Simple,Mild, and Practical Esterification,Thioesterification, and Amide Formation Utilizing p‐Toluenesulfonyl Chloride and N‐Methylimidazole

We have developed an efficient method for the esterification or thioesterification of equimolar amounts of carboxylic acids and alcohols or thiols using a novel reagent, p‐toluenesulfonyl chloride (TsCl) together with N‐methylimidazole. The present method is simple, mild, and reactive, uses readily available and economical reagents. The choice of amine is critical for the present method. The amine, N‐methylimidazole, has two roles: (i) as an HCl scavenger for the initial smooth generation of mixed anhydrides between carboxylic acids and TsCl and (ii) successive formation of highly reactive ammonium intermediates from mixed anhydrides. This method could be applied to various types of carboxylic acids, alcohols, and thiols: a) several functionalities were tolerated; b) two N‐Cbz amino acids were smoothly esterified without racemization; and c) the labile 1β‐methylcarbapenem key intermediate and a pyrethroid insecticide, prallethrin, were successfully prepared. The related amide formation between carboxylic acids and primary or secondary amines was also performed. The proposed reaction mechanism involves a novel method for producing the reactive acylammonium intermediates. The production of these intermediates was rationally supported by a careful ¹H NMR monitoring study.     

Effect of microstructures on dielectric breakdown strength of sintered reaction-bonded silicon nitride ceramics

Silicon nitride (Si₃N₄) was prepared from silicon by a sintered reaction-bonded silicon nitride method using yttria and magnesia as sintering additives. Post-sintering (PS) of nitrided compacts was carried out at 1850°C under a nitrogen pressure of 1 MPa. Effect of PS time on microstructure and dielectric breakdown strength (DBS) of the prepared Si₃N₄ ceramics was evaluated. The DBS was measured using specimens with four different thicknesses (0.30, 0.20, 0.10, and 0.05 mm) in order to examine the thickness dependence. The porosity of the sintered Si₃N₄ decreased by prolonging the PS time, and the full density could be achieved at the PS time of over 6 h. After full densification, rod-like β-Si₃N₄ grains grew up, and their maximum grain size increased from 45.1 to 154.7 μm by prolonging the PS time from 6 to 48 h. The DBS of the thick Si₃N₄ substrates (0.30 mm) showed little variation from 35.4 to 47.0 kV/mm, regardless of the PS time. On the other hand, that of the thin ones (0.05 mm) dramatically decreased from 99.5 to 9.8 kV/mm with increased the PS time from 6 to 48 h. Because the DBS sharply decreased at the thin substrate sintered for longer time in which some large-elongated grains might span the substrate thickness-wise throughout, it was inferred that the interface between β-Si₃N₄ grains and grain boundary phase/intergranular glassy films might be a path of the dielectric breakdown.     

Synthesis of Red-Light-Responsive Pheophorbide-a Tryptamine Conjugated Photosensitizers for Photodynamic Therapy

Six methyl pheophorbide-a derivatives were prepared by linking a tryptamine side chain at the C-13 ¹ , C-15 ² and C-17 ³ positions of pheophorbide-a. P repared conjugates were characterized and evaluated for their photocytotoxicity against A549 cells. The conjugate 6 a with strong absorption at 413 nm (Soret band), 663–671 nm (Q bands) and comparable fluorescence quantum yield (0.26) was found to exhibit significant cytotoxicity (659 nM). Molecular integration of pheophorbide-a and tryptamines showed synergistic effects as the most potent conjugate 6 a was identified with enhanced photocytotoxicity when compared to methyl pheophorbide-a. T he conjugate 6 a was smoothly taken up by A549 cells and exhibited intracellular localization predominantly to lysosome in the cytoplasm. Upon photoirradiation 6 a generated singlet oxygen to show potent cytotoxicity toward A549 cells.     

SOLUBILITY IN ORGANIC DILUENTS AND EXTRACTION BEHAVIOR OF CALIX[4]ARENE CARBOXYLATES WITH DIFFERENT ALKYL CHAINS

ABSTRACT

Two types of alkylcalix[4]arene carboxylates with different alkyl chains, together with three types with the same alkyl chains were synthesized to investigate their solubility in four different organic diluents. The solubility was found to be enhanced by using the calixarene compounds with longer alkyl chains and by using mixtures of compounds with different alkyl chains. The order of solubility in the different organic diluents was found to be:

chloroform > toluene ? EXXSOL D80 ≈ hexane.

The stoichiometry of the copper complex with the compounds having the same alkyl chains was also determined and the maximum loading capacity of copper with each extractant was estimated.     

