Alkane Oxidation with Molecular Oxygen Using a New Efficient Catalytic System: N-Hydroxyphthalimide (NHPI) Combined with Co(acac)(n)() (n = 2 or 3)

A novel class of catalysts for alkane oxidation with molecular oxygen was examined. N-Hydroxyphthalimide (NHPI) combined with Co(acac)(n)() (n = 2 or 3) was found to be an efficient catalytic system for the aerobic oxidation of cycloalkanes and alkylbenzenes under mild conditions. Cycloalkanes were successfully oxidized with molecular oxygen in the presence of a catalytic amount of NHPI and Co(acac)(2) in acetic acid at 100 degrees C to give the corresponding cycloalkanones and dicarboxylic acids. Alkylbenzenes were also oxidized with dioxygen using this catalytic system. For example, toluene was converted into benzoic acid in excellent yield under these conditions. Ethyl- and butylbenzenes were selectively oxidized at their alpha-positions to form the corresponding ketones, acetophenone, and 1-phenyl-1-butanone, respectively, in good yields. A key intermediate in this oxidation is believed to be the phthalimide N-oxyl radical generated from NHPI and molecular oxygen using a Co(II) species. The isotope effect (k(H)/k(D)) in the oxidation of ethylbenzene and ethylbenzene-d(10) with dioxygen using NHPI/Co(acac)(2) was 3.8.     

Catalyzed collapse and enhanced hydrogen storage of BN nanotubes

The novel morphology of BN nanotubes with a collapsed structure has been discovered by a metal-catalyzed treatment. The collapse causes the dramatic enlargement of a specific surface area of BN nanotubes and remarkably enhances the hydrogen storage capacity of BN nanotubes.     

Synthesis of poly (ethylene oxide)-b-polysilane by anionic polymerization of masked disilenes using a macroinitiator method

Poly(ethylene oxide-)-poly(1, 1-dimethyl-2, 2-dihexyldisilene) block copolymers (PEO-b-PMHS) were synthesized by the anionic polymerization of masked disilenes initiated with the potassium alkoxide of poly(ethylene glycol). The block copolymer self-assembled into polymer micelles in water accompanied by a transition in the polysilane conformation.     

Synthesis of Ultrafine SiC Powders from Carbon-Silica Hybridized Precursors with Carbothermic Reduction

Inorganic-organic hybrid gels were prepared by simultaneous condensation of the liquid mixture of ethyl silicate, ethyl borate and water soluble phenol resin with low molecular weight. The liquid mixtures were changed into lightly colored transparent gels after a catalyst addition and stirring. The obtained gels were crushed, dried and fired in controlled conditions to yield the inorganic precursors. Since the tailored inorganic precursors mainly consisted of SiO2 and carbon, silicon carbide was formed with the heat treatments in an Ar atmosphere beyond 1773 K with carbothermic reduction. The properties and morphology of the formed silicon carbide powders in terms of the starting precursor compositions and the conditions of the carbothermic reduction were investigated with SEM, XRD and TG-DTA analysis.     

Photophysics and photochemistry of sterically strained α-haloanthraquinones: The bromo and/or chloro substituted compounds

The steric hindrance between the oxygen and halogen atoms results in the structural deformation of α-haloanthraquinones and their lowest excited triplet (T₁) states are of mixed nπ ^*-ππ ^* or ππ ^* character with unusually short lifetimes. Moreover, the rates of hydrogen-atom abstraction from ethanol by the T₁ states decrease with their increasing ππ ^* character, and the proximity of the halogen atom to the hydroxy group causes the photochemical intramolecular elimination of hydrogen halide from the initial photoproducts (α-haloanthrahydroquinones) yielding α-haloanthraquinones (or anthraquinone) with one less halogen atom than the original molecule; the final product is anthrahydroquinone. The remarkably large structural deformation of 1,8-dihaloanthrasemiquinone radicals which gives rise to the simultaneous formation of 1,8-dihaloanthrahydroquinones and the original anthraquinones. Of particular interest is observation of the absorption band(s) attributable to the second excited triplet (T₂) states of 1,8-dihaloanthraquinones. However, the electron transfer from triethylamine (TEA) to these T₂ states generating the radical anions is observed only in acetonitrile, while that to the T₁ states generating their exciplexes with TEA is observed not only in acetonitrile but also in toluene and ethanol.     

Polyimides having pendant hydroxy and acetoxy groups. I. Synthesis of polyimides from pyromellitimide and bisepoxides

Polyimides having pendant hydroxy groups were prepared by addition of pyromellitimide with bisepoxides. Tertiary amines and quaternary ammonium halides were effective as a catalyst. The polyimides were soluble in dichloroacetic acid and had inherent viscosities in the range 0.16–0.19 dl/g. Thermogravimetric analysis showed that a rapid weight loss of the polymers occurred at about 400°C. The pendant hydroxy groups were easily acetylated by treating the polymers with a mixture of acetic anhydride and pyridine. The acetylated polyimides were soluble in dimethylformamide, dimethylacetamide, and dioxane and melted at 120–150°C.     

Layer-by-layer assembled multilayer films of titanate nanotubes, Ag- or Au-loaded nanotubes, and nanotubes/nanosheets with polycations

Aqueous suspensions of hydrothermally synthesized titanate nanotubes and poly(diallyldimethylammonium chloride) (PDDA) have been employed to fabricate multilayer films on various substrates in a layer-by-layer fashion. Atomic force microscopy displays the dense coverage of the substrate surface by the nanotubes. UV-vis absorption spectroscopy confirms the consecutive growth of PDDA/nanotube layer pairs. Single crystalline Ag and Au nanoparticles with narrow size distribution spatially correlating with the nanotubes have been obtained by treating the nanotubes with AgNO(3) or HAuCl(4) aqueous solution followed by chemical reduction. The noble metal nanoparticles show a strong surface plasmon absorption band. A multilayer film construction of the noble-metal-loaded nanotubes has also been achieved. This process has been further extended to the heteroassembly of nanotubes/nanosheets in different layer sequences.     

Synthetic studies on oxindole spiro-lactones with thalliumd(III) trinitrate: A formal total synthesis of (±)-tryptoquivaline G

(±)-Tryptoquivaline G was formally synthesized through shortened steps from tryptophan, in which oxidation with thallium(III) trinitrate(TTN) was effected at the crucial stage. The present work also constitutes the first synthesis of oxindole lactones carrying 2-alkyl quinazolinones.     

Optically active 2-p-tolylsulfinylacrylate a novel chiral dienophile which exhibits high reactivity and diastereoselectivity

The Diels-Alder reaction of a novel chiral dienophile, alkyl ($\text{S}$)-2-$\text{p}$-tolylsulfinylacrylates 1 with anthracene and cyclopentadiene showed high diastereoselectivity under the chelation controlled condition.