bluuebunny/crossref_metadata_2025 huggingface dataset:
Partial Molar Volumes of Sodium Alkyl Sulfates and Disodium α,ω-Alkanediyl Disulfates in Aqueous Solutions
Authors: Tamaki Kunio , Nagai Keiko , Ohara Yoko
Published: August 2006

The densities of aqueous solutions of sodium alkyl sulfates, H(CH2)nSO4Na (n = 1—6, 8, 10, 12) and disodium α,ω-alkanediyl disulfates, NaO4S(CH2)nSO4Na (n = 2—4, 6, 8, 10) were measured at 25 °C, and the limiting partial molar volumes were calculated. The group partial molar volume of SO4− was estimated to be 44.0 cm3 mol−1.
Iron-Catalyzed Oxidation of 4-Substituted N,N-Dimethylanilines with Molecular Oxygen in the Presence of Benzoyl Cyanide
Authors: Murata Satoru , Teramoto Koji , Miura Masahiro , Nomura Masakatsu
Published: August 2006

The oxidation of 4-substituted N,N-dimethylanilines with molecular oxygen using a catalytic amount of iron(III) chloride efficiently proceeded in the presence of benzoyl cyanide to give the corresponding N-cyanomethyl-N-methylanilines along with N-methylformanilides.
Lactonization of Hydroxy Ester over Hydrous Zirconium(IV) Oxide Modified by Trimethylsilyl Chloride
Authors: Kuno Hideyuki , Shibagaki Makoto , Takahashi Kyoko , Matsushita Hajime
Published: August 2006

The lactonization of hydroxy esters was performed over hydrous zirconium(IV) oxide modified by trimethylsilyl chloride. In the case of both primary and secondary hydroxy esters, lactones were obtained in high yield. In addition, it was elucidated that modified-hydrous zirconium(IV) oxide is superior to hydrous zirconium(IV) oxide regarding selectivity in lactonization.
7Li NMR and 35Cl, 81Br NQR Study of Lithium Ion Conductor LiAlX4 (X = Cl and Br)
Authors: Yamada Koji , Kinoshita Masakazu , Hosokawa Kayoko , Okuda Tsutomu
Published: August 2006

The dynamic behavior of LiAlX4 (X = Cl and Br) was studied by means of 7Li NMR and 35Cl, 81Br NQR spectroscopies. The motional narrowing processes of the 7Li NMR due to Li+ diffusion were observed above room temperature for single crystals of LiAlX4. The activation energies for these processes were 43.4 and 42.1 kJ mol−1 for the chloride and bromide analogs, respectively. A stepwise decrease in the 7Li NMR quadrupole splitting suggested that the Li nucleus sees time averaged electric field gradient (EFG) arising from several different sites. The modulation effect of Li+ diffusion on the NQR relaxation times was detected only for LiAlBr4 but not for the chloride analog.
A DNMR Study of Restricted Methylene Rotations in Pyridyl-, Pyrimidyl-, and Quinolylmethyllithium
Authors: Yoshino Akihiro , Sakakihara Hiroshi , Takahashi Kensuke
Published: August 2006

The thermodynamical parameters for the title rotations were obtained by means of the DNMR technique. The parameters can be explained in terms of both steric and electronic effects of the substituents introduced. The largest activation energy and entropy were found to be about 122 kJ mol−1 and 153 J K−1 mol−1 for 6-methyl-2-quinolylmethyllithium.
Novel Organic Ions of High-Spin States. III. ESR and 1H ENDOR Studies of a Monocation of m-Phenylenebis(phenylmethylene)
Authors: Matsushita Michio , Nakamura Toshihiro , Momose Takamasa , Shida Tadamasa , Teki Yoshio , Takui Takeji , Kinoshita Takamasa , Itoh Koichi
Published: August 2006