Novel High‐Temperature Antiferroelectric‐Based Dielectric NaNbO3–NaTaO3 Solid Solutions Processed in Low Oxygen Partial Pressures

The (1?x)NaNbO₃–(x)NaTaO₃ solid solution was investigated for x ≤ 0.4 in terms of new high‐temperature and high‐permittivity dielectric system that is suitable for base metal inner electrode capacitor applications. The addition of Ta significantly enhanced the resistivity of the dielectric, resulting in superior resistivity than the dielectrics‐formulated BaTiO₃ systems that dominate the multilayer ceramic capacitor dielectric devices. The voltage dependence of the permittivity was also superior to BaTiO₃‐based materials, providing higher capacitance at higher temperatures. A transmission electron microscopy study illustrated that the grains had so‐called core‐shell structure. According to the electron diffraction analysis, the core region had an inhomogeneous structure between antiferroelectric and ferroelectric phases, and shell region had an incommensurate ferroelectric‐like structure. The core and shell region had Nb‐ and Ta‐rich composition, respectively, and their interface was compositionally sharp, implying that shell region was formed via a liquid phase during the sintering process with an incongruent Ta dissolution reprecipitation. We anticipate that these or similar materials based on the alkali‐niobate perovskites can be further enhanced to provide capacitor solutions from 150°C to 250°C, which is an important range for a number of new AC–DC invertor and engine control units.     

Catalytic Rearrangement of Epoxide Compounds

Products formed by rearrangement of epoxide compounds provide useful intermediates in organic syntheses and some of them are valuable as raw materials in the chemical industry. Many studies on the catalytic rearrangement of the epoxides have been made. The reactions which have been used most frequently are homogeneous with acid or base catalysts such as BF3, MgBr2, t-BuOK, or lithium dialkylamides; the acid catalysts form mainly carbonyl compounds (ketone and aldehyde) and the base catalysts in most cases yield allylic alcohols. Recently the heterogeneous reaction over solid catalysts was also investigated, but the catalysts used were just alumina and silica gel, solid acid and base catalysts, and it is very recent that various kinds of the solid acids and bases have been used as catalysts for epoxide isomerization, especially by the authors (Section VI-A). Studies with molten salts are few, and investigations with metal complex and organometal catalysts have just begun.     

Anatase-Type TiO2 and ZrO2-Doped TiO2 Directly Formed from Titanium(III) Sulfate Solution by Thermal Hydrolysis: Effect of the Presence of Ammonium Peroxodisulfate on their Formation and Properties

Anatase-type TiO₂ powder containing sulfur with absorption in the visible region was directly formed as particles with crystallite in the range 15–88 nm by thermal hydrolysis of titanium(III) sulfate (Ti₂(SO₄)₃) solution at 100°–240°C. Because of the presence of ammonium peroxodisulfate ((NH₄)₂S₂O₈), the yield of anatase-type TiO₂ from Ti₂(SO₄)₃ solution was accelerated, and anatase with fine crystallite was formed. Anatase-type TiO₂ doped with ZrO₂ up to 9.8 mol% was directly precipitated as nanometer-sized particles from the acidic precursor solutions of Ti₂(SO₄)₃ and zirconium sulfate in the presence and the absence of (NH₄)₂S₂O₈ by simultaneous hydrolysis under hydrothermal conditions at 200°C. By doping ZrO₂ into TiO₂ and with increasing ZrO₂ content, the crystallite size of anatase was decreased, and the anatase-to-rutile phase transformation was retarded as much as 200°C. The anatase-type structure of ZrO₂-doped TiO₂ was maintained after heating at 1000°C for 1 h. The favorable effect of doping ZrO₂ to anatase-type TiO₂ on the photocatalytic activity was observed.     

Treatment of Groundwater Contaminated with 1,4-Dioxane,Tetrahydrofuran, and Chlorinated Volatile Organic Compounds Using Advanced Oxidation Processes

Ozonation and four types of advanced oxidation processes, including O₃/H₂O₂, O₃/UV, O₃/H₂O₂/UV, and UV/H₂O₂, were evaluated for the treatment of contaminated groundwater at a Superfund site in Simpsonville, South Carolina using bench-scale, batch ozone and UV apparatuses. Although the contaminants of concern were 1,4-dioxane, 1,1-dichloroethene, and trichloroethene, several other chlorinated organics as well as tetrahydrofuran were found in the groundwater samples. The O₃/H₂O₂ treatment with O₃ and H₂O₂ doses of 6 and 1.5 mg/L, respectively, and the UV/H₂O₂ treatment with UV and H₂O₂ doses of 1,000 mJ/cm and 20 mg/L, respectively, were sufficient to degrade 200 µg/L of 1,4-dioxane, 110 µg/L of 1,1-dichloroethene, and 10 µg/L of trichloroethene below their performance standards of 10, 7, and 4 µg/L, respectively. Due to a high bromide concentration (0.35 mg/L) in the groundwater sample, bromate formation was found to be significant in ozone-based treatment, including O₃/H₂O₂.