Kinetics and mechanism of the reaction of <i>para</i>‐chlorophenyl aryl chlorophosphates with anilines in acetonitrile

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

doi:10.1002/kin.10081

Cited by 65 publications

(9 citation statements)

References 38 publications

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“…Examination of the literature reveals that the effects of structure on S N 2 reactions have largely been reported [15][16][17][18][19]. However, the literature lacks a systematic study on the effect of solvent on such reactions.…”

Section: Introductionmentioning

confidence: 99%

Solvent hydrogen bonding and structural effects on nucleophilic substitution reactions: Part 3. Reaction of benzenesulfonyl chloride with anilines in benzene/propan‐2‐ol mixtures

Bhuvaneshwari

Elango

2007

Int J of Chemical Kinetics

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Substitution reactions of 13 para-and meta-substituted anilines with benzenesulfonyl chloride in varying mole fractions of benzene in propan-2-ol have been investigated conductometrically. The second-order rate constants correlate well with pK a values of anilines and with the Hammett's equation. The negative Hammett reaction constant indicates the formation of an electron-deficient transition state. The rate data correlate satisfactorily with macroscopic solvent parameters such as relative permittivity, ε r , and polarity, E T N . Correlation of rate data with Kamlet-Taft solvatochromic parameters (α, β, π *) suggests that both the specific and nonspecific solute-solvent interactions influence the reactivity.

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Section: Introductionmentioning

confidence: 99%

Solvent hydrogen bonding and structural effects on nucleophilic substitution reactions: Part 3. Reaction of benzenesulfonyl chloride with anilines in benzene/propan‐2‐ol mixtures

Bhuvaneshwari

Elango

2007

Int J of Chemical Kinetics

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“…The specific rates of 1 (X = 4-NO2) are faster than of 2 (X = H) at 55.0 o C. This is due to a greater positive charge on the P atom in 1 (TS 1) than in 2 by the electron-withdrawing effect of the 4-NO2 substituent in 1, which indicates of the importance of bond making in the rate-determining step. 13 The phenoxy group (σI = 0.40) has a stronger electronwithdrawing ability than the phenyl group (σI = 0.12).…”

Section: Resultsmentioning

confidence: 99%

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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“…1,2 This indicates that the degree of bond formation is greater as the aniline becomes weaker: the greater the bond formation, the steric congestion becomes greater, and the k H /k D value becomes smaller.…”

Section: -31618mentioning

confidence: 99%

“…In the anilinolysis of 2, the proposed mechanism was the same as in 1, and smaller magnitude of CIC (ρ XY = -0.31) compared to 1 was rationalized by partial electron loss towards the electron-acceptor equatorial ligand (4-ClC 6 H 4 O) in the bipyramidal pentacoordinated TS. 2 In the anilinolysis of 3, on the contrary, a stepwise mechanism with a ratelimiting leaving group departure from the intermediate was proposed on the basis of a large positive CIC (ρ XY = +1.91).…”

mentioning

confidence: 99%

Kinetics and Mechanism of the Anilinolysis of Bis(2,6-dimethylphenyl) Chlorophosphate in Dimethyl Sulfoxide

Barai¹,

Lee²

2011

Bulletin of the Korean Chemical Society

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Continuing the kinetic studies of the anilinolyses of diphenyl chlorophosphate derivatives, Y-aryl phenyl [1: (C 6 3 the nucleophilic substitution reactions of bis(2,6-dimethylphenyl) chlorophosphate {4: [2,6-(CH 3 ) 2 -C 6 H 3 O] 2 P(=O)Cl} with substituted anilines (XC 6 H 4 NH 2 ) and deuterated anilines (XC 6 H 4 ND 2 ) are investigated kinetically in dimethyl sulfoxide (DMSO) at 55.0 ± 0.1 o C (Scheme 1) to gain further information into the substituent effects, steric effects, and deuterium kinetic isotope effects (DKIEs) on the reactivity and anilinolysis mechanism. The numbering of the substrates of 1-4 follows the sequence of the size of the two ligands, R 1 O and R 2 O. Results and DiscussionThe observed pseudo-first-order rate constants (k obsd ) were found to follow eq. (1) for all of the reactions under pseudofirst-order conditions with a large excess of aniline nucleophile. The k 0 values were negligible (k 0 ≈ 0) in DMSO. The second-order rate constants (k H(D) ) were determined for at least five concentrations of anilines. The linear plots of eq. (1) suggest that there is no base-catalysis or noticeable side reaction and that the overall reaction is described by Scheme 1.The k H and k D values are summarized in Table 1, together with the DKIEs (k H /k D ) and the Hammett ρ X and Brönsted β X selectivity parameters. The β X values listed in Table 1 seem to be less reliable since the pK a values used are not those determined in DMSO, but rather in water. Using the pK a values for the anilinium ions determined in DMSO, an approximate straight line is obtained when they are plotted against those determined in water.4 Spillane and coworkers reported that the β X value for the reactions of N-phenyl sulfamoyl chloride (PhNHSO 2 Cl) with X-anilines in DMSO is similar when determined using the pK a values of anilines measured in water (β X = 0.69) and DMSO (β X = 0.62). 5Accordingly, it may be inferred that the β X values in Table 1 are reasonably positive. The pK a and σ values of deuterated anilines are assumed to be the same as those of anilines. The pK a (X) values of deuterated X-anilines may be slightly greater than those of X-anilines, however, the difference is too small to be taken into account.6 Figures 1 and 2 show the Hammett (log k H(D) vs σ X ) and Brönsted [log k H(D) vs pK a (X)] plots, respectively, for substituent X variations in the nucleophiles. The rate consistently increases with a more electrondonating substituent X in the nucleophile, which is consistent with a typical nucleophilic substitution reaction with positive charge development at the nucleophilic N atom in the transition state (TS). The magnitudes of the ρ X and β X values with the deuterated anilines are slightly greater than those with the anilines, suggesting more sensitive to substituent effects of the deuterated anilines compared to the Scheme 1. The studied reaction system.

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Kinetics and mechanism of the reaction of para‐chlorophenyl aryl chlorophosphates with anilines in acetonitrile

Cited by 65 publications

References 38 publications

Solvent hydrogen bonding and structural effects on nucleophilic substitution reactions: Part 3. Reaction of benzenesulfonyl chloride with anilines in benzene/propan‐2‐ol mixtures

Solvent hydrogen bonding and structural effects on nucleophilic substitution reactions: Part 3. Reaction of benzenesulfonyl chloride with anilines in benzene/propan‐2‐ol mixtures

Kinetic Studies of the Solvolyses of 4-Nitrophenyl Phenyl Thiophosphorochloridate

Kinetics and Mechanism of the Anilinolysis of Bis(2,6-dimethylphenyl) Chlorophosphate in Dimethyl Sulfoxide

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