Diiodination of Alkynes in supercritical Carbon dioxide

A general,green and efficient method for the synthesis of transdiiodoalkenes in CO2(sc) has been developed.Trans-diiodoalkenes were obtained stereospecifically in quantitative yields via diiodination of both electron-rich and electron-deficient alkynes in the presence of KI,Ce(SO4)2 and water in supercritical carbon dioxide [CO2(sc)]at 40℃.     

Characteristics of an oxa-diamide–HNO3 extractant in the supercritical fluid extraction of uranium

An extractant is required in the recovery process to drive the uranium to a stage that enables it to be extracted using the extraction solvent. This paper proposes the composition of a composite extractant, N,N,N′,N′-tetrabutyl-3-oxapentane-diamide–HNO₃ (TBODA–HNO₃) as an extractant, to successfully achieve the objective using supercritical carbon dioxide (sc-CO₂). The composite TBODA–HNO₃ extractant has a chemical composition of TBODA(HNO₃)_1.0(H₂O)_1.5. The U(IV) in the UO₂ containing solid phase is directly oxidized to U(VI) in the form of $ {\rm UO}_{2}^{2 + } $ in sc-CO₂, which contains a CO₂-soluble TBODA–HNO₃ extractant at 200 atm and 50 °C. The resulting $ {\rm UO}_{2}^{2 + } $ /TBODA complex can be consequently extracted using acetone-modified sc-CO₂. The chemical composition of the $ {\rm UO}_{2}^{2 + } $ /TBODA complex, which can be extracted by nonpolar sc-CO₂, is proposed in the form of an ion pair: [UO₂(TBODA)₂]²⁺–2( $ {\rm NO}_{3}^{ - } $ ).     

The influence of water on the isomerization of α-pinene in a supercritical aqueous-alcoholic solvent

The influence of water as a cosolvent and catalyst of the isomerization of α-pinene in a supercritical aqueous-alcoholic (ethanol) solvent was studied experimentally. At T = 657 K and p = 230 atm, an increase in the concentration of water in the reaction mixture was found to increase the rate of the reaction and its selectivity with respect to the desired product, limonene. Water exhibited the properties of an acid catalyst because of its ionization. Mathematical experimental data processing was performed to evaluate and separate the contributions of the radical and ionic paths to the total rate of the reactions that occurred during the thermal isomerization of α-pinene.     

Selective hydrogenation of phenol in supercritical carbon dioxide

Liquid phase hydrogenation of phenol over Pt/C catalysts was investigated under conventional conditions and supercritical carbon dioxide (scCO2). The equivalent ration of hydrogen to phenol shows a significant effect on the product selectivity. Hydrogenation of phenol in different solvents was also studied, the experimental results show that polarity of solvents influences the yield of cyclohexanone remarkably, scCO2 has the highest one. Catalytic hydrogenation of phenol in scCO2 or sub-sc…     

Solubility measurement of α-asarone in supercritical carbon dioxide

The solubility of α-asarone in supercritical CO₂ (sc-CO₂) has been measured using the dynamic method. The measurement was conducted in the pressure range from 9.0 to 18.0 MPa at temperature 35–49 °C. The experimental data were correlated using the Chrastil model. The results show that the solubility increases as the pressure rises and decreases as the temperature rises, which is well correlated with the Chrastil model.     

Density dependence of the "escape" yield of hydrated electrons in the low-LET radiolysis of supercritical water at 400 °C

The "spur lifetime" (τ(s)) in the low-linear energy transfer (LET) radiolysis of supercritical water (SCW) at 400 °C has been determined as a function of water density by using a simple model of energy deposition initially in spurs, followed by the random diffusion (Brownian motion) of the species formed until spur expansion is complete. The values of τ(s) are found to decrease from ～5.0 × 10(-6) to 5.0 × 10(-8) s over the density range from 0.15 to 0.6 g cm(-3). Using Monte-Carlo simulations, our calculated density dependence of the "escape" hydrated electron (e(aq)(-)) yield (i.e., at time τ(s)) reproduces fairly well Bartels and co-workers' scavenged e(aq)(-) yield data, suggesting that these data may have been measured at times close to τ(s).     

