Chlorophosphate solvolyses. Evaluation of third-order rate laws and rate–product correlations for diphenyl phosphorochloridate in aqueous alcohols †

Bentley, T. William; Ebdon, David N.; Llewellyn, Gwynnyth; Abduljaber, Mohamad H.; Miller, Bronwyn; Kevill, Dennis N.

doi:10.1039/a703409a

Cited by 22 publications

(44 citation statements)

References 29 publications

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“…Although both the N T and Y X scales are based on standard systems involving substitution reaction at an sp 3 -hybridized carbon [3,4], the scales have also been used with considerable success in the correlation analyses of solvolysis reactions of substrates which have attack at the sp 2 -hybridized carbon of acyl halides [5][6][7] and chloroformate esters [8][9][10][11][12][13][14][15], at the phosphorus atom of phosphorochloridate esters [16,17] or amides [18], and at the sulfur atom of arenesulfonyl chlorides [19].…”

Section: Introductionmentioning

confidence: 99%

Application of the Extended Grunwald-Winstein Equation to Solvolyses of n-Propyl Chloroformate

Kyong

Won

Kevill

2005

IJMS

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Application of the extended Grunwald-Winstein equation to solvolyses of n-propyl chloroformate in a variety of pure and binary solvents indicates an addition-elimination pathway in the majority of the solvents but an ionization pathway in the solvents of highest ionizing power and lowest nucleophilicity. For methanolysis, a solvent deuterium isotope effect of 2.17 is compatible with the incorporation of general-base catalysis into the substitution process. Activation parameters are consistent with the duality of mechanism. Very modest positive salt effects are observed on adding chloride or bromide salts to the ethanolysis.

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Section: Introductionmentioning

confidence: 99%

Application of the Extended Grunwald-Winstein Equation to Solvolyses of n-Propyl Chloroformate

Kyong

Won

Kevill

2005

IJMS

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“…8 In the reported studies, a direct SN2 reaction mechanism is shown for the solvolytic reactions of dialkyl, 7 diaryl 9 and phosphorochloridates possessing phosphorus reaction center as shown a good correlation fitted into the equation.…”

Section: Introductionmentioning

confidence: 76%

Kinetic Studies of the Solvolyses of 4-Nitrophenyl Phenyl Thiophosphorochloridate

Koh

Kang²

2009

Bulletin of the Korean Chemical Society

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Rates of solvolyses of 4-nitrophenyl phenyl thiophosphorochloridate (4-NO2PhOP(S)(Cl)OPh, 1) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, and 2,2,2-trifluroethanol (TFE) are reported. Thermodynamic parameters were determined at several temperatures in three representative solvents. The extended Grunwald-Winstein equation was applied to 29 solvents and the correlation coefficient (R) showed 0.959. The sensitivities (l = 1.37 and m = 0.62) are similar to those obtained for diphenyl thiophosphorochloridate ((PhO)2PSCl, 2), diphenyl phosphorochloridate ( (PhO)2POCl, 3), diphenyl phosphinic chloride (Ph2POCl, 4), and diphenyl thiophosphinic chloride (Ph2PSCl, 5). The solvolytic reaction mechanism of 4-nitrophenyl phenyl thiophosphorochloridate (1) is suggested to be proceeded a SN2 process as previously reported result. The activation enthalpies are shown as slightly low as ∆H ≠ = 9.62 to 11.9 kcal·mol -1 and the activation entropies are shown as slightly high negative value as ∆S ≠ = -34.1 to -44.9 cal·mol -1 ·K -1 compared to the expected SN2 reaction mechanism. Kinetic solvent isotope effects are accord with a typical SN2 mechanism as shown in the range of 2.41 in MeOH/ MeOD and 2.57 in H2O/D2O solvent mixtures.

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“…9 The extended Grunwald-Winstein plot for solvolyses of those substrates containing the P-atom as the reaction center, led to acceptable correlations with very similar l and m values except for the poorly correlated solvolyses of diaryl phosphorochloridates with phenyl or p-chlorophenyl as the aryl group. 6 The mechanisms of reactions of phosphinothioyl compounds such as diphenyl thiophosphorochloridate ((PhO) 2 PSCl, 1) have been less studied, in spite of their importance as highly reactive chemical intermediates. In this work, to gain further understanding of the mechanism of phosphoryl transfer, we carried out kinetic investigations of the solvolysis of diphenyl thiophosphorochloridate ((PhO) 2 PSCl, 1) in a variety of pure and binary solvents at 55.0 o C, eq.…”

Section: 2mentioning

confidence: 99%

“…Measurements in deuterated methanol (MeOD) and deuterated water (D2O) also allow the determination of the kinetic solvent isotope effect (KSIE). This study could be helpful in clarifying the phosphoryl transfer mechanism, as well as to compare the reactivities among diphenyl phosphorochloridate ((PhO) 2 -POCl, 2), 6 diphenylphosphinyl chloride (Ph 2 -POCl, 3) 9 and diphenylthiophosphinyl chloride (Ph 2 PSCl, 4). …”

Section: 2mentioning

confidence: 99%

A Kinetic Study on Solvolysis of Diphenyl Thiophosphorochloridate

Koh

Kang²,

Kevill³

2009

Bulletin of the Korean Chemical Society

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Rates of solvolyses of diphenyl thiophosphorochloridate ((PhO)2PSCl, 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)2PSCl, 1) were similar to those obtained for diphenyl phosphorochloridate ((PhO)2POCl, 2), diphenylphosphinyl chloride (Ph2POCl, 3) and diphenylthiophosphinyl chloride (Ph2PSCl, 4). As with the previously studied of 3~4 solvolyses, an SN2 pathway is proposed for the solvolyses of diphenyl thiophosphorochloridate (1). The activation parameters, ∆H ≠ (= 11.6~13.9 kcal․mol ․K -1 ), were determined, and they were in line with values expected for an SN2 reaction. The large kinetic solvent isotope effects (KSIE, 2.44 in MeOH/MeOD and 3.46 in H2O/D2O) are also well explained by the proposed SN2 mechanism.

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Chlorophosphate solvolyses. Evaluation of third-order rate laws and rate–product correlations for diphenyl phosphorochloridate in aqueous alcohols †

Cited by 22 publications

References 29 publications

Application of the Extended Grunwald-Winstein Equation to Solvolyses of n-Propyl Chloroformate

Application of the Extended Grunwald-Winstein Equation to Solvolyses of n-Propyl Chloroformate

Kinetic Studies of the Solvolyses of 4-Nitrophenyl Phenyl Thiophosphorochloridate

A Kinetic Study on Solvolysis of Diphenyl Thiophosphorochloridate

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