Kinetics of the Nucleophilic Substitution Reactions of Methyl 2,4-Dichloro-3,5-Dinitrobenzoate with Piperidine, Piperazine, Morpholine and Thiomorpholine in Methanol and Benzene

Fathalla, Magda F.; Hamed, Ezzat A.

doi:10.3184/030823406777980646

Cited by 10 publications

(10 citation statements)

References 26 publications

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“…This agrees with the rate determining formation of the zwitterionic intermediate I., Scheme 4. This is in line with the nucleophilic aromatic displacements of a good leaving group in polar and dipolar solvents (Khattab, Hamed, Albericio, & El-Faham, 2011;El-Mallah, Nabil, Senior, Ramadan, & Hamed, 2010;Asghar, Fathalla, & Hamed, 2009;Fathalla, Kassem, & Hamed, 2008;Khattab, Hassan, Hamed, & El-Faham, 2007;Al-Howsaway, Fathalla, El-Bardan, & Hamed, 2007;Fathalla & Hamed, 2006;Fathalla, Ibrahim, & Hamed, 2004;El-Hegazy, Abdel-Fathah, Hamed, & Sharaf, 2000;Hamed, El-Bardan, Saad, Gohar, & Hassan, 1997;Hamed, 1997aHamed, , 1997b. The plot of H # against log -S # for the reaction of 2 with hydrazine in MeOH, MeCN and DMSO gave straight line (r = 0.99) indicating a common mechanism for the reaction of 2 with hydrazine in these solvents.…”

Section: Reactions Of 1-chloro-24-dinitrobenzene 2 With Hydrazine Insupporting

confidence: 61%

Nucleophilic Substitution Reactions of 2,4-Dinitrobenzene Derivatives with Hydrazine: Leaving Group and Solvent Effects

Ibrahim¹,

Abdel-Reheem²,

Khattab³

et al. 2013

IJC

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The hydrazinolysis of 2,4-dinitrophenyl acetate in methanol proceed exclusively through acyl-oxygen scission by a concerted mechanism. The reaction of 1-chloro-2,4-dinitrobenzene with hydrazine in methanol, acetonitrile and dimethyl sulfoxide undergo uncatalyzed substitution and the formation of the zwitterionic intermediate is the rate-determining step. While 2,4-dinitrobenzene derivatives 1, 2, 3, 4, 5a-i, 6 with hydrazine in DMSO undergo uncatalyzed substitution and the departure of the leaving group is the rate-determining step. The process depends on the basicity of the leaving group and its steric hindrance as well as the possible intramolecular hydrogen bond in the transition state. The reactivity of compounds 5a-i depends on the substituent of the thioaryl ring while the small ρ Y value is due to the sulfides existing preferentially in the skew conformation. The small β lg value (-0.18, r = 0.99) indicated that the reaction of sulfides with hydrazine proceeds with advanced bond formation to the nucleophile and the bond cleavage proceed in a slow extent in the transition state.

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Section: Reactions Of 1-chloro-24-dinitrobenzene 2 With Hydrazine Insupporting

confidence: 61%

Nucleophilic Substitution Reactions of 2,4-Dinitrobenzene Derivatives with Hydrazine: Leaving Group and Solvent Effects

Ibrahim¹,

Abdel-Reheem²,

Khattab³

et al. 2013

IJC

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“…Here nucleophilic attack is rate limiting and the effect of variations in the nature of the nucleophile and solvent were discussed. 8 The hydroxy-dehalogenation of activated haloarenes in alkaline water or water-DMF solvents has been shown to be accelerated by the addition of hydrogen peroxide. The mechanism is likely to involve aryl hydroperoxide intermediates.…”

Section: The S N Ar Mechanismmentioning

confidence: 99%

“…28 It has been shown that the use of copper(II) salts as catalysts with oxygen as the oxidant may be effective in the oxidative substitution of ring hydrogen by nucleophiles including halides and acetoxy ions; a mechanism involving single electron transfer (SET) is likely. 29 Catalysis by cobalt(II) has been reported in the reaction of the aryl copper compound (8) with aryl fluorides to produce polyfunctional biophenyls. 30 Cu(CN)MgCl CN (8) There has been a summary explaining how the use of reaction kinetics may help in the interpretation of complex catalytic reaction schemes; examples include palladiumcatalysed coupling reactions of aryl halides.…”

Section: The S N Ar Mechanismmentioning

confidence: 99%

“…29 Catalysis by cobalt(II) has been reported in the reaction of the aryl copper compound (8) with aryl fluorides to produce polyfunctional biophenyls. 30 Cu(CN)MgCl CN (8) There has been a summary explaining how the use of reaction kinetics may help in the interpretation of complex catalytic reaction schemes; examples include palladiumcatalysed coupling reactions of aryl halides. 31 A short review has been published on the use of hydrophilic ligands for palladium in aqueous-phase reactions involving aryl halides.…”

Section: The S N Ar Mechanismmentioning

confidence: 99%

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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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“…In benzylic carbon is of broad synthetic utility and has received exceptionally detailed attention by chemists. Fundamental concepts like steric effects, polar effects, nucleophilicity, solvent property and structure action correlations have been urbanized through this study 5 . The effect of nucelophile and the effect of substituent on the rate of the reaction.…”

Section: Introductionmentioning

confidence: 99%

Conductance Study of Benzyl Bromide Reaction with Cyclicamines in Aqueous-Ethanol Medium

Radhika¹,

2018

IJET

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Nucleophilic substitution reaction of benzyl bromide and cyclicamines in ethanol aqueous intermediate reactivity can suggest that the nucleophile increases through their pKa values. A linear correlation exists between computed values of the dipole moment, rate and electronegativity of the nucelophiles. The two reactants suggest that frontier molecular orbital interactions ion-solvation and correlation of time with the HOMO-LUMO breach of that the reaction. But it is not orbital controlled as well as forbidden by the electrostatic interactions along with mixed solvent composition between the reactants. The influence on the solvation of ions before reaction has been discuss with facilitate by R-factor. Thermodynamic properties are evaluate and report. The consequences of the learning to be interpreted in terms of ion-solvent exchanges and solvent properties comparing with electrostatic interaction between the reactants.

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Kinetics of the Nucleophilic Substitution Reactions of Methyl 2,4-Dichloro-3,5-Dinitrobenzoate with Piperidine, Piperazine, Morpholine and Thiomorpholine in Methanol and Benzene

Cited by 10 publications

References 26 publications

Nucleophilic Substitution Reactions of 2,4-Dinitrobenzene Derivatives with Hydrazine: Leaving Group and Solvent Effects

Nucleophilic Substitution Reactions of 2,4-Dinitrobenzene Derivatives with Hydrazine: Leaving Group and Solvent Effects

Nucleophilic Aromatic Substitution

Conductance Study of Benzyl Bromide Reaction with Cyclicamines in Aqueous-Ethanol Medium

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