• Bulletin of the Korean Chemical Society
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• 제29권10호
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• pp.1927-1931
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• 2008

Rate of solvolysis of diphenylthiophosphinyl chloride in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluoroethanol (TFE) or 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) are reported. Solvolyses were also carried out in TFE-ethanol mixtures. For five representative solvents, studies were made at several temperatures and activation parameters determined. The 29 solvents gave a reasonably precise extended Grunwald-Winstein equation plot, correlation coefficient (R) of 0.933, which improved to 0.983 when the four TFE-ethanol points were excluded. The sensitivities (l = 1.00 and m = 0.64) were similar to those obtained for dimethyl phosphorochloridate and phosphorochloridothionate and diphenylphosphinyl chloride (1). As with the four previously studied solvolyses, an $SN_2$ pathway is proposed for the solvolyses of diphenylthiophosphinyl chloride. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for an $S_N2$ reaction.

• 대한화학회지
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• 제61권1호
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• pp.25-28
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• 2017

Solvolyses with the reaction center being the sulfur of 4-(chlorosulfonyl)biphenyl ($C_6H_5C_6H_4SO_2Cl$, 1) was studied under solvolytic conditions and the extended Grunwald-Winstein equation was applied. The thirty five kinds of solvents gave a reasonable extended Grunwald-Winstein plot with a correlation coefficient (R) of 0.940. The sensitivity values (l = 0.60 and m = 0.47) of 1 were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, 2; l = 1.10 and m = 0.61) proposed to undergo dissociative $S_N2$ mechanism. These l and m values for the solvolyses of 1 can be considered to support a $S_N2$ pathway with some ionization reaction. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for a bimolecular reaction. The kinetic solvent isotope effect (KSIE) of 1.26 is also in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

• Bulletin of the Korean Chemical Society
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• 제33권11호
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• pp.3657-3664
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• 2012

Reactions of 1-adamantylmethyl chloroformate ($1-AdCH_2OCOCl$, 1) and 1-adamantylmethyl fluoroformate ($1-AdCH_2OCOF$, 2) in hydroxylic solvents have been studied. Application of the extended Grunwald-Winstein (G-W) equation to solvolyses of 1 in a variety of pure and binary solvents indicates an addition-elimination pathway in the majority of the solvents except an ionization pathway in the solvents of relatively low nucleophilcity and high ionizing power. The solvolyses of 2 show an addition-elimination pathway in all of the mixed solvents. The leaving group effects ($k_F/k_{Cl}$), the kinetic solvent isotope effects (KSIEs, $k_{MeOH}/k_{MeOD}$), and the enthalpy and entropy of activation for the solvolyses of 1 and 2 were also calculated. The selectivity values (S) for each solvent composition are reported and discussed. These observations are compared with those previously reported for other alkyl haloformate esters.

• Bulletin of the Korean Chemical Society
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• 제30권2호
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• pp.383-388
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• 2009

Rates of solvolyses of diphenyl thiophosphorochloridate ($(PhO)_2$PSCl, 1) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone and 2,2,2-trifluoroethanol (TFE) are reported. For four representative solvents, studies were made at several temperatures and activation parameters were determined. The 30 solvents gave a reasonably precise extended Grunwald-Winstein plot, correlation coefficient (R) of 0.989. The sensitivity values (l = 1.29 and m = 0.64) of diphenyl thiophosphorochloridate ($(PhO)_2$PSCl, 1) were similar to those obtained for diphenyl phosphorochloridate ($(PhO)_2$POCl, 2), diphenylphosphinyl chloride ($Ph_2$POCl, 3) and diphenylthiophosphinyl chloride ($Ph_2$PSCl, 4). As with the previously studied of 3~4 solvolyses, an $S_N$ pathway is proposed for the solvolyses of diphenyl thiophosphorochloridate (1). The activation parameters, ${\Delta}H^{\neq}\;(=11.6{\sim}13.9\;kcal{\cdot}mol^{-1})\;and\;{\Delta}S^{\neq}\; (=\;-32.1\;{\sim}\;-42.7\;cal{\cdot}mol^{-1}{\cdot}K^{-1})$, were determined, and they were in line with values expected for an $S_N$2 reaction. The large kinetic solvent isotope effects (KSIE, 2.44 in MeOH/MeOD and 3.46 in $H_2O/D_2$O) are also well explained by the proposed $S_N$2 mechanism.

