Nucleophilic substitution reaction of benzyl benzenesulfonates with anilines in MeOH-MeCN mixtures-I

Lee, Ikchoon; Lee, Won Heui; Sohn, Se Chul; Kim, Choong Shik

doi:10.1016/s0040-4020(01)96365-3

Cited by 26 publications

(8 citation statements)

References 24 publications

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“…This is expectable in nucleophilic substitution reactions. The high magnitude of ρ values suggests preferable influence of nucleophilicity of the substituted anilines on the reaction rate, which confirms that the formation of the intermediate is the rate‐limiting step in all solvent compositions.…”

Section: Resultsmentioning

confidence: 62%

Reaction kinetics investigation of 1‐fluoro‐2,4‐dinitrobenzene with substituted anilines in ethyl acetate–methanol mixtures using linear and nonlinear free energy relationships

Jamali-Paghaleh

Harifi‐Mood²,

Gholami

2011

J of Physical Organic Chem

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Aromatic nucleophilic substitution reaction of 1-fluoro-2,4-dinitrobenzene with para-substituted and metasubstituted anilines was kinetically investigated in the mixtures of ethyl acetate and methanol at room temperature. The correlation of second-order rate coefficients with Hammett's substituent constants yields a fairly linear straight line with negative slope in different mole fractions of ethyl acetate-methanol mixtures. The measured rate coefficients of the reaction demonstrated a dramatic variation in ethyl acetate-methanol mixtures with the increasing mole fraction of ethyl acetate. Linear free energy relationship (LFER) investigations confirm that polarity has a major effect on the reaction rate whereas the hydrogen-bonding ability of the media has a slight effect on it. Nonlinear free energy relationship based on preferential solvation hypothesis showed differences between the microsphere solvation of the solute and the bulk composition of the solvents, and non-ideal behavior is observed in the trend of the rate coefficients, which cover the LFER results. a Standard deviation. b Intercept of the single or multiparameter correlation. c e, a, and b are the coefficients of E N T , α, and β, respectively. ETHYL ACETATE-METHANOL MIXTURES

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Section: Resultsmentioning

confidence: 62%

Reaction kinetics investigation of 1‐fluoro‐2,4‐dinitrobenzene with substituted anilines in ethyl acetate–methanol mixtures using linear and nonlinear free energy relationships

Jamali-Paghaleh

Harifi‐Mood²,

Gholami

2011

J of Physical Organic Chem

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“…4. The slope of this plot (the Bronsted slope, β) provides a measure of the sensitivity of the reaction to the basicity of the nucleophile [16]. There is a good correlation (0.981 < r < 0.984, 0.02 < SD < 0.05, −0.270 ± 0.01 < ρ < −0.469 ± 0.03) between the rate and the Hammett's substituent constants also (Fig.…”

Section: Structure-reactivity Correlationmentioning

confidence: 94%

“…The results reveal that ρ values are negative, implying that positive charge develops on the N-atom as the TS is formed. Furthermore, the magnitude of both ρ and β are low, which suggest an easier bond cleavage in the TS [16]. …”

Section: Structure-reactivity Correlationmentioning

confidence: 99%

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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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“…Anilines were redistilled or recrystallized before use as previously described. 17 Hz, NH), 6.9 (1H, t, J = 7.6 Hz), 7.0 (2H, d, J = 7.6 Hz), 7.1 (2H, t, J = 7.6 Hz), 7.4 (4H, m), 7.5 (2H, m), 7.8-7.9 (4H, m); ,4.6;N,4.3. Found: C,65.7;H,4.7;N,4.5. …”

Section: Methodsmentioning

confidence: 99%

Kinetics and Mechanism of the Aminolysis of Diphenyl Phosphinic Chloride with Anilines

2007

Bulletin of the Korean Chemical Society

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The aminolyses of diphenyl phosphinic chloride (1) with substituted anilines in acetonitrile at 55.0 o C are investigated kinetically. Large Hammett ρ X (ρ nuc = -4.78) and Brönsted β X (β nuc = 1.69) values suggest extensive bond formation in the transition state. The primary normal kinetic isotope effects (k H /k D = 1.42-1.82) involving deuterated aniline (XC 6 H 4 ND 2 ) nucleophiles indicate that hydrogen bonding results in partial deprotonation of the aniline nucleophile in the rate-limiting step. The faster rate of diphenyl phosphinic chloride (1) than diphenyl chlorophosphate (2) is rationalized by the large proportion of a frontside attack in the reaction of 1. These results are consistent with a concerted mechanism involving a partial frontside nucleophilic attack through a hydrogen-bonded, four-center type transition state.

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Nucleophilic substitution reaction of benzyl benzenesulfonates with anilines in MeOH-MeCN mixtures-I

Cited by 26 publications

References 24 publications

Reaction kinetics investigation of 1‐fluoro‐2,4‐dinitrobenzene with substituted anilines in ethyl acetate–methanol mixtures using linear and nonlinear free energy relationships

Reaction kinetics investigation of 1‐fluoro‐2,4‐dinitrobenzene with substituted anilines in ethyl acetate–methanol mixtures using linear and nonlinear free energy relationships

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

Kinetics and Mechanism of the Aminolysis of Diphenyl Phosphinic Chloride with Anilines

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