Solvent hydrogen bonding and structural effects on nucleophilic substitution reactions: Part 4 — Reaction of 2-chloro-5-nitropyridine with para-substituted anilines in acetonitrile/dimethylformamide mixtures

Bhuvaneshwari, D. S.; Elango, K. P.

doi:10.1016/j.molliq.2008.07.008

Cited by 19 publications

(13 citation statements)

References 36 publications

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“…The order of magnitude of the ρ value depends on both the molecular structure of reactants and solvent effects. For instance, the reaction of 2‐chloro‐5‐nitropyridine or benzenesulfonyl chloride with substituted anilines in binary molecular solvents exhibits low values for ρ about ten times less than the values in this study . However, the similar ρ values have been observed for the studied reaction in binary mixtures of methanol and ethyl acetate .…”

Section: Resultssupporting

confidence: 64%

“…Methodical studies of the substituent effects of the chemical reactions in solution have been carried out comprehensively by many researchers since the proposal of Hammett's equation . In some studies, the relationships between the proportionality constant, ρ , values and the environmental changes have also been the major subject of the reports . It has been confirmed that a solvent as environment in chemical reactions plays an important role in many chemical and physical processes.…”

Section: Introductionmentioning

confidence: 99%

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Deep eutectic solvent as an operative media on structure‐reactivity relationships

Harifi‐Mood

Khorshahi

2019

Int J of Chemical Kinetics

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Deep eutectic solvents seem to be environmentally friendly solvents, particularly because they are prepared easily and have very low‐vapor pressures under ambient conditions. They are suitable candidates as green solvents for reaction media with special properties. To present this behavior, substitution reactions of some para‐ and meta‐substituted anilines with 1‐fluoro‐2,4‐dinitrobenzene have been spectrophotometrically investigated in varying mole fractions of ethaline as a deep eutectic solvent in dimethyl sulfoxide (DMSO). The measured rate coefficients of the reaction demonstrated a noticeable variation with the increasing mole fraction of ethaline in ethaline‐DMSO mixtures. The linear free energy relationship (LFER) of second‐order rate coefficients based on Hammett's substituent constants demonstrates a reasonably linear straight line with a negative slope in different mole fractions of ethaline‐DMSO mixtures. Another LFER investigation based on the polarity parameters of the media showed a good agreement with hydrogen bond donor and acceptor abilities of the solvent. Non‐LFER assay according to the preferential solvation model confirmed differences between the microsphere solvation of the solute molecules and the bulk composition of the solvents.

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Section: Resultssupporting

confidence: 64%

Section: Introductionmentioning

confidence: 99%

Deep eutectic solvent as an operative media on structure‐reactivity relationships

Harifi‐Mood

Khorshahi

2019

Int J of Chemical Kinetics

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“…Such a specific solvation of the NH 2 moiety by HBD solvents has already been demonstrated by us using electronic spectral and cyclic voltammetric techniques [22,23]. When the mole fraction of benzene (a typical non-HBD solvent) in the mixture is increased, the mild block has been removed progressively, the formation of transition state has increasingly become easier and consequently increased the rate of oxidation, as observed.…”

Section: Solvent-reactivity Correlationmentioning

confidence: 64%

Preferential solvational effects on the Cr(VI) oxidation of benzylamines in benzene/2‐methylpropan‐2‐ol mixtures

Thirumoorthi

Bhuvaneshwari

Elango

2010

Int J of Chemical Kinetics

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Imidazolium fluorochromate (IFC) oxidation of 11 meta-and para-substituted benzylamines, in varying mole fractions of benzene/2-methylpropan-2-ol binary mixtures, is first order in IFC and acid and zero order in substrate. The Hammett correlation yielded a U-shaped curve, indicating a change in the relative importance of bond formation and bond fission in the transition state. The rate data failed to correlate with macroscopic solvent parameters such as ε r and E N T . The correlation of k obs with Kamlet-Taft solvatochromic parameters suggests that H-bonding between the reacting species and the solvent plays a major role in governing the reactivity. C 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: [159][160][161][162][163][164][165][166][167] 2010

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“…Hence, the reaction rate increases with the dipolarity/polarisability of medium. Bhuvaneshwari and Elango [14] found that in the reaction of 2-chloro-5-nitropyridine with parasubstitued anilines in AN/DMF mixtures, the dipolarity/polarisability of the medium increased the reaction rate and the π* parameter had the greatest highest effect on reaction rate compared to the other parameters. Similar structures and interactions in IL/1-propanol and IL/2-propanol lead to similar behaviour in these mixtures, which are shown in Figure 1.…”

Section: Resultsmentioning

confidence: 99%

Systems Designed with an Ionic Liquid and Molecular Solvents to Investigate the Kinetics of an S_NAr Reaction

Salari

Hallett

Padervand

et al. 2013

Progress in Reaction Kinetics and Mechanism

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The microscopic features of binary solvent systems formed by molecular solvents (methanol, ethanol, 2-methylpropan-2-ol, water, pyridine, acetonitrile, 1-propanol, 2-propanol, dimethylformamide) and the ionic liquid ([bmim]BF 4 ) as cosolvent were used to select mixed solvents with particular characteristics. Molecular-microscopic solvent parameters corresponding to these binary mixtures were utilised to study the kinetics of the nucleophilic substitution reaction between 2-chloro-3,5-dinitropyridine and aniline to investigate and compare the effects of the solvents on a model chemical reaction. For these mixtures, the solvation behaviour is dominated by both the dipolarity/ polarisability and hydrogen bonding interactions of the media. In these solutions, the rate constants of the reaction decrease with the mole fraction of ionic liquid.

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Solvent hydrogen bonding and structural effects on nucleophilic substitution reactions: Part 4 — Reaction of 2-chloro-5-nitropyridine with para-substituted anilines in acetonitrile/dimethylformamide mixtures

Cited by 19 publications

References 36 publications

Deep eutectic solvent as an operative media on structure‐reactivity relationships

Deep eutectic solvent as an operative media on structure‐reactivity relationships

Preferential solvational effects on the Cr(VI) oxidation of benzylamines in benzene/2‐methylpropan‐2‐ol mixtures

Systems Designed with an Ionic Liquid and Molecular Solvents to Investigate the Kinetics of an S_NAr Reaction

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Solvent hydrogen bonding and structural effects on nucleophilic substitution reactions: Part 4 — Reaction of 2-chloro-5-nitropyridine with para-substituted anilines in acetonitrile/dimethylformamide mixtures

Cited by 19 publications

References 36 publications

Deep eutectic solvent as an operative media on structure‐reactivity relationships

Deep eutectic solvent as an operative media on structure‐reactivity relationships

Preferential solvational effects on the Cr(VI) oxidation of benzylamines in benzene/2‐methylpropan‐2‐ol mixtures

Systems Designed with an Ionic Liquid and Molecular Solvents to Investigate the Kinetics of an SNAr Reaction

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Product

Resources

About

Systems Designed with an Ionic Liquid and Molecular Solvents to Investigate the Kinetics of an S_NAr Reaction