The monocation of m-phenylenebis (phenylmethylene)(m-PBPM), the first high-spin hydrocarbon cation, has been generated by γ-radiolysis and subsequent photolysis of 1,3-bis(α-diazobenzyl)benzene in s-butyl chloride at 77 K. The system is studied by ESR and 1H ENDOR spectroscopy. Two conformers of the monocation are detected which are associated with spin Hamiltonian parameters of S = 3/2, g = 2.003, D = 0.1350 cm−1, and |E| = 0.0040 cm−1 and S = 3/2, g = 2.003, D = 0.1285 cm−1, and |E| = 0.0055 cm−1, respectively. The off-axis extra lines characteristic of the quartet-state powder pattern ESR spectra were identified. The ground state of both the cations is confirmed to be spin-quartet by the measurement of their ESR intensity at low temperatures. The 1H ENDOR measurement has shown that the electron in the nonbonding π-orbital is removed upon ionization to yield the π-cation. The hyperfine structure due to the divalent 13C was found to be consistent with the electronic structure of the π-cation. A semiempirical calculation of the fine structure parameters D and E has been carried out in terms of spin–spin interaction. The semiempirical calculation and the electronic structure suggest that both the cations are in a trans–trans conformation in contrast to a cis–trans for the neutral m-PBPM. The result is discussed in comparison with the monoanion of m-PBPM.
Behavior of Surfactants in a Highly Loaded Coal–Water Slurry. I. Effects of Surfactant Concentration on Its Properties
Authors: Ogura Tsugitoshi , Tanoura Masazumi , Hiraki Akio
Published: August 2006

Two types of anionic surfactants and one type of nonionic surfactant were investigated in order to clarify their roles and behaviors in a highly loaded coal–water slurry (CWM) of high coal concentration. Both saturated adsorption of the surfactant on coal particles and its presence in water were found to be necessary to prepare a practical CWM. The adsorption isotherms of the surfactants were described using the “Langmuir” equation. Each surfactant had a characteristic value of saturated adsorption. An estimation method of the required amount of the surfactant to prepare a practical CWM was proposed. The zeta potential of the CWM was found to vary with the coal concentration, and to be controlable using surfactants, thus failing to be a proper measure of the CWM at high coal concentrations.
CMC of Alkylammonium Nitrate Determined by a Novel Method
Authors: Yamauchi Akira , Inoue Minako , Ohgi Hironori , Mito Takatoshi
Published: August 2006

A novel method for the determination of the critical concentration of a micelle formation based on the measurement of liquid junction potential was presented in this paper. The CMC values of the typical anionic and cationic surfactants and the new compounds, alkylammonium nitrates were obtained by using the method. The CMC values of the new compounds were confirmed by means of the conventional methods. In addition, the transport numbers of those compounds relating to the dynamic behavior in solution were estimated and the physical meaning was discussed.
Critical Consideration on the Phase Diagrams of Monolayers Drawn from the π–A Isotherms
Authors: Kato Teiji , Tatehana Atsushi , Suzuki Noboru
Published: August 2006

The shape of π–A isotherms of insoluble monolayers on a water surface was determined by balancing the relaxation times of the molecular processes which occur during the compression of monolayers and the time of observation (tob). Here, tob is defined in terms of the reciprocal of the strain rate of compression; to keep tob constant during compression, monolayers should be compressed under a constant strain rate rather than a constant speed. π–A isotherms of high-purity pentadecanoic acid monolayers were measured under two different tob (300 and 3000 s). Phase diagrams of the pentadecanoic acid in monolayers drawn from the π–A isotherms differ considerably upon changing tob by ten times. Therefore, if one wishes to draw a phase diagram from the results of the temperature dependence of the π–A isotherm, tob of the measurements should be annexed to compare these results with those of other investigators. The so-called solid film region of the monolayers at low temperatures disappeared for isotherms measured at longer tob than 3000 s, in contrast to the general sense of relaxation phenomena. This was explained by the large deviation from πesp of the pentadecanoic acid at the lower end of the solid film region (21 mN m−1) at lower temperatures.
In-Plane Anisotropy in Mixed Langmuir–Blodgett Films of Triphenylene Derivatives and 2,4,7-Trinitro-9-fluorenone
Authors: Ogawa Kimiya , Yonehara Hisatomo , Pac Chyongjin , Maekawa Eturô
Published: August 2006

