Palladium-catalyzed denitrogenation reaction of 1,2,3-benzotriazin-4(3H)-ones incorporating isocyanides

1,2,3-Benzotriazin-4(3H)-ones and 1,2,3,4-benzothiatriazine 1,1(2H)-dioxide reacted with isocyanides in the presence of a palladium catalyst to give 3-(imino)isoindolin-1-ones and 3-(imino)thiaisoindoline 1,1-dioxides, respectively, in high yield. An intermediate azapalladacycle was generated through denitrogenation of the triazine moiety, and an isocyanide was incorporated therein.     

Formation of a silicato complex of zinc in aqueous solution and its accelerating effect on the formation of silica scales in cooling water systems

This study elucidates the effect of zinc (Zn), which is an anticorrosive water additive, on the formation of silica scales from cooling water. In these experiments, the silica scales were analyzed by EPMA, and the results indicate that Zn is sorbed into the silica scales during formation. Measurements of the solubility of Zn(OH)(2) at various concentrations of silicic acid demonstrate that Zn is present as a silicato complex of Zn (SCZ) in cooling water. From adsorption experiments of the SCZ on silica and alumina, which are major components of the silica scales, it can be concluded that the SCZ accelerates the formation of silica scales from cooling water.     

A divergent synthesis of dihydropyridazinones,N‐substituted dihydropyrazoles,and O‐substituted pyrazoles

Dihydropyridazinones 4a , 4b , N‐substituted dihydropyrazoles 5b , 5c , 5d , and O‐substituted pyrazoles 6a , 6b , 6c , 6d have been synthesized starting from spirocyclopropanepyrazole derivative 2 . Treatment of 2 with α‐chloro esters, e.g., methyl chloroacetate, ethyl chloroacetate, isopropyl chloroacetate, and tert‐butyl chloroacetate, in potassium carbonate/sodium iodide system caused ring opening and subsequent C‐ or N‐attack nucleophilic substitution to give the corresponding dihydropyridazinones 4a , 4b and N‐substituted dihydropyrazoles 5b , 5c , 5d . On the other hand, in the absence of sodium iodide, O‐substituted pyrazoles 6a , 6b , 6c , 6d were obtained from 2 via an O‐attack nucleophilic substitution. J. Heterocyclic Chem., 2011.     

Surface treatment of silicon carbide using TiO2(IV) photocatalyst

Silicon carbide (SiC) and diamond were decomposed to CO(2)(g) by the photocatalysis with TiO(2) at room temperature, although the decomposition rate of diamond was very slow. According to the XPS spectra of Si2p on the SiC surface, SiO(2) was simultaneously formed on the surface by the TiO(2) photocatalysis. The thickness of the SiO(2) formed on the SiC surface during the photocatalytic oxidation for 1 h was estimated to be about 40 A from the depth profile of the XPS spectra using Ar etching. The SiC surface was oxidized by the TiO(2) photocatalysis even under the condition without a direct contact with the TiO(2). This indicates that the photocatalytic oxidation of the SiC occurs due to active oxygen species photogenerated on the TiO(2) surface, but not by hole produced in the valence band of the TiO(2). Moreover, a remote surface treatment system using the quartz beads coated with TiO(2) was developed for the SiC surface oxidation. Consequently, the TiO(2) photocatalysis will be very useful for the surface treatment of SiC such as photopatterning without defects and damage to the substrate because the photocatalytic reaction is carried out under mild conditions.     

Dynamic anisotropy and heterogeneity of polystyrene thin films as studied by inelastic neutron scattering

We studied the dynamic anisotropy and heterogeniety of polystyrene thin films in glassy state with inelastic neutorn scattering. Adjusting the scattering vector to the directions parallel and perpendicular to the film surface, we observed the elastic scattering intensities as a function of temperature. It was found for the 200 A film that the elastic intesity decreased with increasing temperature more rapidly in the perpendicular direction than in the pararell direction, showing the higher mobility in the perpendicular direction. However, such dynamical anisotropy was not observed in the 1000 A film. The decrease in the mobility was observed with the film thickness in both the directions. These results were explained in terms of an interface hard layer. We also evelauated the dynamical heterogeniety from the non-Gaussian parameter A0, which increased with decreasing the film thickness, showing the increase in the dynamical heterogeneity. Assuming a simple bi-layer model consisting of the interface hard layer and the bulk-like layer, we analyzed the thickness dependence of the non-Gaussian parameter A0 and the mean square displacement (u2) to find that the hard layer has a thickness of approximately 130 A and a mean square displacement of approximately 0.018 A2 at 230 K.     

Synthesis,Crystal Structures,and Properties of 6,12‐Diaryl‐Substituted Indeno[1,2‐b]fluorenes

Fused polycyclic indeno[1,2‐b]fluorene derivatives with aryl substituents at the 6,12‐positions have been prepared as a potential antiaromatic 20π electronic system. They showed strong absorptions in the visible region and amphoteric redox properties. The quinoid‐type molecular structures were revealed by X‐ray crystal‐structure analysis, which indicated that the bond lengths of the quinoid unit depend on the aryl substituents. Whereas nucleus‐independent chemical shift NICS(1) calculations indicate the antiaromatic nature of the s‐indacene core, they have higher stability than substituted acene derivatives. The derivatives with difluorophenyl or anthryl groups were stable in solution. Vapor‐deposited thin films showed ambipolar carrier transportation in the field‐effect transistor devices.     

High Frequency and High Mode Purity Operations of Gyrotron FU IVA

The cavity of the newest gyrotron, Gyrotron FU IVA in the high frequency series of Fukui University gyrotrons (the Gyrotron FU series) is designed to minimize the mode conversion from the main cavity mode to the higher modes. In this paper, the experimental results are compared with simulations for the complete gyrotron oscillator. The gyrotron has an additional advantage to cover the wide frequency range in submillimeter wave region.