Rate and Product Studies on the Solvolyses of Allyl Chloroformate

Koh, Han Joong; Kang, Suk Jin; September, Received

doi:10.5012/bkcs.2012.33.12.4117

Cited by 5 publications

(13 citation statements)

References 35 publications

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“…In the aqueous HFIP mixtures, the rate of 3 is the greatest in the very strongly hydrogen bonding 97% HFIP. The 80% EtOH and 100% MeOH values documented in Table 1 for 3 are within the margin of error when compared to those reported at 25.0 °C by Koh and Kang [60]. However our ethanolyses rate for 3 is almost three times faster than the previously reported value [60].…”

Section: Resultssupporting

confidence: 83%

“…The 80% EtOH and 100% MeOH values documented in Table 1 for 3 are within the margin of error when compared to those reported at 25.0 °C by Koh and Kang [60]. However our ethanolyses rate for 3 is almost three times faster than the previously reported value [60]. We have since repeated this determination six times using different batches of purified solvent to make sure that our reported EtOH value is correct.…”

Section: Resultssupporting

confidence: 78%

Section: Introductionmentioning

confidence: 99%

“…The solvolyses of allyl chloroformate ( 3 ) was recently evaluated in 35 solvents at 35.0 °C [60]. The authors Koh and Kang proposed a lose bimolecular S N 2 reaction based on the magnitudes of the Grunwald-Winstein l and m values obtained, the activation parameters and KSIE determinations, and the product selectivity data in alcohol/water mixtures [60]. The rate data reported for the ethanolysis of allyl chloroformate at 25.0 °C [60] was found to be smaller than the corresponding value obtained for benzyl chloroformate ( 5 ) at the same temperature [56].…”

Section: Introductionmentioning

confidence: 99%

“…To further probe the potential of any accelerating or deshielding π-conjugation effects, we now present the analysis of our experimental first-order specific rates of solvolysis of allyl (3) and vinyl (4) chloroformates at 25.0 °C. We also reanalyze the Koh and Kang data [60] for 3 at 35.0 °C. We compare the solvolytic data obtained at 25.0 °C to the available literature values of phenyl (1) [21–23,26,27] and benzyl (5) [56] chloroformate at the same temperature.…”

Section: Introductionmentioning

confidence: 99%

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Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters

D’Souza

Givens

Lorchak

et al. 2013

IJMS

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At 25.0 °C the specific rates of solvolysis for allyl and vinyl chloroformates have been determined in a wide mix of pure and aqueous organic mixtures. In all the solvents studied, vinyl chloroformate was found to react significantly faster than allyl chloroformate. Multiple correlation analyses of these rates are completed using the extended (two-term) Grunwald-Winstein equation with incorporation of literature values for solvent nucleophilicity (NT) and solvent ionizing power (YCl). Both substrates were found to solvolyze by similar dual bimolecular carbonyl-addition and unimolecular ionization channels, each heavily dependent upon the solvents nucleophilicity and ionizing ability.

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Section: Resultssupporting

confidence: 83%

Section: Resultssupporting

confidence: 78%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters

D’Souza

Givens

Lorchak

et al. 2013

IJMS

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Correlation of Rates of Solvolysis of Diphenylacetyl Chloride Using Extended Grunwald–Winstein Equation

Koh

Kang

2015

Bulletin Korean Chem Soc

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Product-Rate Correlations for Solvolyses of 2,4-Dimethoxybenzenesulfonyl Chloride

Kim¹,

Choi²,

Park³

et al. 2014

Bulletin of the Korean Chemical Society

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The solvolysis rate constants of 2,4-dimethoxybenzenesulfonyl chloride (1) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale and YCl solvent ionizing scale, with sensitivity values of 0.93 ± 0.14 and 0.65 ± 0.06 for l and m, respectively. These l and m values can be considered to support a SN2 reaction pathway. The activation enthalpies (H  ) were 12.4 to 14.6 kcal·mol 1 and the activation entropies (S, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effects (SKIE) were 1.74 to 1.86, which is also in accord with the SN2 mechanism and was possibly assisted using a general-base catalysis. The values of product selectivity (S) for solvolyses of 1 in alcohol/water mixtures was 0.57 to 6.5, which is also consistent with the proposed bimolecular reaction mechanism. Third-order rate constants, kww and kaa, were calculated from the rate constants (kobs), together with kaw and kwa calculated from the intercept and slope of the plot of 1/S vs.[water]/[alcohol]. The calculated rate constants, kcalc (kww, kaw, kwa and kaa), are in satisfactory agreement with the experimental values, supporting the stoichiometric solvation effect analysis.

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Rate and Product Studies on the Solvolyses of Allyl Chloroformate

Cited by 5 publications

References 35 publications

Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters

Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters

Correlation of Rates of Solvolysis of Diphenylacetyl Chloride Using Extended Grunwald–Winstein Equation

Product-Rate Correlations for Solvolyses of 2,4-Dimethoxybenzenesulfonyl Chloride

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