Kinetics and mechanism of the aminolysis of phenyl substituted phenyl chlorophosphates with anilines in acetonitrile

Guha, Ankur Kanti; Lee, Hai Whang; Lee, Ikchoon

doi:10.1039/a809704f

Cited by 28 publications

(44 citation statements)

References 29 publications

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“…These β values are much smaller than those obtained for the anilinolysis reactions of the same substrates [20]; nevertheless, they are similar to those found in the concerted pyridinolysis and SA aminolysis of phosphorylated 3-methoxypyridine and phosphorylated 4-morpholinopyridine, with β = 0.17-0.19 and 0.22-0.28, respectively [22,23].…”

Section: Introductionsupporting

confidence: 56%

Nucleophilic substitution reactions of diethyl 4‐nitrophenyl phosphate triester: Kinetics and mechanism

Castro

Ugarte

Rojas

et al. 2011

Int J of Chemical Kinetics

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The reactions of diethyl 4-nitrophenyl phosphate (1) with a series of nucleophiles: phenoxides, secondary alicyclic (SA) amines, and pyridines are subjected to a kinetic study. Under excess of nucleophile, all the reactions obey pseudo-first-order kinetics and are first order in the nucleophile. The nucleophilic rate constants (k N ) obtained are pH independent for all the reactions studied. The Brønsted-type plot (log k N vs. pK a nucleophile) obtained for the phenolysis is linear with slope β = 0.21; no break was found at pK a 7.5, consistent with a concerted mechanism. The Brønsted-type plots for the SA aminolysis and pyridinolysis are linear with slopes β = 0.39 and 0.43, respectively, also suggesting concerted processes. The concerted mechanisms for the latter reactions are proposed on the basis of the lack of break in the Brønsted-type plots and the instability of the hypothetical pentacoordinate intermediates formed in these reactions. C 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: [708][709][710][711][712][713][714] 2011

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Section: Introductionsupporting

confidence: 56%

Nucleophilic substitution reactions of diethyl 4‐nitrophenyl phosphate triester: Kinetics and mechanism

Castro

Ugarte

Rojas

et al. 2011

Int J of Chemical Kinetics

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“…[7][8][9] The former, involving a pentacoordinate intermediate, should undergo a change in the rate-limiting step, yielding a nonlinear Brønsted plot with a break point at pK a 0 , where the nucleophile has the same leaving ability from the intermediates as the leaving group of the substrate. 10 For the concerted path, a linear plot without such a break point is obtained, providing evidence for a single TS. The experimental studies have also provided indirect evidence for the formation of a trigonal bipyramidal pentavalent intermediate under certain reaction conditions, which was subsequently confirmed by theoretical studies in the alkaline media.…”

Section: Introductionmentioning

confidence: 99%

Ab initio and DFT studies on hydrolyses of phosphorus halides

et al. 2004

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Hydrolyses of phosphorus halides, (RO)(2)POX where R = H or Me and X = F or Cl, in the gas phase and in the reaction field have been investigated theoretically with ab initio and the density functional theory (DFT). The free energy of activation in the reaction field was also estimated using the Onsager method with a correction of entropy change and basis set superposition error (BSSE). The reaction of (MeO)(2)POF proceeds through a path with bifunctional catalysis regardless of the medium, but the reaction of (MeO)(2)POCl proceeds through bifunctional and general base catalysis in the gas phase and in water, respectively. The estimated free energy barrier of 23 kcal/mol for the hydrolysis of (MeO)(2)POF is in good agreement with the experimental values of 24 kcal/mol, and relative barrier of 3 kcal/mol to the (MeO)(2)POCl is also in good agreement with the experimental values of 5 kcal/mol of diisopropyl phosphorus halides ((Pr(i)O)(2)POX, X = F and Cl).

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“…Similar reactions at the phosphorus center of 4-chlorophenyl aryl chlorophosphates with an electron-acceptor ligand, 4-ClC 6 H 4 OP(=O)(Cl)OC 6 H 4 Y, have been reported in MeCN 132 . In this case, the large β X (= 1.45) and small k H /k D (0.64-0.87) values observed are quite similar to those for the substrate lacking a 4-Cl electron-accepting substituent 131 , but the magnitude of ρ Y (0.21) and ρ XY (−0.31) is much smaller. This is attributed to the partial loss of electronic transmission from the aniline (NX in Scheme 16) through P to the Y-substrate ring in the TS due to the electron-acceptor ligand, ClC 6 H 4 O.…”

Section: B Phosphorus and Other Heteroatomsmentioning

confidence: 65%

“…The reactions of aryl phenyl chlorophosphates with anilines in MeCN (equation 14) are found to proceed by a direct displacement (S N 2) at the phosphorus atom 131 …”

Section: B Phosphorus and Other Heteroatomsmentioning

confidence: 99%

Anilines as Nucleophiles

Lee

Sung

2009

Patai's Chemistry of Functional Groups

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Introduction Nucleophilic Reactions at Aliphatic Carbons Nucleophilic Reactions at Unsaturated Carbons Nucleophilic Reactions at Heteroatoms Anilines as C ‐Nucleophiles Kinetic Isotope Effects Involving Deuteriated Anilines Acknowledgments

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Kinetics and mechanism of the aminolysis of phenyl substituted phenyl chlorophosphates with anilines in acetonitrile

Cited by 28 publications

References 29 publications

Nucleophilic substitution reactions of diethyl 4‐nitrophenyl phosphate triester: Kinetics and mechanism

Nucleophilic substitution reactions of diethyl 4‐nitrophenyl phosphate triester: Kinetics and mechanism

Ab initio and DFT studies on hydrolyses of phosphorus halides

Anilines as Nucleophiles

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