Sharif Digital Repository

A task-specific Brønsted acidic ionic liquid (BAIL), 1-benzyl-3-methylimidazolium hydrogensulfate ([BnMIm]HSO4), was prepared and confined onto the high surface area silica gel. The catalyst has shown extraordinary activity in comparison of homogeneous ionic liquid (IL) system for Fischer esterification of fatty acid with ethanol. The ester derivatives were synthesized in high yields and catalyst was easily separated from the reaction mixture by simple filtration. The structure of the catalyst is theoretically modelized to investigate the unusual catalytic activity. Hence, a hydroxylated cage-like nano-cluster, H6Si8O12(OH)2, was selected to mimic the surface of silica gel. The interactions... 

The sole industrial process which currently used for adipic acid production is nitric acid oxidation of either cyclohexanol or cyclohexanol/cyclohexanone mixture. Emission of greenhouse nitrous oxide (N2O) gas from this process strongly contributes to global warming, resulting in acid rain and ozone depletion. Herein, we report a catalytic application of a novel dual task-specific ionic liquid (an ionic liquid with two catalytic functions) for oxidation of cyclohexene to adipic acid using 30% hydrogen peroxide. The catalyst showed desirable activity toward oxidation of cyclohexene and some cyclic olefins to produce their corresponding dicarboxylic acids  

Exploring deprotonation properties of silica-functionalized propylsulfonic acid catalyst (silica-propyl-SO3H) is the subject of various experimental and theoretical researches. In the current study, the structure of the silica-propyl-SO3H has been simulated using density functional theory (DFT) methods by mimicking the surface of the silica in the form of cubic cage-like nanoclusters of silicon and oxygen. The values of ΔHacidity for gas-phase deprotonation are calculated considering various possible interactions of the propylsulfonic acid on the surface of the silica. Our investigations indicate that interactions of sulfonic acid (-SO3H) head... 

The current work deals with the catalytic application of bis(1-butyl-3-methylimidazolium) tungstate ([BMIm]2WO4) for green synthesize of glutaric acid (GA) through oxidative cleavage of cyclopentene. In this method, 30% hydrogen peroxide (H2O2) was used as oxidant with water as the sole by-product of the reaction. Compared to the current synthetic procedures, this protocol is significantly improved in the environmental point of view. Moreover, the effect of the various parameters was investigated on the reaction efficiency. It was found that high yield of GA could obtain without using special methodologies or precautions. The catalytic system is reusable for several times  

A novel silica-functionalized ammonium tungstate interphase catalyst has been reported as a non-nitric acid route for adipic acid production from one-pot oxidative cleavage of 30% hydrogen peroxide and catalytic amounts of p-toluenesulfonic acid (PTSA). The catalyst has been simply prepared by commercially available starting material. The structure of the catalyst has been investigated using FT-IR spectroscopy, atomic absorption, TEM, SEM and XRD analysis. The catalyst has shown good to high activity even up to 10 runs of reaction. Simple preparation of the catalyst, avoids using harmful phase transfer catalyst (PTC) and/or chlorinated additives are among the other benefits of this work  

A green and facile method for oxidation of cyclohexene to adipic acid is introduced using 30% H2O2 as oxidant. The catalytic system comprises small amounts of Ag2WO4 nano-rods and a Brønsted acidic ionic liquid (1,2-dimethyl-3-dodecylidazolium hydrogensulfate)  

In recent years, polyethylene glycol (PEG) has attracted special attention as a green and inexpensive solvent in various chemical transformations. The current critical review deals with breakthrough achievements for the applications of PEG as an alternative reaction media well-known coupling reactions such as Suzuki, Heck, Stille, Sonogashira, Hiyama and some challenging organic reactions for carbon-carbon bond formation  

1-Butyl-3-methylimidazolium tungstate ([BMIm] 2WO 4) ionic liquid supported onto silica sulphamic acid demonstrated desirable performance for oxidation of cyclohexene to adipic acid. Simple experimental procedure, easy product isolation, catalyst recovery and reusability are some attractive features of this protocol  

A novel silica-functionalized dual Brønsted acidic ionic liquid (ionic liquid with two Brønsted acidic species) has been reported as a highly efficient catalyst for thioacetalization of carbonyl compounds. The reaction was efficiently performed in water as an environmentally benign solvent with good to high yields. Thermal gravimetric analysis showed that the catalyst is stable at least up to 350 C. Furthermore, the catalyst can be recycled and reused for six runs of reaction without appreciable loss of activity. The structure of the catalyst is modelized to gain more realistic structural insight about the functionalized ionic liquid  

Owing to the inherent incompatibility with water, cyanation of aryl halides may be the most challenging category of palladium-catalyzed coupling reactions. The major challenges are attributed to the catalyst deactivation by the soluble cyanide (CN−) ions and desirable conversions only could be obtained by employing toxic organic solvents. The current minireview highlights mechanistic insights and breakthrough achievements for this reaction in the aqueous media  

A phenolic-based ionic liquid (IL), 1-(2-hydroxyethyl)-2,3-dimethylimidazolium phenoxide has been introduced for 1.5 molar carbon dioxide (CO2) absorption at ambient conditions without using special methodologies or precautions. The structure of the IL was characterized by various methods such as FT-IR, 1H NMR, 13C NMR, elemental analysis (EA) and thermogravimetric analysis (TGA). The ability of this IL for CO2 uptake reaches to its maximum value after 2 h. The IL has been reused fr several times with constant efficiency. Density functional theory (DFT) calculations at the B3LYP/6-311++G∗∗ level of calculation have been carried out to gain more structural knowledge... 

