Theoretical and Experimental Studies on the Regioselectivity of Epoxide Ring Opening by Nucleophiles in Nitromethane without any Catalyst: Nucleophilic-Chain Attack Mechanism

Mohseni, S H; Bakavoli, Mehdi; Morsali, Ali

doi:10.3184/97809059274714x13874723178403

Cited by 20 publications

(21 citation statements)

References 41 publications

(36 reference statements)

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“…The 6-31G(d,p) basis sets were employed except for Fe where the LANL2DZ basis set [21] was used with effective core potential (ECP) functions. The solvent has an important role in chemical reactions explicitly [22][23][24][25] or implicitly. The implicit effects of the solvent were considered by using the polarised continuum model (PCM) [26].…”

Section: Computational Detailsmentioning

confidence: 99%

Density Functional Theoretical Study on the Mechanism of Adsorption of 2-Chlorophenol from Water Using γ-Fe₂O₃ Nanoparticles

Magham

Morsali

Es’haghi

et al. 2015

Progress in Reaction Kinetics and Mechanism

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Using density functional theory, the mechanism of adsorption of 2-chlorophenol from water in the presence of γ-Fe 2 O 3 nanoparticles was investigated. Fe 2 O 3 nanoparticles were modelled using Fe 6 (OH) 18 (H 2 O) 6 ring clusters. 2-chlorophenol can coordinate to the γ-Fe 2 O 3 nanoparticles via its own OH or Cl groups. The process produces two intermediates which will be converted into final products through two pathways (Cl pathway and OH pathway). The activation energy and activation Gibbs free energy of the two pathways have been calculated and compared with each other. It was found that the OH pathway is under thermodynamic control and the C1 pathway is under kinetic control. All of the calculations were performed using a hybrid density functional method (B3LYP) in the solution phase (PCM model).

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Section: Computational Detailsmentioning

confidence: 99%

Density Functional Theoretical Study on the Mechanism of Adsorption of 2-Chlorophenol from Water Using γ-Fe₂O₃ Nanoparticles

Magham

Morsali

Es’haghi

et al. 2015

Progress in Reaction Kinetics and Mechanism

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“…The unsuccessful reaction in aqueous media and less fruitful reaction in ethanol encouraged us to explore the organic polar solvents. [37] Two factors, use of catalysts [15,[18][19] and high molar ratio of the epoxide [27] or amine [38] are broadly responsible for the efficiency of the ring opening reactions. Considering the complexities of these reactions, we attempted the ring opening reactions in the presence polar solvents (i.e.…”

Section: Resultsmentioning

confidence: 99%

“…aniline), which is one of the major drawbacks of these reported reactions. [38] Therefore, nitromethane was selected for the ring opening tert-butyl(1-(oxiran-2-yl)-2phenylethyl)carbamate (1) with p-toluidine (2a) (1.0 mmol) under microwave conditions and the yield of the product (3a) was significantly improved. The optimization of reaction conditions (i.e.…”

Section: Resultsmentioning

confidence: 99%

Catalyst Free, Nitromethane Assisted Facile Ring Opening of Epoxide with Less Reactive Aromatic Amines

Kumar¹,

Bansal²,

Upadhyay³

et al. 2020

Preprint

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<p>Nucleophilic ring opening reactions of epoxides with aromatic amines are in the forefront of the synthetic organic chemistry research to build new bioactive scaffolds. Here, a convenient, green and highly efficient regioselective ring opening of sterically hindered (2R,3S)-3-(<i>N</i>-Boc-amino)-1-oxirane-4-phenylbutane with various poorly reactive aromatic amines are accomplished under microwave irradiation in nitromethane. All the reactions effectively implemented for various aromatic amines involves reuse of nitromethane that supports its dual role as a solvent and catalyst. The corresponding new β-alcohol analogs of hydroxyethylamine (HEA) are isolated in 41-98% yields. The reactions proceed under mild conditions for a broad range of less reactive and sterically hindered aromatic amines. Proton NMR and UV-visible spectroscopic studies suggest that the nucleophilicity of amines is influenced by nitromethane, which is substantiated by the extensive computational studies. Overall, this methodology elucidates the first time use of nitromethane as a solvent for the ring opening reactions under microwave conditions involving equimolar ratio of epoxide and aromatic amine without any catalyst, facile ring opening of complex epoxide by less reactive aromatic amines, low reaction time, less energy consumption, recycling of the solvent and simple workup procedures.</p>

