The SN2-SN1 spectrum. 4. The SN2 (intermediate) mechanism for solvolyses of tert-butyl chloride: a revised Y scale of solvent ionizing power based on solvolyses of 1-adamantyl chloride

Bentley, T. William; Carter, Gillian E.

doi:10.1021/ja00385a031

Cited by 240 publications

(177 citation statements)

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“…The specific rates are the averages from at least four independent kinetic runs. The specific rates are reported within Differences in Y X values for a given solvent are believed to be primarily due to differences in electrophilic solvent assistance [6] and the halide series, showing a reduction in electrophilicity as one moves down the periodic table, is a useful one for assessing the significance of the specific anion solvation [14].…”

Section: Resultsmentioning

confidence: 99%

“…A subsequent extension of the previous [6,10] kinetic study of 1-adamantyl chloride solvolyses has led to the availability of Y Cl values for more aqueous HFIP-H 2 O mixtures [8]. In the present study, we determine the specific rates of solvolysis of 1-adamantyl bromide and 1-adamantyl iodide in these more aqueous mixtures, which allows the determination of the corresponding Y Br and Y I values.…”

Section: Introductionmentioning

confidence: 93%

“…A further development as regards solvent ionizing power scales involved the recognition that the Y scale based on tert-butyl chloride solvolyses included a necleophilic component [6][7][8][9], which could be avoided by the use of the bridgehead 1-adamantyl chloride [6] as the standard substrate. Further, the solvent ionizing power scale was found to be leaving-group dependent and scales have been independently determined for several leaving-groups(X) and termed, in general, Y X scales [10].…”

Section: Introductionmentioning

confidence: 99%

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Additional Solvent Ionizing Power Values for Binary Water- 1,1,1,3,3,3-Hexafluoro-2-propanol Solvents

Kevill

Ryu

2006

IJMS

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Abstract:Determinations of the specific rates of solvolysis of 1-adamantyl bromide and 1-adamantyl iodide in 1,1,1,3,3,3-hexafluoro-2-propanol-water mixtures, in conjunction with earlier reported values in 80% ethanol, have led to additional YBr and YI solvent ionizing power values. These new values will be especially important in avoiding multicollinearity when the extended Grunwald-Winstein equation (extended by addition of a term involving solvent nucleophilicity) is used to correlate solvent-induced changes in the specific rates of solvolyses involving a bromide or iodide ion leaving group.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

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Additional Solvent Ionizing Power Values for Binary Water- 1,1,1,3,3,3-Hexafluoro-2-propanol Solvents

Kevill

Ryu

2006

IJMS

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“…[9, 10]; Y Cl values from refs. [5, 6]; the 70-0% MeOH, 80-10% Acetone, 100TFE, 70TFE(w/w), 50TFE(w/w) values are from ref. [23]; n is the number of solvents.…”

Section: Figurementioning

confidence: 99%

“…It was realized [3] that as the solvolyses of 1-, and 2-adamantyl derivatives (Figure 1) cannot be subject to rearside nucleophilic participation and elimination, they could provide improved standard substrates for establishing scales of solvent ionizing power [4, 5] and listings of Y x values are available [6]. …”

Section: Introductionmentioning

confidence: 99%

On the Importance of the Aromatic Ring Parameter in Studies of the Solvolyses of Cinnamyl and Cinnamoyl Halides

D’Souza

Darrington

Kevill

2010

Organic Chemistry International

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In solvolysis studies using Grunwald-Winstein plots, dispersions were observed for substrates with aromatic rings at the α-carbon. Several examples for the unimolecular solvolysis of monoaryl benzylic derivatives and related diaryl- or naphthyl- substituted derivatives have now been reported, where the application of the aromatic ring parameter (I) removes this dispersion. A recent claim suggesting the presence of an appreciable nucleophilic component to the I scale, has now been shown, in a review of the solvolysis of highly-hindered alkyl halides, to be unlikely to be correct. Attention is now focused on the application of the hI term for the solvolysis of compounds containing a double bond in the vicinity of any developing carbocation. Available specific rates of solvolysis (plus some new values) at 25°C of cinnamyl chloride, cinnamyl bromide, cinnamoyl chloride, p-chlorocinnamoyl chloride, and p-nitrocinnamoyl chloride are analyzed using the simple and extended (including the hI term) Grunwald-Winstein equations.

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The Grunwald-Winstein type correlation for 2-chloro-2,4,4-trimethylpentane: A simple tertiary alkyl chloride that shows essentially limiting behaviour in solvolysis

Takeuchi¹,

Ohga²,

Ushino³

et al. 1996

J. Phys. Org. Chem.

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Evaluation of the rates of solvolysis of 2-chloro-2,4,4-trimethylpentane (4) in 17 solvents on the basis of the Grunwald-Winstein type equation [log(k/k,) = lNT + my,, + el gives an excellent correlation with 1 = -0.01 f 0.02 and rn = 0.74i 0.01. The neopentyl group in 4 more effectively shields the rear side of the reaction center than the tert-butyl group in 2-chloro-2,3,3-trimethylbutane. The rate ratio between 4 and 2chloro-2-methylpropane (3) at 25 "C is 275 in trifluoroethanol and predicted to increase to 950 in trifluoroacetic acid. The previous 4:3 rate ratio of 22 in 80% ethanol evidently underestimated the B-strain effect on the solvolysis rate of 4 by a factor of at least 40.

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The SN2-SN1 spectrum. 4. The SN2 (intermediate) mechanism for solvolyses of tert-butyl chloride: a revised Y scale of solvent ionizing power based on solvolyses of 1-adamantyl chloride

Cited by 240 publications

References 1 publication

Additional Solvent Ionizing Power Values for Binary Water- 1,1,1,3,3,3-Hexafluoro-2-propanol Solvents

Additional Solvent Ionizing Power Values for Binary Water- 1,1,1,3,3,3-Hexafluoro-2-propanol Solvents

On the Importance of the Aromatic Ring Parameter in Studies of the Solvolyses of Cinnamyl and Cinnamoyl Halides

The Grunwald-Winstein type correlation for 2-chloro-2,4,4-trimethylpentane: A simple tertiary alkyl chloride that shows essentially limiting behaviour in solvolysis

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