Characteristic profiles of the inclusion complex of omeprazole/peracylated-β-cyclodextrin formed in supercritical carbon dioxide

Inclusion properties of the drug omeprazole (OMP) with peracetylated-beta-cyclodextrin (PAc-β-CD) prepared by green method, following supercritical carbon-dioxide (scCO₂), were characterized through thermal (TGA and DSC), crystalline (XRD), NMR spectroscopic and dissolution studies. Comparison amongst PAc-β-CD, OMP, physical binary mixture (equimolar ratio of OMP: PAc-β-CD) and the solid inclusion complex (OMP/PAc-β-CD) revealed scCO₂ as a successful technique for inclusion complex formation as well, identified characteristics performances of PAc-β-CD/OMP interactions. For instance, absence of characteristic DSC or XRD peaks of either chemical in the complex was quite noticeable with the shift of proton peaks in ¹H NMR spectra. The formed inclusion complex also showed an important dissolution performance of OMP for controlled release applications partly due to the hydrophobic nature of PAc-β-CD.     

A comparative FMR study of the reduction of Co-containing catalysts for the Fischer–Tropsch process in hydrogen and supercritical isopropanol

An in situ comparative study of the reduction of Co-containing catalysts for the Fischer–Tropsch process in hydrogen and supercritical (SC) isopropanol is performed by ferromagnetic resonance (FMR) spectroscopy. According to the FMR data, the reduction of cobalt-containing oxide particles to metal in hydrogen starts at temperatures of ~360°C, which is substantially lower than a temperature of the formation of metal particles of the active phase according to powder X-ray diffraction and differential thermogravimetry data (Т ~ 450°C). In SC isopropanol, the reduction to Co metal occurs at lower temperatures (T ~ 245°C) as compared with the reduction temperature for these catalysts in hydrogen. It is shown that the reduction in SC isopropanol can lead to the formation of superparamagnetic Co nanoparticles with a narrow particle size distribution.     

Transformations of α- and β-ionones in the presence of Al2O3 in a supercritical solvent in a flow reactor

The reactivity of α- and β-ionones under the supercritical conditions in a flow type reactor in the presence of Al₂O₃ at 200–230°C was studied. α-Ionone was reduced to α-ionol, while β-ionol was unstable already at 200°C and underwent dehydration. The secondary reaction products were the corresponding megastigmatrienes.     

Application of the perturbed Lennard–Jones chain equation of state to solute solubility in supercritical carbon dioxide

The perturbed Lennard–Jones chain (PLJC) equation of state is a thermodynamic model based on the perturbation theory of liquid state. This equation has been shown in the past to be a successful model for phase equilibria calculations of binary and ternary fluid mixtures and polymer solutions. In this work, we employed for the first time the PLJC equation to model the solubility of 39 solids in supercritical carbon dioxide. It was shown that the model achieves good correlation with three temperature independent parameters. A comparison of the PLJC with the commonly used Peng–Robinson equation reveals the PLJC equation gives better correlation to the solubility data than the Peng–Robinson model that utilizes temperature dependent parameters.     

Why do co-solvents enhance the solubility of solutes in supercritical fluids? New evidence and opinion

The effects of two polar co-solvents, chlorodifluoromethane and acetone, on the solubility and enthalpy of a solution of 1,4-naphthoquinone in supercritical (SC) CO2 were studied. We found that the dissolution process becomes less exothermic in the presence of the co-solvents relative to that in pure CO2, although the solubility is enhanced significantly by the co-solvents. This indicates that the increase in the solubility by adding co-solvents results from the increase of the entropy of solution. On the basis of the unexpected results we propose a new mechanism for the solubility enhancement of the solute by the co-solvents in supercritical fluids (SCF); this should be applicable to cases in which the local density of the SC solvent around the solute and the co-solvent is larger, and the co-solvent associates preferentially with the solute. The results are also very important for the understanding of other fundamental questions of SCF science, such as the effect of co-solvents on the thermodynamic and kinetic properties of the reactions in SCFs.     

Density of supercritical CO_2-tetrahydrofuran binary mixture and the partial molar volume of the cosolvent

The densities of supercritical CO2-tetrahydrofuran (cosolvent) binary mixture weremeasured at temperatures in range of 308.15 to 323.15 K and at pressure up to 16.5 MPa.The concentrations of tetrahydrofuran were from 0 to 0.57 mol/L.The partial molar volume of tetrahydrofuran was calculated based on the relationship between the density of the mixture and the concentration of the cosolvent.It is observed that the partial molar volume of the cosolvent is negative and the absolute value decreases with increasing pressure and the concentration of the cosolvent.     

