Selective O-methylation of phenols and benzyl alcohols in simple pyridinium based ionic liquids

Das, Pranab Jyoti; Das, Jupitara

doi:10.1016/j.molliq.2015.05.028

Cited by 10 publications

(2 citation statements)

References 32 publications

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“…The [p-C 4 Pic]Br and [o-C 4 Pic]Br were obtained as white solids with yields of 91% and 72%, while the [m-C 4 Pic]Br was precipitated as transparent liquid (yield of 87%). All the synthesized compounds were washed three times with THF, accurately dried under vacuum and characterized using NMR spectroscopy, and the obtained spectra were in agreement with the data reported in the literature [ 30 , 32 , 33 ].…”

Section: Experimental Partsupporting

confidence: 83%

A Specific Interaction between Ionic Liquids’ Cations and Reichardt’s Dye

et al. 2022

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Solvatochromic probes are often used to understand solvation environments at the molecular scale. In the case of ionic liquids constituted by an anion and a cation, which are designed and paired in order to obtain a low melting point and other desirable physicochemical properties, these two indivisible components can interact in a very different way with the probe. This is the case with one of the most common probes: Reichardt’s Dye. In the cases where the positive charge of the cation is delocalized on an aromatic ring such as imidazolium, the antibonding orbitals of the positively charged aromatic system are very similar in nature and energy to the LUMO of Reichardt’s Dye. This leads to an interesting, specific cation-probe interaction that can be used to elucidate the nature of the ionic liquids’ cations. Parallel computational and experimental investigations have been conducted to elucidate the nature of this interaction with respect to the molecular structure of the cation.

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Section: Experimental Partsupporting

confidence: 83%

A Specific Interaction between Ionic Liquids’ Cations and Reichardt’s Dye

et al. 2022

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“…(lit. 115.6‐116.1°С), 1 H NMR (δ, ppm; J , Hz; (СD 3 ) 2 SO): 3.67 s (3H; СH 3 ), 7.33 d (2H, СH aryl J 8.8), 7.49 d (2H, СH aryl , J 8.8), 9.79 s (1H; NH).…”

Section: Methodsmentioning

confidence: 99%

Interaction of dimethyl carbonate with anilines in the presence of potassium methylate: Kinetics and the role of the base

Mantrov

Gordeev

Dashkin

et al. 2019

Int J of Chemical Kinetics

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The kinetic patterns of the reaction between dimethyl carbonate and anilines in the presence of a potassium methylate as a catalyst were studied. The mechanism of aminolysis was clarified, which includes the detachment of the proton from the amino group of aniline and the subsequent attack of the resulting anion on the carbonyl group of dimethyl carbonate. It is shown that when the reaction occurs in the dimethyl carbonate‐methanol 3:1 system, the process can be described as an irreversible first‐order reaction in the aniline though the target reaction is complicated by side interaction between potassium methylate and dimethyl carbonate. The rate constants of the target reaction with substituted anilines and of the side reaction in the temperature range of 70‐90°C were determined. It is shown that the influence of the substituent on the reaction rate is described by the Hammett equation, with the constant of the reaction series being positive and the best correlation being achieved for Ïƒ‐scale. The results obtained are consistent with the proposed mechanism of the reaction and are explained by the facilitation of the aniline deprotonation with increasing acceptor properties of the substituent. Effective activation energies for the reaction of various anilines with dimethyl carbonate are found.

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Electrochemically Driven Nickel‐Catalyzed Halogenation of Unsaturated Halide and Triflate Derivatives

Chen,

Charvet,

Payard

et al. 2023

Angewandte Chemie

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A robust electrochemically driven nickel‐catalyzed halogen exchange of unsaturated halides and triflates (Br to Cl, I to Cl, I to Br, and OTf to Cl) is reported. A combination of NiCl2 ⋅ glyme as the precatalyst, 2,2′‐bipyridine as a ligand, NMP as the solvent, and electrochemistry allowed the generation of a nickel species that promotes reductive elimination of the desired product. This paired electrochemical halogenation is compatible with a range of unsaturated halides and triflates, including heterocycles, dihaloarenes, and alkenes with good functional‐group tolerance. Joint experimental and theoretical mechanistic investigations highlighted three catalytic events: i) oxidative addition of the aryl halide to a Ni(0) species to deliver a Ni(II) intermediate; ii) halide metathesis at Ni(II); iii) electrochemical oxidation of Ni(II) to Ni(III) to enable the formation of the desired aryl halide upon reductive elimination. This methodology allows the replacement of heavy halogens (I or Br) or polar atoms (O) with the corresponding lighter and more lipophilic Cl group to block undesired reactivity or modify the properties of drug and agrochemical candidates.

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Selective O-methylation of phenols and benzyl alcohols in simple pyridinium based ionic liquids

Cited by 10 publications

References 32 publications

A Specific Interaction between Ionic Liquids’ Cations and Reichardt’s Dye

A Specific Interaction between Ionic Liquids’ Cations and Reichardt’s Dye

Interaction of dimethyl carbonate with anilines in the presence of potassium methylate: Kinetics and the role of the base

Electrochemically Driven Nickel‐Catalyzed Halogenation of Unsaturated Halide and Triflate Derivatives

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