Monolayers and Langmuir–Blodgett (LB) films of 2,3,6,7,10,11-hexaalkoxytriphenylenes (CnOTP; n denotes the number of carbon atoms per alkyl chain substituent; n = 3—6) and their charge transfer (CT) complexes with 2,4,7-trinitro-9-fluorenone (TNF) were studied. It was found that the surface pressure applicable for the deposition of LB film increases as the length of alkyl chain of the peripheral substituents decreases. Polarized UV-vis and infrared spectra for the LB films of the CT complexes can be explained consistently with the following model of molecular assembly: The long axes of one-dimensionally stacked molecular columns are preferentially oriented along the dipping direction in the LB films. Marked in-plane dichroism was observed for the LB films of the CT complexes while the LB film of CnOTP without TNF showed only a little dichroism.
Ligand Effect on the Electrochemical Oxidation of trans-[Ru(NO2)X(py)4]n (n = 0 for X = NO2, n = + for X = NH3). Reactivity of Coordinated Nitro (RuII–NO2) to Give Monooxygen Moiety (RuIV=O) Depends on the Ambient Ligand (X)
Authors: Nagao Noriharu , Nagao Hirotaka , Nishimura Hisatoshi , Kuroda Hiroshi , Satoh Katsuyuki , Howell F Scott , Mukaida Masao
Published: August 2006

The electrochemical behavior of trans-[Ru(NO2)X(py)4]n(n = 0 for X = NO2 and n = + for NH3) in CH3CN was investigated at various temperatures. trans-[RuII(NO2)2(py)4] undergoes a one-electron oxidation to give trans-[RuIII(NO2)2(py)4]+. Rapid chemical reactions (nitro–nitrito isomerization, dimeric intermediate formation, and its disintegration) follow in succession until nearly equal amounts of trans-[Ru(NO)(NO2)(py)4]2+ and trans-[RuII(NO2)(solvent)(py)4]+ are generated as the final products. Essentially the same result was found in trans-[Ru(NO2)(NH3)(py)4]+. These results were quite different from those observed previously in the electrochemical oxidation of trans-[RuIICl(NO2)(py)4], where both trans-[RuIVCl(O)(py)4]+ and trans-[Ru(NO)Cl(py)4]2+ were generated directly by one-electron oxidation. We conclude that the different electrochemical behavior between trans-[RuCl(NO2)(py)4] and trans-[Ru(NO2)X(py)4]n (X = NO2 and NH3) stems primarily from a different disintegration mode of the above-mentioned dimeric intermediate species.
Separation and Concentration of Tin(IV) by Co-precipitation with Gallium Phosphate for Electrothermal Atomization Atomic Absorption Spectrometry
Authors: Kagaya Shigehiro , Ueda Joichi
Published: August 2006

Gallium phosphate co-precipitates quantitatively 0.5—5.0 μg of tin(IV) from 100 to 500 cm3 of a sample solution at pH 3.0—6.0. After co-precipitation, tin(IV) can be sensitively determined by electrothermal atomization atomic absorption spectrometry. The atomic absorbance of tin(IV) increases by about 1.7 times in the presence of gallium. Although many ions interfere with the determination, interference from the majority can be eliminated by using a graphite furnace impregnated with hafnium, which also improves the sensitivity and reproducibility of the determination. Tellurium(IV) and zirconium(IV) interfere seriously. The calibration curve is linear from 0.02 to 0.20 μg cm−3 for tin(IV), and the detection limit (signal/noise = 2) is 0.23 ng cm−3 of tin(IV) in 500 cm3 of the initial sample solution. This method is applicable to the analyses of water samples for tin(IV).
Preparation of Cyclodextrin Precipitates with Volatile Hydrocarbons in Aqueous Media, and Determination of Hydrocarbon/Cyclodextrin Molar Ratios in the Precipitates
Authors: Sanemasa Isao , Wu Yue , Koide Yuuki , Shigenaga Masako , Ishibashi Kazunari , Deguchi Toshio
Published: August 2006

