Structure of Sol-Gel-Derived Sodium Dititanate Glass

The sodium dititanate, Na₂O·2TiO₂ glass was prepared by the sol-gel method. The structure of the glass, especially local environment of Ti⁴⁺ ions was examined using X-ray diffraction and X-ray absorption fine structure (XAFS) analyses, and was compared with that of the melt-derived glass with the same composition. It was found that Ti⁴⁺ ions are rather in five-fold coordination state, forming TiO₅ pyramids with one doubly bonded Ti=O in the gel-glass, while they were in lower coordination state or four-fold coordination in the melt-derived glass.     

Synthesis and ion selectivity of macrocyclic metacyclophanes analogous to spherand-type calixarenes

Novel macrocyclic compounds, hexahydroxy[1.0.1.0.1.0]- (2b) and octahydroxy[1.0.1.0.1.0.1.0]metacyclophane (2c) have been prepared in 50–70% yield by base-catalyzed condensation of 5,5-di-tert-butyl-2,2-dihydroxybiphenyl (1) with formaldehyde in refluxing xylene. An attempted alkylation of the flexible macrocycles2b and2c with ethyl bromoacetate in the presence of Cs₂CO₃ under acetonitrile reflux gave only one pure stereoisomer3 and4, respectively, while other possible isomers were not observed. The structural characterization of these products is also discussed. The two-phase solvent extraction data indicated that hexaethyl ester3 and octaethyl ester4 show strong metal affinity, comparable with that of the corresponding calix[n]arenes, and a high K⁺ selectivity was observed for octaethyl ester4.¹H-NMR titration of hexaethyl ester3 and octaethyl ester4 with KSCN clearly demonstrate that a 11 complex is formed which is stable on the NMR time scale.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

Rapid ruthenium-catalyzed synthesis of pyranopyrandiones by reconstructive carbonylation of cyclopropenones involving C[bond]C bond cleavage

Pyranopyrandiones were prepared by a novel ruthenium-catalyzed carbonylative dimerization of cyclopropenones via C-C bond cleavage. For example, treatment of dipropylcyclopropenone with a catalytic amount of Ru3(CO)12 and NEt3 in THF under 15 atm of carbon monoxide at 140 degrees C for 20 h gave a novel functional monomer, 3,4,7,8-tetrapropylpyrano[6,5-e]pyran-2,6-dione, in an isolated yield of 81%. Unsymmetrically substituted pyranopyrandiones were also obtained by ruthenium-catalyzed carbonylative coupling of cyclopropenones with alkynes under similar reaction conditions.     

Enantioselective ring cleavage of dioxane acetals mediated by a chiral Lewis acid: application to asymmetric desymmetrization of meso-1,3-diols

[reaction: see text]. Phenylalanine-derived B-aryl-N-tosyloxazaborolidinones selectively activate one of two enantiotopic oxygen atoms in prochiral anti dioxane acetals derived from meso-1,3-diols, leading to enantioselective formation of ring-cleavage products. The reaction is utilized as a key step in asymmetric desymmetrization of meso-1,3-diols.     

The synthesis of isoquinoline alkaloid and its related compounds using alanine derivatives as chiral auxiliaries

Chiral 1-substituted isoquinoline derivatives, which were obtained by the reaction using alanine derivatives as chiral auxiliaries, were transformed to (S)-2,3,9,10,11-pentamethoxyhomoprotoberberine (7) and a synthetic intermediate for O-methylkreysigine (9) in good yields and high stereoselectivity. The corresponding chiral allyl derivative of isoquinoline was transformed to a pyrrolidinoisoquinoline (16) in a highly enantioselective manner.     

