of methylation of a solvatochromic vinylogous ?-pyridone in different solvents

1999

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“…Swain-Scott susceptibility constants have been measured for various substrates in aqueous solution; results tend to vary extensively, even within S N 2 reactions. Substrates with a carbon electrophilic center that is sp 3 -hybridized exhibit s values ranging from 0.25 to 1.8 [7,[16][17][18][19][20]. If we restrict consideration to S N 2 reactions for substrates with primary carbons, good leaving groups, and minimal substituent effects (e.g., methyl 4-nitrobenzenesulfonate, ethyl tosylate, methyl perchlorate, and methyl iodide), s values range from 0.66 to 1.3 [7,16,18].…”

Section: Discussionmentioning

confidence: 99%

“…The Swain-Scott model has been applied to the nucleophilic displacement reactions of a wealth of saturated carbon substrates [10,[15][16][17][18][19][20] in addition to nucleophilic addition reactions at acetal [21] and carbocation [15,22,23] centers in several solvent systems including aqueous solution or aqueous organic mixtures. In applying the Swain-Scott model for predicting the relative importance of environmental nucleophiles, the simplifying assumption may be made that the substrate parameter s is close to 1.…”

Section: Swain-scott Modelmentioning

confidence: 99%

Correlation analyses for bimolecular nucleophilic substitution reactions of chloroacetanilide herbicides and their structural analogs with environmentally relevant nucleophiles

Lippa

Roberts

2005

Enviro Toxic and Chemistry

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Second-order rate constants (kNuc) for aqueous-phase bimolecular nucleophilic substitution (SN2) reactions of a range of anionic nucleophiles with alachlor, propachlor, and two analogs of propachlor (a thioacetanilide and a beta-anilide) were fit to the Swain-Scott and Edwards models. Correlations of literature kNuc values for analogous reactions of methyl chloride and methyl benzenesulfonate were included for comparison. The Swain-Scott correlation yielded poor to fair results for chloroacetanilides and their analogs, with adjusted (adj) r2 values ranging from 0.67 to 0.89, which are comparable to correlations for CH3Cl and CH3OSO2Ph (r2 (adj) = 0.80 and 0.85, respectively). Both the one- and two-parameter Edwards models yielded improved correlations for the majority of substrates. A pronounced dependence on the substrate polarizability (alpha) factor generally was observed for the Edwards model, with a negligible dependence on the substrate basicity (beta) factor. Substrate polarizability factors for the one-parameter Edwards model were significantly larger for alachlor, propachlor, and the beta-anilide analog of propachlor than for methyl chloride and methyl benzenesulfonate. This indicates that the chloroacetanilides are activated toward SN2 reactions with highly reactive nucleophiles (e.g., HS-, PhS-, and Sn(2-)) relative to other saturated carbon substrates. At best, the Swain-Scott and Edwards models only furnish order-of-magnitude predictions of kNuc for the substrates investigated.

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“…20 A similar shift in transition state structure has been proposed to rationalize the smaller selectivity of methyl perchlorate compared to methyl iodide towards reaction with nucleophilic anions. 19 …”

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Formation and Stability of the 4-Methoxyphenonium Ion in Aqueous Solution

et al. 2011

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The reaction of 2-methoxyphenylethyl tosylate (MeO-1-Ts) is first-order in [N3−]. A carbon-13 NMR analysis of the products of the reactions of MeO-1-[α–13C]Ts shows the formation of MeO-1-[β–13C]OH and MeO-1-[β–13C]N3 from the trapping of a symmetrical 4-methoxyphenonium ion reaction intermediate 2+. An analysis of the rate and product data provides a value of kaz/ks = 83 M−1 for partitioning of 2+ between addition of azide ion and solvent. These data set a limit for the lifetime of 2+ in aqueous solution.

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Nucleophilic Reactivity. Part II. Kinetics of Reactions of Methyl Perchlorate with Nucleophiles in Water.

Cited by 37 publications

References 0 publications

Kinetics of methylation of a solvatochromic vinylogous ?-pyridone in different solvents

Kinetics of methylation of a solvatochromic vinylogous ?-pyridone in different solvents

Correlation analyses for bimolecular nucleophilic substitution reactions of chloroacetanilide herbicides and their structural analogs with environmentally relevant nucleophiles

Formation and Stability of the 4-Methoxyphenonium Ion in Aqueous Solution

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