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“…A.02) 34 were used for the optimization of all degrees of freedom for all geometries in the solution phase. The solvent plays a key role in chemical systems explicitly [35][36][37][38][39][40][41][42][43] or implicitly. The polarized continuum model (PCM) 44,45 was used for the consideration of the implicit effects of the solvent.…”

Section: Computational Detailsmentioning

confidence: 99%

Mechanistic, energetic and structural studies of single-walled carbon nanotubes functionalized with penicillamine

Shaki

Morsali

Raissi

et al. 2018

JSCS

Self Cite

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Using the density functional theory, the possible non-covalent interactions and six mechanisms of covalent functionalization of the drug penicillamine with functionalized carbon nanotubes (CNT) were investigated. Quantum molecular descriptors of the non-covalent configurations were studied. It was determined that binding of the drug penicillamine with functionalized CNT is thermodynamically viable. COOH functionalized CNT (NTCOOH) has more binding energy than COCl functionalized CNT (NTCOCl) and could act as a favorable system for penicillamine drug delivery within biological and chemical systems (non-covalent). NTCOOH and NTCOCl can bond to the NH 2 , OH and SH groups of penicillamine through OH (COOH mechanism) and Cl (COCl mechanism) groups, respectively. The activation energies, activation enthalpies and activation Gibbs energies of six pathways were calculated and compared with each other. The activation parameters related to the COOH mechanism are higher than those related to the COCl mechanism and therefore, the COCl mechanism is suitable for covalent functionalization. These results could be generalized to other similar drugs.

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Theoretical and Experimental Studies on the Regioselectivity of Epoxide Ring Opening by Nucleophiles in Nitromethane without any Catalyst: Nucleophilic-Chain Attack Mechanism

Cited by 20 publications

References 41 publications

Density Functional Theoretical Study on the Mechanism of Adsorption of 2-Chlorophenol from Water Using γ-Fe₂O₃ Nanoparticles

Density Functional Theoretical Study on the Mechanism of Adsorption of 2-Chlorophenol from Water Using γ-Fe₂O₃ Nanoparticles

Catalyst Free, Nitromethane Assisted Facile Ring Opening of Epoxide with Less Reactive Aromatic Amines

Mechanistic, energetic and structural studies of single-walled carbon nanotubes functionalized with penicillamine

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Theoretical and Experimental Studies on the Regioselectivity of Epoxide Ring Opening by Nucleophiles in Nitromethane without any Catalyst: Nucleophilic-Chain Attack Mechanism

Cited by 20 publications

References 41 publications

Density Functional Theoretical Study on the Mechanism of Adsorption of 2-Chlorophenol from Water Using γ-Fe2O3 Nanoparticles

Density Functional Theoretical Study on the Mechanism of Adsorption of 2-Chlorophenol from Water Using γ-Fe2O3 Nanoparticles

Catalyst Free, Nitromethane Assisted Facile Ring Opening of Epoxide with Less Reactive Aromatic Amines

Mechanistic, energetic and structural studies of single-walled carbon nanotubes functionalized with penicillamine

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Density Functional Theoretical Study on the Mechanism of Adsorption of 2-Chlorophenol from Water Using γ-Fe₂O₃ Nanoparticles

Density Functional Theoretical Study on the Mechanism of Adsorption of 2-Chlorophenol from Water Using γ-Fe₂O₃ Nanoparticles