One-Pot Formation of Carbonates from the Reactions of Carbonyl Compounds with Samarium Diiodide and Methyl Chloroformate

Treatment of carbonyl compounds with SmI₂ and methyl chloroformate in the presence of molecular sieves provides the cyclic carbonates or biscarbonates of pinacols. This one-pot reaction proceeds rapidly even with aliphatic ketones. The stereochemistry obtained by this procedure is different from that of conventional pinacolic couplings.     

Resolution of the non-steady-state kinetics of the two-step mechanism for the Diels-Alder reaction between anthracene and tetracyanoethylene in acetonitrile

The Diels-Alder reaction between anthracene and tetracyanoethylene in acetonitrile does not reach a steady-state during the first half-life. The reaction follows the reversible consecutive second-order mechanism accompanied by the formation of a kinetically significant intermediate. The experimental observations consistent with this mechanism include extent of reaction-time profiles which deviate markedly from those expected for the irreversible second-order mechanism and initial pseudo first-order rate constants which differ significantly from those measured at longer times. It is concluded that the reaction intermediate giving rise to these deviations cannot be the charge-transfer (CT) complex, which is formed during the time of mixing, but rather a more intimate complex with a geometry favorable to the formation of the Diels-Alder adduct. The kinetics of the reaction were resolved into the microscopic rate constants for the individual steps. The rate constants, as shown in equation 1, at 293 K were observed to be 5.46 M(-)(1) s(-)(1) (k(f)), 14.8 s(-)(1) (k(b)), and 12.4 s(-)(1) (k(p)). Concentration profiles calculated under all conditions show that intermediate concentrations increase to maximum values early in the reaction and then continually decay during the first half-life. It is concluded that the charge-transfer complex may be an intermediate preceding the formation of the reactant complex, but due to its rapid formation and dissociation it is not detected by the kinetic measurements.     

Meso-tetraaryl cofacial bisporphyrins delivered by Suzuki cross-coupling

The Suzuki cross-coupling methodology provides a facile synthetic approach for the modular preparation of meso-tetraaryl cofacial bisporphyrins anchored by xanthene and dibenzofuran. This synthetic method furnishes cofacial bisporphyrin templates with enhanced steric and electronic protection from mu-oxo formation and oxidative degradation. The ability of these platforms to support multielectron oxidation chemistry mediated by proton-coupled electron transfer (PCET) is demonstrated by their reactivity for the catalytic disproportionation of hydrogen peroxide to oxygen and water.     

Taxumairols X--Z,new taxoids from Taiwanese Taxus mairei

In addition to 19-dydroxybaccatin III, 1beta-hydroxy-5 alpha-deacetylbaccatin I, taxayuntin G and 13-O-deacetyltaxumairol Z (4), three new taxane diterpenoids, taxumairols X (1), Y (2), Z (3) have been isolated from extracts of the Formosan Taxus mairei (LEMEE & LEVL.) S. Y. HU. Compounds 1-2 belong to the 11(15-->1)-abeo-taxane system, having a tetrahydrofuran ring at C-2, C-3, C-4 and C-20. The new compound 3 and 4, which was misidentified previously are derivatives of 11(15-->1)-abeo-taxane with an intact oxirane system. The structures of compounds 1-4 were elucidated on the basis of extensive two dimensional (2D)-NMR analysis.     

Acceleration of Organic Reactions Using Microwave

The use of microwave technology in accelerating organic reactions has received intense attention leading to immense growth recently. Accordingly, we have been interested in improving the efficacy of organic processes by microwave irradiation. Here we report our results on the microwave assisted direct amide formation from carboxylic acid and amine, the hydrolysis of biopolymers, and nucleophilic aromatic substitution reaction. The reactions carried out under microwave irradiation, in general, …     

A preliminary study on the initial elastic adhesion behavior of leucocytes

By treating the cell body as an elastic colloid and applied with the Hertz contact theory of linear elasticity and the lubrication equation of fluid dynamics, the elastic adhesion behavior of leucocytes in close motion toward a plane surface is investigated. The effect of the Stokes number on the deformation profile of the cell is considered during the adhesion period. From the results of numerical simulation, it is found that under certain conditions (i.e. regardless of the magnitude of F for the cases of ST=1 and 3 and ε0.0055 for ST=10), after exhausting all of the incoming kinetic energy, the cell can rest at an equilibrium separation which is close to the ligand–receptor bond length formed between two interacting surfaces.     

Application of Iodide Ion Selective Electrode to the Study of Stepwise Formation Constant and Solubility Product of Lead Iodide

Iodide ion-selective electrode were studied, prepared and applied for the complex formations and solubility product determination. The thermodynamic formation constant of PbI⁺ and the solubility product of PbI₃ were found to be 54 and 9.2 × 10^?9, respectively. The formation constant of PbNO₃⁺ was calculated to be 4.6 from the different formation constant of PbI⁺ in perchlorate and nitrate media.     

Concentration and determination of trace organic pollutants in water

Organic pollutants in water are isolated on a mini-sampler tube containing a macroporous resin. The sorbed pollutants are next thermally transferred to a second sorption tube and then to an analytical column where they are separated and determined by temperature-programmed gas chromatography. Excellent recoveries were obtained for tests in which model organic compounds of various classes were added to water. The water sample is much smaller than that required with previous analytical methods.     

Facile cyclization of amidyl radicals generated from N-acyltriazenes

N-Acyltriazenes serve as a tin-free and initiator-free source for amidyl radicals. Thermal decomposition of N,N′-diaryl-N-(4-pentenoyl)triazenes in refluxing toluene led to the formation of monocyclic and tricyclic lactams in satisfactory yields via 5-exo amidyl radical cyclization.     

Solid Phase Synthesis of 4H-Pyrimido[2,1-b] Benzothiazol-4-ones from Resin-Bound Cyclic Malonic Ester

The solid phase synthesis of 4H-pyrimido[2,1-6] benzothizaol-4-ones has been reported.