Solvent effect on the alkaline hydrolysis of 2‐thiophenyl‐ 3,5‐dinitropyridine

Fathalla, Magda F.

doi:10.1002/kin.20146

Cited by 10 publications

(9 citation statements)

References 35 publications

(29 reference statements)

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“…The mechanism and reactivity for the reaction of nitroaryl derivatives with amines have interested chemists for some years and continue to attract their attention 1–11. Many studies showed the effect of aromatic ring substituents, amine, as well as the nature of the solvent on the reactivity and mechanism of nucleophilic aromatic substitution reactions 12–16. The solvent effect includes the interaction of the substrate and/or the intermediate(s) with the solvent molecules, which may be extensive and complex 17–19, whereas electronic and hydrogen bonding effects have been identified as important factors that influenced reactivity [7–11,16–23].…”

Section: Introductionmentioning

confidence: 99%

Solvent and substituent effects on the reaction of 2‐ and 4‐chloro‐3,5‐dinitrobenzotrifluorides with substituted anilines

Asghar¹,

Fathalla²,

Hamed³

2009

Int J of Chemical Kinetics

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The solvent effect on a nucleophilic substitution reaction of 2-and 4-chloro-3,5-dinitrobenzotrifluoride with substituted anilines was studied in methanol, acetonitrile, and toluene at 25 • C. This reaction is of second order, except 2-chloro-3,5-dinitrobenzotrifluoride in toluene shows third order. The k A values are found to be dependent on the substituent in aniline and give good Hammett correlations. The obtained ρ values are −4.07 and −4.62, for the reaction of anilines with 2-chloro-3,5-dinitrobenzotrifluoride in methanol and acetonitrile, respectively. The ρ values for the reaction of the anilines with 4-chloro-3,5-dinitrobenzotrifluoride are −3.38, −4.11, and −4.34 in methanol, acetonitrile, and toluene, respectively. The reaction of the former compound with anilines in toluene shows a second order in aniline. The dependence of the reaction on the external base such as DABCO suggests a proton transfer controlling step.

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Section: Introductionmentioning

confidence: 99%

Solvent and substituent effects on the reaction of 2‐ and 4‐chloro‐3,5‐dinitrobenzotrifluorides with substituted anilines

Asghar¹,

Fathalla²,

Hamed³

2009

Int J of Chemical Kinetics

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“…Pathway a represents the uncatalyzed reaction, it is first order in amine and its attack is rate limiting. When the rate constants show a parabolic dependence on the amine concentration, it can be explained by a dimer mechanism [22] (pathway b). Pathway c represents the third order by assistance of external base.…”

Section: Effect Of Pyridine Additivementioning

confidence: 99%

“…It has been widely observed in catalysed S N Ar, the deprotonation of the zwitterionic intermediate is the rate determine step. [22] The overall reaction comes from the conventional addition-elimination mechanism which is given by Eq. 1.…”

Section: Effect Of Aniline Concentrationsmentioning

confidence: 99%

Kinetics of the Reaction of 2‐Chloro‐3,5‐dinitrobenzotriflouride with Aniline in Toluene and Methanol‐Toluene Mixed Solvents

Fathalla¹

2012

Chin. J. Chem.

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Kinetics of the reaction of 2-chloro-3,5-dinitrobenzotriflouride with aniline were studied in toluene, methanol-toluene binary solvents, benzene and chloroform. The reaction in toluene exhibits third-order kinetics consistent with aggregates of aniline. Thermodynamic parameters ΔH # , ΔS # and ΔG # are calculated and discussed for the reaction of 2-chloro-3,5-dinitrobenzotriflouride with aniline in methanol-toluene. Molecular complexes between aniline and the substrate are rejected spectrophotometricaly. The mechanism is studied and compared with the reaction in presence of pyridine. It shows an amine dependence and formation of homo and/or hetero mixed aggregates between aniline and pyridine i.e. dimer mechanism.

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“…42 Solvent effects on the kinetics of the alkaline hydrolysis of 2-phenylthio-3,5-dinitropyridine in aqueous organic solvents have been analysed. 43 Reaction of 9-chloroacridine with aryl sulfonyl hydrazides results in aminodechlorination to give the corresponding N -acridinylbenzenesulfonyl hydrazides; kinetic studies in methanol and DMSO have been reported. 44 Reaction of electron-deficient heteroaryl chlorides with tertiary amines may proceed by quaternization and dealkylation, as shown in Scheme 3.…”

Section: Heterocyclic Systemsmentioning

confidence: 99%

Nucleophilic Aromatic Substitution

Crampton

2010

Organic Reaction Mechanisms · 2006

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There has been a study of the dediazoniation of 4-nitrobenzenediazonium ions in methanol-water mixtures under acidic conditions using kinetic, spectrophotometric, and chromatographic methods. Two decomposition routes were identified: an ionic pathway yielding nitrophenol and nitroanisole, and a radical pathway involving transient diazo ethers which undergo homolytic fragmentation giving nitrobenzene or 4,4 -dinitrobiphenyl. 1 Catalysis by the Cu(I)-Cu(II)-1,10-phenanthroline system has been reported in the reaction of arenediazonium salts with potassium thiocyanate to yield aryl thiocyanates. 2 Bis(trifluoromethanesulfonyl)amide anions (Tf 2 N − ) are usually considered to have very low nucleophilic reactivity. However, in imidazolium ionic liquids this anion has been shown to have higher reactivity than bromide ions in heterolytic dediazoniation reactions. 3 It has been shown that displacement of the iodo substituent in 4-iodo-1,1,2,2,9,9,10, 10-octafluoro[2.2]paracyclophane by arenethiolates or by stabilized enolates occurs by the radical chain S RN 1 mechanism. The reaction occurs in DMF with photochemical stimulation. 4 The S N Ar MechanismThere has been a review of relationships between activation parameters and mechanisms for biomolecular reactions in solution, including both nucleophilic substitutions and additions. 5 Several studies have been reported involving substitutions by amine nucleophiles where both electronic and steric effects may be important. Kinetic studies of the reactions of 2,4-dinitrophenyl 2,4,6-trinitrophenyl ether (1) with ring-substituted 175

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Solvent effect on the alkaline hydrolysis of 2‐thiophenyl‐ 3,5‐dinitropyridine

Cited by 10 publications

References 35 publications

Solvent and substituent effects on the reaction of 2‐ and 4‐chloro‐3,5‐dinitrobenzotrifluorides with substituted anilines

Solvent and substituent effects on the reaction of 2‐ and 4‐chloro‐3,5‐dinitrobenzotrifluorides with substituted anilines

Kinetics of the Reaction of 2‐Chloro‐3,5‐dinitrobenzotriflouride with Aniline in Toluene and Methanol‐Toluene Mixed Solvents

Nucleophilic Aromatic Substitution

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