• Bulletin of the Korean Chemical Society
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• 제34권2호
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• pp.615-621
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• 2013

Solvolyses of isobutyl chloroformate (4) in 43 binary solvent mixtures including highly aqueous media, water, $D_2O$, $CH_3OD$, 2,2,2-trifluoroethanol (TFE) as well as aqueous 1,1,1,3,3,3-hexafluoro-isopropanol (HFIP) solvents were performed at $45^{\circ}C$, in order to further investigate the recent results of D'Souza, M. $J^1$. et al.; solvolyses of 4 are found to be consistent with the proposed mechanism ($Ad_E$). The variety of solvent systems was extended to comprise highly ionizing power solvent media ($Y_{Cl}$ > 2.7 excepted for aqueous fluorinated solvents and pure TFE solvent) to investigate whether a mechanistic change occurs as solvent compositions are varied. However, in case of 18-solvent ranges having aqueous fluorinated solvent systems (TFE-$H_2O$ and HFIP-$H_2O$) and/or having $Y_{Cl}$ > 2.7 solvent systems, the solvent effect on reactivity for those of 4 are evaluated by the multiple regression analysis as competition with $S_N2$ - type mechanism. And in pure TFE and 97 w/w % HFIP solvents with high $Y_{Cl}$ and weak $N_T$, these solvolyses are understood as reactions which proceed through an ionization ($S_N1$) pathway.

• 대한화학회지
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• 제34권1호
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• pp.10-18
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• 1990

파라-치환 브롬화 벤질의 가용매 분해반응을 DMSO-$H_2O$과 DMF-$H_2O$ 혼합용매계에서 속도론적으로 연구 하였다. 이 두 혼합용매계의 이온화력(Y)와 친핵도($N_{BS}$)를 결정하기 위하여 같은 혼합용매속에서 1-adamantyl halides, t-butyl halides 그리고 methyl tosylate를 가용매 분해반응시켰다. 각 DMSO-$H_2O$ 혼합용매에 대한 분광용매화 파라미터는 측정된 νmax를 Taft의 관계식에 대입시켜 결정하였다. 파라-치환 브롬화 벤질의 가용매 분해반응은 m, l값과 ${\beta},{\rho}_s$값으로 보아 전이상태에서 결합형성이 약간 우세한 경계반응 메카니즘으로 진행함을 알았다.

• Bulletin of the Korean Chemical Society
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• 제19권9호
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• pp.968-973
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• 1998

Solvolyses of para-substituted phenyl chloroformates in water, $D_2O,\;CH_3OD$, 50% $D_2O-CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol are investigated at 25.0 ℃. Product selectivities are reported for a wide range of ethanol-water and methanol-water solvent compositions. These data are interpreted using the Grunwald-Winstein relationship, Hammett equation, and quantum mechanical model. Grunwald-Winstein plots of the first-order rate constants for phenyl chloroformates with $Y_{Cl}$ (based on 1-adamantyl chloride) show marked dispersions into three separate curves for the three aqueous mixtures with a small m value and a rate maximum for aqueous alcohol solvents. To account for these results, third-order rate constants, $k_{ww},\;k_{aw},\;k_{wa}$, and $k_{aa}$ were calculated from the observed $k_{ww}\;and\;k_{aa}$ values together with $k_{aw}\;and\;k_{wa}$ calculated from the computer fit. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed carbonyl addition-elimination for para-substituted phenyl chloroformates solvolyses based on mass law and stoichiometric salvation effect studies. This study has shown that the quantum mechanical model predicts transition state variation correctly for $S_N2\;like\;S_AN$ reaction mechanism of para-substituted phenyl chloroformates.

• Bulletin of the Korean Chemical Society
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• 제17권6호
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• pp.520-524
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• 1996

Solvolyses of phenyl chloroformate in water, D2O, CH3OD, 50% D2O-CH3OD, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25.0 ℃. Product selectivities are reported at 25 ℃ for a wide range of ethanol-water and methanol-water solvent compositions. The Grunwald-Winstein plots of first-order rate constants for phenyl chloroformate with YCl (based on 2-adamantyl chloride) show marked dispersions into three separate lines for the three aqueous mixtures with a small m value (m< 0.2) and a rate maximum for aqueous alcohol solvents. Third-order rate constants, kww, kaw, kwa and kaa were calculated from the observed kww and kaa values together with kaw and kwa calculated from the intercept and slope of the plot of 1/S vs. [alcohol]/[water]. The calculated rate constants, kcalc and mol % of ester agree satisfactorily with those of the observed rate constants, kobs and mol % of ester, supporting the stoichiometric solvation effect analysis. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed and/or carbonyl addition for phenyl chloroformate solvolyses based on mass law and stoichiometric solvation effect studies.

• Bulletin of the Korean Chemical Society
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• 제17권6호
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• pp.491-493
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• 1996

• Bulletin of the Korean Chemical Society
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• 제21권6호
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• pp.662-664
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• 2000