The thermolysis of α-pinene and verbenone epoxides in supercritical solvents

Thermal transformations of α-pinene and verbenone epoxides were studied in supercritical solvents with complex compositions, including CO₂, lower alcohols (ethanol and isopropanol), and water, over the temperature and pressure ranges 387–575 K and 135–215 atm. The main product from α-pinene epoxide in a supercritical solvent containing water was campholenic aldehyde and pinocamphone; the total content of these products in the reaction mixture was 80%. Suggestions concerning the mechanism of the thermal isomerization of α-pinene epoxide depending on the acidity of supercritical solvents were made. The direction of verbenone epoxide transformations was independent of the presence of water in the mixture. The main identified products were ketoalcohols with para-menthane and camphane frameworks.     

Retention behaviour of carboxylic acid methyl esters in supercritical fluid chromatography

The study on retention behavior in supercritical fluid chromatography (SFC) is necessary to understand the mechanism of the various interactions in SFC. The retention of SFC in carboxylic acid methyl ester/polymethylsiloxane/CO2 system was studied systematically and the retention behavior of this kind of compounds under various typical operation conditions was described using the method of an alternative unified theory of chromatographic retention. The results illustrated that expression: Ink.= a + b/T + cp + dp/T + ep2/T can be used to describe quantitatively the retention behavior of carboxylic acid methyl ester/polymethylsiloxane/CO2 system in the ranges of reduced density from 0.549 to 1.411. It was also found that the entropy of solute in stationary phase is dependent on the density of supercritical fluid (SF) under typical operating conditions of SFC.     

Palladium-catalyzed homo-coupling of boronic acids with supported reagents in supercritical carbon dioxide

Palladium-catalyzed homo-coupling of arylboronic acids could proceed smoothly with a commercially available resin functionlised by phosphino or amino group as the ligand in supercritical carbon dioxide thereby offering a simple and efficient protocol for the synthesis of symmetrical bi-aryl molecules and their higher homologues.     

Solubility of monocrotaline in supercritical carbon dioxide and carbon dioxide—ethanol mixtures

The solubility of monocrotaline, a chemotherapeutic drug precursor, in supercritical carbon dioxide and carbon dioxide—ethanol mixtures has been measured from 308.15 to 328.15 K and from 8.86 to 27.41 MPa. The solubility ranges from 6.0 × 10⁻⁶ to 2.21 × 10⁻⁴ mol fraction increasing up to 25-fold with the addition of ethanol. A new method for the estimation of the sublimation pressure of monocrotaline was developed based on the measured solubilities of monocrotaline in water. The sublimation pressure was then used in the compressed gas model to correlate the behavior of carbon dioxide—monocrotaline and carbon dioxide—ethanol—monocrotaline systems with reasonable success.     

Carbon nanotubes-supported palladium nanoparticles for the Suzuki reaction in supercritical carbon dioxide: A facile method for the synthesis of tetrasubstituted olefins

A facile and efficient method for the synthesis of tetrasubstituted olefins in supercritical carbon dioxide was developed by using carbon nanotubes-supported palladium nanoparticles (Pd/CNTs) as the catalyst. Compared with common Pd/C, Pd/CNTs could more effectively catalyze the reaction of dibromo-substituted olefins with boronic acids, affording the corresponding tetrasubstituted olefins with moderate to good yields. This environmentally benign route with an easy-to-handle catalyst provides an appealing alternative to the currently available methods.     

A new tool for the study of polymerization under supercritical conditions – preliminary results

Efficient stirring is needed to realize heat flow analysis with a thermally homogeneous medium. Because dispersion polymerization with supercritical fluids can be destabilized under stirring, a preliminary target has been to find a compromise between synthesis and basic reaction calorimetry requirements. This paper describes the use of poly (dimethylsiloxane) macromonomer with a molecular weight 5000 g/mol as stabilizer for the dispersion polymerization of methyl methacrylate in supercritical carbon dioxide. The effect of stirring speed and stabilizer concentration has been examined. This study has shown that poly (methyl methacrylate) can be produced at high yield and molecular weight using 10 wt% (respect to monomer) poly (dimethylsiloxane) macromonomer at stirring speeds up to 600 rpm. A polymerization enthalpy of −57.6±2 kJ/mol has been calculated being in good agreement with previously reported data. Thus, preliminary results for the heat balance using the newly developed high pressure reaction calorimeter for supercritical fluid applications have shown the important potential of reaction calorimetry to promote supercritical fluid technologies at industrial scale allowing for the determination of kinetics and thermodynamic and safety data, respectively.     

Photooxidation of carbonyl sulfide in the presence of the typical oxides in atmospheric aerosol

Carbonyl sulfide (COS) is one of the most abun-dant sulfur containing gases in the troposphere andlower stratosphere[1,2]. It is relatively inert in the tro-posphere and can be transported into the stratosphere,where it dissociates under the solar ultravi…