Kinetic and equilibrium studies of σ-adduct formation and nucleophilic substitution in the reactions of 2-chloro-3,5-dinitropyridine and 2-ethoxy-3,5-dinitropyridine with p-substituted anilines in DMSO

Asghar, Basim H.

doi:10.1007/s00706-012-0860-z

Cited by 5 publications

(1 citation statement)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…There is evidence of complexation in the reported experimental reaction of 2‐chloro‐3,5‐dinitropyridine with a series of anilines in DMSO and in the presence of DABCO. The reaction was considered to proceed through a two‐step mechanism where the formation of the MC intermediate was observed which could have been followed by either a base‐catalysed or uncatalyzed pathway; however, no accumulation of intermediates was detected spectrophotometrically [35] . The relative values of the calculated rate constants are in line with these observations.…”

Section: Resultssupporting

confidence: 52%

DFT Study of the S_NAr Reactions of 1‐Chloro‐2‐nitro‐ and 1‐Phenoxy‐2‐nitro‐benzenes with Aniline in Acetonitrile and Toluene: Concerted or Multistep Mechanism?

Oloba‐Whenu,

Isanbor

2023

ChemistrySelect

View full text Add to dashboard Cite

Computational studies to determine the rate constants and thermodynamic properties of the nucleophilic aromatic substitution reactions of 4‐R‐1‐chloro‐2,6‐dinitrobenzenes 1, 6‐R‐1‐chloro‐2,4‐dinitrobenzenes 2 and some of the corresponding 1‐phenoxy derivatives 3 and 4 with aniline in the gas phase, acetonitrile and toluene is reported at the M06‐2x/6‐31g+(d,p) level of theory; R=H, NO2, CF3, CN and ring N. Formation of the Meisenheimer complex intermediate was observed in all cases and its stability was dependent on the number of electron‐withdrawing groups present on the ring and their relative position. The overall reaction was found to be exothermic and exergonic in all cases. From kinetics calculations, the initial attack of the aniline nucleophile on the dinitrobenzene to form the intermediate is rate limiting with the chloride ion as the leaving group in acetonitrile and decomposition of the MC was rate limiting in vacuum and toluene. With the phenoxide ion as the leaving group, the decomposition of the MC intermediate is rate limiting in all cases. The observation of MC and thermodynamic data obtained are suggestive of the prevalence of a multistep SNAr mechanism and ring activation by electron withdrawing group increased the rate of reaction.

show abstract

Section: Resultssupporting

confidence: 52%

DFT Study of the S_NAr Reactions of 1‐Chloro‐2‐nitro‐ and 1‐Phenoxy‐2‐nitro‐benzenes with Aniline in Acetonitrile and Toluene: Concerted or Multistep Mechanism?

Oloba‐Whenu,

Isanbor

2023

ChemistrySelect

View full text Add to dashboard Cite

show abstract

Aromatic Substitution

Crampton¹

2016

Organic Reaction Mechanisms · 2013

View full text Add to dashboard Cite

Dinitropyridines: Synthesis and Reactions

Starosotnikov,

Bastrakov

2024

Asian J Org Chem

View full text Add to dashboard Cite

Dinitropyridines are one of the promising classes of heterocyclic compounds. They are considered as useful precursors of explosives and energetic compounds, agrochemicals, biosensors and biologically active compounds with diverse properties: antitumor, antiviral, anti‐neurodegenerative. Preliminary analysis of literature data shows that the chemistry of polynitropyridines has been actively developing over the past few decades. This is evidenced by the steadily growing annual number of publications. In this review the literature on the synthesis, reactions and practical application of isomeric dinitropyridines over a period of 2010‐2024 is analyzed.

show abstract

Kinetic and equilibrium studies of σ-adduct formation and nucleophilic substitution in the reactions of 2-chloro-3,5-dinitropyridine and 2-ethoxy-3,5-dinitropyridine with p-substituted anilines in DMSO

Cited by 5 publications

References 36 publications

DFT Study of the S_NAr Reactions of 1‐Chloro‐2‐nitro‐ and 1‐Phenoxy‐2‐nitro‐benzenes with Aniline in Acetonitrile and Toluene: Concerted or Multistep Mechanism?

DFT Study of the S_NAr Reactions of 1‐Chloro‐2‐nitro‐ and 1‐Phenoxy‐2‐nitro‐benzenes with Aniline in Acetonitrile and Toluene: Concerted or Multistep Mechanism?

Aromatic Substitution

Dinitropyridines: Synthesis and Reactions

Contact Info

Product

Resources

About

Kinetic and equilibrium studies of σ-adduct formation and nucleophilic substitution in the reactions of 2-chloro-3,5-dinitropyridine and 2-ethoxy-3,5-dinitropyridine with p-substituted anilines in DMSO

Cited by 5 publications

References 36 publications

DFT Study of the SNAr Reactions of 1‐Chloro‐2‐nitro‐ and 1‐Phenoxy‐2‐nitro‐benzenes with Aniline in Acetonitrile and Toluene: Concerted or Multistep Mechanism?

DFT Study of the SNAr Reactions of 1‐Chloro‐2‐nitro‐ and 1‐Phenoxy‐2‐nitro‐benzenes with Aniline in Acetonitrile and Toluene: Concerted or Multistep Mechanism?

Aromatic Substitution

Dinitropyridines: Synthesis and Reactions

Contact Info

Product

Resources

About

DFT Study of the S_NAr Reactions of 1‐Chloro‐2‐nitro‐ and 1‐Phenoxy‐2‐nitro‐benzenes with Aniline in Acetonitrile and Toluene: Concerted or Multistep Mechanism?

DFT Study of the S_NAr Reactions of 1‐Chloro‐2‐nitro‐ and 1‐Phenoxy‐2‐nitro‐benzenes with Aniline in Acetonitrile and Toluene: Concerted or Multistep Mechanism?