Sulfur nitride in organic chemistry. 9. The reaction of tetrasulfur tetranitride with benzyl ketones. Preparation of 3,4-disubstituted-1,2,5-thiadiazoles

The reaction of tetrasulfur tetranitride ( 1 ) with various aryl and alkyl benzyl ketones ( 2a-o ), oxindole ( 11 ), benzyl α-pyridyl ketone ( 12 ) and α-phenacylpyridine ( 13 ) afforded the corresponding 1,2,5-thiadiazoles ( 3a-n, 11 and 14 ). The scope and limitations of the above reaction were investigated and the evidences suggesting the radical anion mechanism are presented.     

Synthesis, structure, and physical properties of 1,11-o-benzeno[2]orthocyclo[2](1,2)tropyliophane

The title compound (2) has been synthesized, the structure and the physical properties of which are investigated by X-ray, spectroscopic analyses, and MO calculations. There exists charge transfer (CT) interaction between the tropylium ion and the facing phenyl ring. From the pK_R⁺ value of 2, it can be clear that the cation 2 is stabilized by the CT interaction. In spite of the presence of bond weakening σ-π orbital mixing, the cation 2 withstands retro[4+4]type bond cleavage, which is quite interesting when compared to a facile cleavage for the congener with anthracene photodimer type structure.     

Cyclopolymerization of diallylamine derivatives in dimethyl sulfoxide

Diallyl quaternary ammonium chlorides, bromides and N-alkyldiallylamine hydrochlorides were polymerized with ammonium persulfate (APS) in dimethyl sulfoxide (DMSO). The dependences of yield and molecular weight of polymers on polymerization conditions were examined and quaternary ammonium chlorides were found to have better polymerizability than bromides. The poly(diallyl quaternary ammonium chlorides) obtained with APS—DMSO system are expected to have quite high molecular weights, as determined from the measurement of limiting viscosity numbers of the polymers in NaCl aqueous solution.     

Multiplex amplified product-length polymorphism analysis of 36 mitochondrial single-nucleotide polymorphisms for haplogrouping of East Asian populations

We present a reliable, rapid, and economical multiplex amplified product-length polymorphism (APLP) method for analyzing the haplogroup-diagnostic mitochondrial single-nucleotide polymorphisms (mtSNPs) in East Asian populations. By examining only 36 haplogroup-specific mtSNPs in the coding region by using four 9-multiplex polymerase chain reaction (PCR) and subsequent electrophoresis, we could safely assign 1815 individuals from 8 populations of Japanese, Korean, Chinese, and Germans to 45 relevant haplogroups. This multiplex APLP analysis of coding-region mtSNPs for haplogrouping is especially useful not only for molecular phylogenetic studies but also for large-scale association studies due to its rapid and economical nature. This is the first panel of mtSNPs in the coding region to be used for haplogrouping of East Asian populations.     

Photochemical preparation of poly(N-vinyl-2-pyrrolidone)-stabilized platinum colloids and their deposition on titanium dioxide

Preparation processes for Pt-deposited TiO(2) (Pt/TiO(2)) by the synthesis of Pt nanoparticles and their deposition were pursued by transmission electron microscopy, extended X-ray absorption fine structure, UV-vis spectroscopy, and Fourier transform infrared spectroscopic studies. Colloidal dispersions of Pt particles stabilized by poly(N-vinyl-2-pyrrolidone) (PVP) were photochemically synthesized in aqueous ethanol solution. The average diameter of Pt particles was estimated to be 2.0 +/- 0.5 nm, which was almost unchanged by changing the reducing agent from ethanol to methanol and 2-propanol. The PVP-stabilized Pt particles were distributed over a TiO(2) surface only by mixing the Pt colloidal dispersions and TiO(2). CO was chemically coordinated on the Pt particles on a TiO(2) surface after heat treatment was carried out in an O(2) flow at 673 K to completely remove the residual PVP on Pt/TiO(2). Hydrogen reduction at 473 K did not increase the amount of CO adsorbed on Pt sites. The Pt/TiO(2) catalyst after the oxidation treatment showed higher activity for CO photooxidation than that obtained for pure TiO(2) catalyst. The CO photooxidation rate was not unchanged by the H(2) reduction.