Catalytic effects of hydrogen-bond acceptor solvent on nucleophilic aromatic substitution reactions in non-polar aprotic solvent: reactions of phenyl 2,4,6-trinitrophenyl ether with amines in benzene–acetonitrile mixtures

Banjoko, Olayinka; Babatunde, Ibitola A.

doi:10.1016/j.tet.2005.06.009

Cited by 19 publications

(24 citation statements)

References 15 publications

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“…[20] Recent kinetic or solvent studies support the hydrogen-bond (HB) hypothesis, without rigorously demonstrating it. [21][22][23][24][25] The computational study presented here allows us to rationalize all these experimental results.…”

Section: Introductionmentioning

confidence: 76%

Evidences for the Key Role of Hydrogen Bonds in Nucleophilic Aromatic Substitution Reactions

Chéron

Kaı̈m

Grimaud

et al. 2011

Chemistry A European J

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The effect of hydrogen bonds on the fate of nucleophilic aromatic substitutions (S(N)Ar) has been studied in silico using a density functional theory approach in the condensed phase. The importance of these hydrogen bonds can explain the "built-in solvation" model of Bunnett concerning intermolecular processes between halogenonitrobenzenes and amines. It is also demonstrated that it can explain experimental results for a multicomponent reaction (the Ugi-Smiles coupling), involving an intramolecular S(N)Ar (the Smiles rearrangement) as the key step of the process. Modeling reveals that when an intramolecular hydrogen bond is present, it lowers the activation barrier of this step and enables the multicomponent reaction to proceed.

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Section: Introductionmentioning

confidence: 76%

Evidences for the Key Role of Hydrogen Bonds in Nucleophilic Aromatic Substitution Reactions

Chéron

Kaı̈m

Grimaud

et al. 2011

Chemistry A European J

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“…The reaction is so slow that it is inconvenient to wait for its completion. Therefore, the Guggenheim method 29 was used to evaluate the rate constants by carrying out the kinetic runs for up to 3 h. The second‐order rate constants, k A , were obtained from the observed rate constants as reported earlier 28. Regression coefficients of all the reaction rate constants were around 0.99.…”

Section: Methodsmentioning

confidence: 99%

“…Examination of the literature revealed that the effects of structure on S N Ar2 reactions have largely been reported 9–23. However, only very few attempts have been made to study on the effect of solvent on such reactions in a more systematic manner 24–30. Hence, in this article, the reaction of few parasubsutituted anilines with 2‐bromo‐5‐nitropyridine and with 2‐chloro‐5‐nitropyridine in dimethylsulfoxide (DMSO)/acetonitrile (AcN) (both polar, aprotic, Hydrogen Bond Acceptor, PAHBA solvents) mixtures of varying compositions has been reported.…”

Section: Introductionmentioning

confidence: 99%

Solvent hydrogen bonding and structural effects on the reaction of 2‐halo‐5‐nitropyridines with parasubstituted anilines in dimethylsulfoxide/acetonitrile mixtures

Kalaimani¹,

Rathinam²,

Bhuvaneshwari³

2011

Int J of Chemical Kinetics

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Substitution reactions of some parasubstituted anilines with 2-chloro-5-nitropyridine and 2-bromo-5-nitropyridine were carried out conductometrically in dimethylsulfoxide/acetonitrile mixtures. The correlation of second order rate constants with Hammett's substituent constants yields a fairly linear straight line with a negative slope. The correlation of rate data with Kamlet-Taft's solvatochromic parameters is excellent (100R 2 = 97%) in both the substrates. The solvation model proposed is well supported by the solvatochromism exhibited by aniline in the solvent mixture under investigation. The molar extinction coefficient (ε max ) of aniline varies appreciably up to ∼25% with the change in composition of the mixture. The multivariate correlation analysis of ε max (with α, β, π *) suggests that the solvation around NH 2 moiety of aniline through hydrogen bond donor (HBD) property is found to be dominant in the solvation process and consequently in altering the rate. The observation is that the dominance of HBD property in solvation is further confirmed by the cyclic voltammetric oxidation of aniline in the solvent mixture. C

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“…The reaction is so slow that it is inconvenient to wait for its completion. Therefore, the Guggenheim method [20] was used to evaluate the rate constants by carrying out the kinetic runs for up to 3 h. The second-order rate constants, k 2 , were obtained from the observed rate constants as reported earlier [8]. All rate determinations were carried out at least in duplicate, and the rate constants are accurate to within ±2%.…”

Section: Kinetic Studiesmentioning

confidence: 99%

“…Correspondence to: K. P. Elango; e-mail: drkpelango@ rediffmail.com. c 2007 Wiley Periodicals, Inc. eters affords important mechanistic information [3][4][5][6][7][8]. Accumulated information on the correlation of reaction rates with the properties of the solvent through linear solvation energy relationships (LSER) has led to some significant results.…”

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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Catalytic effects of hydrogen-bond acceptor solvent on nucleophilic aromatic substitution reactions in non-polar aprotic solvent: reactions of phenyl 2,4,6-trinitrophenyl ether with amines in benzene–acetonitrile mixtures

Cited by 19 publications

References 15 publications

Evidences for the Key Role of Hydrogen Bonds in Nucleophilic Aromatic Substitution Reactions

Evidences for the Key Role of Hydrogen Bonds in Nucleophilic Aromatic Substitution Reactions

Solvent hydrogen bonding and structural effects on the reaction of 2‐halo‐5‐nitropyridines with parasubstituted anilines in dimethylsulfoxide/acetonitrile 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

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