An Easy One-Pot Procedure for the Synthesis of <Emphasis Type="Italic">N</Emphasis>-Sulfonyl Phosphorous Ylides and Sulfonyl Iminophosphoranes

Summary. Reaction of triphenylphosphine and an electron deficient acetylenic ester in the presence of strong N–H acid such as alkyl and aryl sulfamides or acetamide produces phosphorous ylides at room temperature in CH₂Cl₂. The aryl sulfamide phosphoranes undergo a smooth transformation reaction in boiling toluene and produce iminophosphoranes.     

Carboxymethylated nanofibrillated cellulose: effect of monovalent electrolytes on the rheological properties

The effect of the ionic strength on the properties of a carboxymethylated nanofibrillated cellulose (NFC) system was investigated through rheological studies. It was shown that homogenization of pulp suspensions containing a high amount of a monovalent electrolyte leads to the production of NFC systems displaying a lower magnitude in the rheological response as compared with systems prepared at lower ionic strengths conditions. It was further shown that increasing the ionic strength of NFC suspensions after their manufacturing also results in a lowering of the rheological response. The decreased rheological response in the former case was postulated to be caused by a lowering of the delamination deficiency of the homogenization process, due to decreased swelling of the carboxymethylated pulp, caused by the screening of the charges. In the latter case (post-addition of the electrolyte), the lowering of the rheological response was postulated to be due to the compression of the electrostatic double layer, when the electrostatic repulsion between the charged fibrils diminished in the presence of the electrolyte.     

Host (Nanocavity of Aluminium-Incorporated Mesoporous KIT-6)–guest (12-tungesto(molybdato) Phosphoric Acid) Nanocomposite Material: Efficient and Reusable Catalysts for the Hosomi–Sakurai Three-Component Coupling Reaction

Abstract

The immobilization of heteropoly acids (HPAs) into the Al-functionalized KIT-6 mesoporous molecular sieve has been carried out to see the effect of Al-KIT-6 as a host matrix on the HPA activities. These modified mesoporous molecular sieves are effective catalysts for the Hosomi–Sakurai three-component coupling reaction via condensation of aldehydes, silyl ethers, and allylsilanes.

Supplemental materials are available for this paper. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Synthesis of MnAl2O4 nanocrystallites by Pechini and sequential homogenous precipitation methods: characterization, product comparison, photocatalytic effect, and Taguchi optimization

Nanocrystalline manganese aluminate (MnAl₂O₄) has been synthesized by Pechini and sequential homogenous precipitation methods and the results have been compared. The Taguchi L₄ statistical design was utilized to optimize the production of MnAl₂O₄ nanoparticles by Pechini method. The MnAl₂O₄ nanocrystallites obtained by Pechini and sequential homogenous precipitation methods had the average particle size of 26.5 and 49.5 nm, respectively. The products were characterized with X-ray diffraction, laser light scattering, thermogravimetry analysis, Fourier transform infrared, UV–visible, energy dispersive X-ray, scanning electron microscope and inductively coupled plasma analyses. The photocatalytic activities of MnAl₂O₄ nanoparticles synthesized by two methods were investigated using aqueous solution of methylene blue under irradiation of visible light.     

Polymerization of Methylene Dichloride and Sodium Tetrasulfide: Synthesis and Kinetic Studies

The kinetics of the condensation polymerization of a novel polysulfide polymer based on methylene dichloride and sodium tetrasulfide is studied. The results of the experiments indicated that the reaction order is two. The activation energy obtained from the Arrhenius plot is 1.879 kcal mol^?1, and the pre-exponential frequency factor is A = 27.11 min^?1 at temperature range of 40～60°C. The polymer is characterized by using Fourier transform-infrared and CHN analysis. Thermal properties were evaluated by differential scanning calorimetry. The TGA-DTA was used to find out the thermal stability of polymer. The solvent resistance of the polymer was investigated by the swelling method.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Carboxymethylated nanofibrillated cellulose: rheological studies

The rheological properties of carboxymethylated nanofibrillated cellulose (NFC), investigated with controlled shear rate- and oscillatory measurements, are reported for the first time. It was shown that the rheological properties of the studied system are similar to those reported for other NFC systems. The carboxymethylated NFC systems showed among other things high elasticity and a shear thinning behaviour when subjected to increasing shear rates. Further, the shear viscosity and storage modulus of the system displayed power-law relations with respect to the dry content of the NFC suspension. The exponential values, 2 and 2.4 respectively, were found to be in good agreement with both theoretical predictions and published experimental work. Furthermore, it was found that the pulp consistency at which NFC is produced affects the properties of the system. The rheological studies imply that there exists a critical pulp concentration below which the efficiency of the delamination process diminishes; the same adverse effect is also observed when the critical concentration is significantly exceeded due to a lower energy input during delamination.     

Exo/endo stereocontrolled synthesis of spiroindoloindolizidines by using classical and microwave conditions via the 1,3-dipolar cycloaddition reaction

Using both classical reflux and microwave-mediated conditions, a series of new spiroindoloindolizidines was synthesized by multicomponent 1,3-dipolar cycloaddition of azomethine ylides in unprecedented exo/endo stereocontrolled. Both conditions easily afforded two identical and separable exo/endo diastereomeric ratios of cycloadducts. However, the ratio of two diastereomeric products obtained from conventional conditions was reversed in all examined cases when the reactions were explored under microwave-mediated conditions. As expected, utilizing the microwave-assisted conditions produced higher yields and reaction rates compared to classical conditions. The structure and exact stereochemistry of synthesized cycloadducts were determined by applying various 2D-NMR spectroscopic techniques and single-crystal X-ray diffraction. Finally, the mechanism of the reaction has been briefly investigated by using density functional theory (DFT) calculations.     

Two‐dimensional modeling for stability analysis of two‐phase stratified flow

The effect of wavelength and relative velocity on the disturbed interface of two‐phase stratified regime is modeled and discussed. To analyze the stability, a small perturbation is imposed on the interface. Growth or decline of the disturbed wave, relative velocity, and surface tension with respect to time will be discussed numerically. Newly developed scheme applied to a two‐dimensional flow field and the governing Navier–Stokes equations in laminar regime are solved. Finite volume method together with non‐staggered curvilinear grid is a very effective approach to capture interface shape with time. Because of the interface shape, for any time advancement, a new grid is performed separately on each stratified field, liquid, and gas regime. The results are compared with the analytical characteristics method and one‐dimensional modeling. This comparison shows that solving the momentum equation including viscosity term leads to physically more realistic results. In addition, the newly developed method is capable of predicting two‐phase stratified flow behavior more precisely than one‐dimensional modeling. It was perceived that the surface tension has an inevitable role in dissipation of interface instability and convergence of the two‐phase flow model. Copyright © 2009 John Wiley & Sons, Ltd.