Insertion reactions of organochlorosilanes with cyclic ethers

Phenyl glycidyl ether and allyl glycidyl ether (3-phenoxy- and 3-allyloxy-1,2-epoxypropane) cause fission of the silicon---chlorine bonds in a number of alkylchlorosilanes to form chloro-substituted alkoxysilanes. Relative reactivities of cyclic ethers with chlorosilanes have been discussed. Structures of the adducts are suggested on the basis of their IR and proton magnetic resonance spectra.     

Novel regiochemistry in the aqueous singlet oxygen ene reactions of carboxylic acid salts: a comparison of substrate structure

The singlet oxygen (¹Δ_g) photooxidations of angelic acid salt (1), tiglic acid salt (2), 2,3-dimethyl-2-butenoic acid salt (3), 3-ethoxycarbonyl-5,6-dihydro-2-methyl-4H-pyrane acid salt (4), cis-3-hexenoic acid salt (5), and trans-3-hexenoic acid salt (6) were conducted in deuterated water. The major and minor ene allylic hydroperoxide products were quantified and indicate that the allylic hydrogen geminal to the carboxylate group is preferentially abstracted in 1-4, whereas the allylic hydrogen α to the carboxylate is slightly favored for 5 and 6. We have attributed the observed regiochemistry in 1-4 to stabilizing hydrogen bonding interactions between the solvent and the perepoxide, which leads to the major ene product.     

Oxidation of triethylamine by molecular oxygen catalyzed by Ru(III)-ion

The kinetics of Ru(III) catalyzed oxidation of triethylamine by molecular oxygen has been investigated in the pH range 1.5 to 2.5 at 35°C and I=0.1 M KCl. The reaction is first order with respect to substrate, catalyst and molecular oxygen concentrations. The rate of the reaction increases with the increase of pH from 1.5 to 2.5 and then there is a slight decrease in the rate above pH 2.5. Based on the kinetic data, a mechanism for the catalytic oxidation of triethylamine is proposed. The major products in the oxidation of triethylamine are the N-oxide, diethylamine and acetaldehyde.

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, Ru(III), pH=1,5+2,5 35°C I=0,1M KCl. , . pH 1,5 2,5, pH 2,5. , . N-, .

     

Kinetics and mechanism of ruthenium(III) and ruthenium(III)-EDTA catalyzed oxidation of cyclohexanol by molecular oxygen

The kinetics of the oxidation of cyclohexanol by molecular O₂ catalyzed by Ru(III) and Ru(III)-EDTA complexes has been investigated by oxygen absorption method in the pH range 1.75–3.00 at 30°C (=0.1M KNO₃) in a 11 ethanol-water medium. In both cases the reaction was found to be first order with respect to substrate and catalyst concentration. The rate was found to decrease with the decrease of pH in case of Ru(III)-EDTA complex. Ethanol is not oxidized under the reaction conditions. A possible mechanism for the catalytic oxidation of cyclohexanol is proposed.

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O₂, Ru(III) Ru(III)-EDTA, pH 1,75–3,00 30°C (=0,1M KNO₃) - (11). . pH Ru(III)-EDTA. . .

     

Detection of OH on photolysis of styrene oxide at 193 nm in gas phase

Photodissociation of styrene oxide at 193 nm in gas phase generates OH, as detected by laser-induced fluorescence technique. Under similar conditions, OH was not observed from ethylene and propylene oxides, primarily because of their low absorption cross-sections at 193 nm. Mechanism of OH formation involves first opening of the three-membered ring from the ground electronic state via cleavage of either of two CO bonds, followed by isomerization to enolic forms of phenylacetaldehyde and acetophenone, and finally scission of the COH bond of enols. Ab initio molecular orbital calculations support the proposed mechanism.     

Confinement and controlled release of quinine on chitosan–montmorillonite bionanocomposites

To accomplish the controlled‐release systems based on layered clay minerals, one of the best ways is to intercalate organic molecules into the interlayer gallery of clay minerals. Into a series of chitosan (CS) intercalated montmorillonite (MMT) nanocomposites, prepared via ion‐exchange route, antimalarial drug [quinine (QUI)] was loaded to act as effective drug delivery systems. Among the CS–MMT nanocomposites, higher drug adsorption with decreasing CS concentration was observed. CS–MMT and CS–MMT/QUI intercalated compounds were characterized by powder X‐ray diffraction, Fourier transform infrared spectroscopy, and thermal analysis. The synthesized nanocomposites, filled in the gelatin capsules followed by coating of Eudragit® L 100, were tested for in vitro drug release performance in the sequential buffer environments at 37 ± 0.5 °C. As no drug release (0%) was observed in the gastric fluid, the coating of Eudragit® L 100 to the capsules is highly adequate. However, the drug release rate was comparatively faster from the CS intercalated clay with compare with pure clay. The drug release kinetic data revealed that the release of QUI from the nanocomposites can be explained by modified Freundlich model. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Oxazoline‐Based Organocatalyst for Enantioselective Strecker Reactions: A Protocol for the Synthesis of Levamisole

A chiral oxazoline‐based organocatalyst has been found to efficiently catalyze asymmetric Strecker reactions of various aromatic and aliphatic N‐benzhydrylimines with trimethylsilyl cyanide (TMSCN) as a cyanide source at ?20 °C to give α‐aminonitriles in high yield (96 %) with excellent chiral induction (up to 98 % ee). DFT calculations have been performed to rationalize the enantioselective formation of the product with the organocatalyst in these reactions. The organocatalyst has been characterized by single‐crystal X‐ray diffraction analysis, as well as by other analytical methods. This protocol has been extended to the synthesis of the pharmaceutically important drug molecule levamisole in high yield and with high enantioselectivity.     

In memory of Professor Ali H. Nayfeh

Nonlinear Dynamics - In this paper, we propose and numerically study a nonlinear, asymmetric, passive metamaterial that achieves giant non-reciprocity with (i) broadband frequency operation and...     

Topochemical models for anti-HIV activity of 1-alkoxy-5-alkyl-6-(arylthio)uracils

Relationship between topochemical indices and anti-HIV-1 (HTLV-III) inhibitory activity of 1-alkoxy-5-alkyl-6-(arylthio)uracils has been studied. Superadjacency, an adjacency-cum-distance-based, topochemical index and Wiener’s, a distance-based, topochemical index were calculated for a set of 36 1-alkoxy-5-alkyl-6-(arylthio)uracils. Resulting data were analyzed and suitable models were developed after identification of the active ranges. Subsequently, a biological activity was assigned to each of the compounds using these models and compared with the reported anti-HIV-1 activity. High accuracy of prediction was observed using these models. Statistical analysis revealed significance of the proposed models as well as a lack of correlation between the topochemical indices employed for the chosen data set.     

Viscoelastic flow in a two-dimensional collapsible channel

We compute the flow of three viscoelastic fluids (Oldroyd-B, FENE-P, and Owens blood model) in a two-dimensional channel partly bounded by a tensioned membrane, a benchmark geometry for fluid–structure interactions. The predicted flow patterns are compared to those of a Newtonian liquid. We find that computations fail beyond a limiting Weissenberg number. Flow fields and membrane shape differ significantly because of the different degree of shear thinning and molecular extensibility underlying the three different microstructural models.