The current work deals with modification of the surface of a silica-polyamine with amine-based ionic liquid (IL) and its application for removal of Cu2+ from an aqueous media. The absorbent is simply prepared from commercially available reagents. The material is characterized by FT-IR spectroscopy, thermogravimetric analysis (TGA), N2 adsorption-desorption, and transmission electronic microscopy (TEM). Effects of several parameters on absorption efficiency, as well as activity of the absorbent to other metals, are also investigated. Moreover, the reusability of the absorbent is studied at the optimized condition. © The Royal Society of Chemistry 2016  

Influence of the addition of water molecules (n = 1-6) on the interaction energy between Li +, Na +, K + cations and indole molecule as tryptophan amino acid residue is considered at MP2(FULL)/6-311++G(d, p)//B3LYP/6-311++G(d,p) levels of theory. The calculations suggest that the size of cation and the number of water molecules are two important factors that affect the interaction energy between the hydrated metal cation and indole molecule. The strength of cation-π interactions get substantially reduced when the metal ion is solvated or the size of metal cation increases. Quantum theory of atoms in molecules analysis of cation-π interaction indicates that there is a correlation between the... 

The effects of six synthetic imidazolium-based ionic liquids (ILs) on the CuII-catalyzed chemiluminescence of lucigenin (Luc-CL) in the pH range 6.0-11 were investigated. Preliminary experiments found that the CL emission was strongly enhanced or inhibited in the presence of the ILs. The degree of enhancement or inhibition of the CL intensity in the presence of each IL was related to the molecular structure of the IL, the medium used, and the pH. The maximum enhancement of the CL intensity was observed at pH 9.0 (amplification factor=443). This decrease in the pH at which maximum CL enhancement occurred and the substantial signal amplification of the Luc-CL may be related to a strong... 

Abstract: The current study deals with the applications of a surfactant-like Brønsted acidic ionic liquid (IL) 1-dodecyl-3-methylimidazolium hydrogen sulfate ([DMIm]HSO4) for Mannich reaction at room temperature. The reaction was efficiently preceded in water as solvent without using any harmful and expensive organic additives. Our findings showed that the reaction is selective for cyclohexanone and no Mannich product was observed when cyclopentanone was used as starting material. Density functional theory (DFT) calculations were performed to provide an evidence about the nature of reactivity of the cyclohexanone/cyclopentanone. The activity of the catalyst was also tested for biodiesel... 

(Equation present) Density functional theory (DFT) was used to investigate the acidity of the various silica alkyl sulfonic acids. In this regard, cluster models with various alkyl spacer lengths were selected to mimic the surface of silica gel. The effects of distance from the surface and the role of hydrogen bond (H-bond) on the ΔHacidity values of these catalysts were investigated. DFT calculations revealed that a notable gap of ΔH acidity values exists between the structures considering lateral hydrogen bonding with the surface of the silica HB structure and the structures with omitted surface interactions (non-HB structures). Natural bonding orbital (NBO) and quantum theory of atoms in... 

A novel mesoporous silica-functionalized dual Brønsted acidic species has been introduced as an efficient catalyst for solvent-free esterification of fatty acids with ethanol. The structure of the catalyst has been characterized by FT-IR spectroscopy, thermal gravimetric analysis (TGA), TEM and N2 adsorption-desorption. TGA of catalyst 1 showed no weight loss before 200 °C, indicating a high degree of hydrophobicity of the surface of the mesoporous silica. TEM images and nitrogen adsorption-desorption showed no noticeable changes to the structure of the catalyst before and after acid treatment. pH metric analysis was performed for the catalyst to determine the loading of the acidic sites.... 

Silica gel-confined ionic liquid (IL) is a class of heterogeneous catalysts with broad catalytic applications. Leaching of the IL from the surface of the support is the major drawback of these catalysts, which reduce the catalyst efficiency during the chemical reactions. To investigate the effect of the hydrogen bonding on the leaching phenomena, the interaction between the 1-ethyl-3-methylimidazolium-based IL with various anions (Cl-, Br-, HSO4 -, NO3 -, BF 4 -, and PF6 -) and the surface of the silica gel were studied using density functional theory. Hence, a hydroxylated cage-like cluster of silica gel, Si4O6(OH), was selected to mimic the surface. The values of ÎEinteraction show that... 

For the first time, the mechanism of Fischer esterification between acetic acid and ethanol over silica-functionalized propylsulfonic acid (silica-propyl-SO3H) catalyst was explored by means of computational modeling techniques. For this purpose, 6-edge-atom cage-like cluster comprising Si-O-Si sequences has been selected to represent the surface of the catalyst. The results indicate that the reaction goes through concerted transition states. In all optimized structures no proton (H+) transfer occurs from catalyst to the substrates and the role of the catalyst is via the activation of the substrates through the formation of strong hydrogen bonds (H-bonds). Furthermore, the energetic diagram...