A technique is proposed to prepare cyclodextrin (CyD) precipitates with volatile hydrocarbons. On introducing the vapor of a liquid or solid hydrocarbon into α-, β-, or γ-CyD in an aqueous solution and circulating it in a closed system, CyD can be easily precipitated. The CyD precipitates isolated from aqueous solutions were analyzed for the hydrocarbon/CyD molar ratio. The concentration of CyD in the supernatant aqueous solution was also measured. The technique has been applied at 25 °C to such hydrocarbons as n-alkanes (C5 to C10), cyclohexane, halobenzenes(fluoro-, chloro-, bromo-, and iodo-benzene), p-difluorobenzene, benzene, naphthalene, biphenyl, and diphenylmethane. Precipitates were also prepared in β-CyD solutions with the vapor of C5—C9 mixtures at various mixing ratios.
Optical Resolution and Asymmetric Transformation of (RS)-N-Alkyl- and (RS)-N,N-Dialkyl-2-phenylglycines
Authors: Shiraiwa Tadashi , Baba Yoshihisa , Miyazaki Hideya , Sakata Shinji , Kawamura Seiko , Uehara Masashi , Kurokawa Hidemoto
Published: August 2006

Optical resolution of (RS)-N-methyl-2-phenylglycine [(RS)-Mpg] and (RS)-N-ethyl-2-phenylglycine [(RS)-Epg] was carried out by using (1S)-10-camphorsulfonic acid [(S)-CS] as resolving agents, and that of (RS)-N-ethyl-N-methyl-2-phenylglycine [(RS)-Emp] by (R)- and (S)-1-phenylethylamine. Racemization rates of optically active Mpg, Epg, Emp, N,N-dimethyl-2-phenylglycine [Dmp], and six α-amino acids were measured by heating in carboxylic acids. The electron-donating amino acid side chain and N-substituted alkyl group decreased the rate to inhibit the formation of intermediary carbanions, whereas the electron-withdrawing side chain increased it. Asymmetric transformation of (RS)-Mpg, (RS)-Epg, and (RS)-Dmp was carried out on the basis of the results of optical resolution and racemization to give the corresponding enantiomers of approximately 100% optical purities in over 70% yield based on the starting racemates.
Syntheses of Acetomycin-Related (2R,3S,4R)- and (2S,3R,4R)-2-Acetoxy-4-acetyl-3,4-dimethyltetrahydrofuran and Their Growth Inhibition Activity against Tumor Cells
Authors: Ishihara Jun , Terato Nahoko , Sumino Akihiko , Tadano Kin-ichi , Ogawa Seiichiro
Published: August 2006

The syntheses of two tetrahydrofuran derivatives structurally related to the antitumor agent acetomycin are described. These compounds were synthesized starting from known d-glucose-derived functionalized tetrahydrofuran derivatives.
Photocontrolled Binding of Metal Ions with Thioindigo Derivatives Containing Oxyethylene Chains
Authors: Rahman S M Fatah-ur , Fukunishi Koushi , Kuwabara Masaki , Yamanaka Hiroki , Nomura Mototeru
Published: August 2006

Binding ability of a series of thioindigo derivatives(Ia—g), which possess a molecular architecture, capable of capturing different metal ions was examined. From the results of solvent extraction the order of extractibility for metal ions by cis-Ig was found as Ag+ >> Cs+ > Rb+ > K+ > Na+ > Li+. Enhancement of excellent binding ability by trans to cis photoisomerization of Ig, the highest amount of transported Ag+ across a liquid membrane by Ig when irradiated with 550 and 480 nm light alternately, and the considerable suppression for thermal cis-to-trans isomerization in presence of Ag+ were found.
Ferrocene-Appended Cyclodextrins. The Effects of Temperature, Organic Solvent, Length of Spacer, and Cavity Size on the Complexation Behavior
Authors: Suzuki Iwao , Chen Qiang , Ueno Akihiko , Osa Tetsuo
Published: August 2006

Inclusion phenomena of cyclodextrins (CyDs) bearing a ferrocene moiety, 1—4, which have different cavity sizes and spacer lengths, were investigated by circular dichroism (CD) spectroscopy in pure ethylene glycol (EG) and 20% EG aqueous solution. β-CyD derivatives, 1 and 3, and a γ-CyD derivative, 4, form intramolecular complexes, including the ferrocene moiety in the CyD cavity with orientation similar to that in corresponding native CyD–ferrocene complexes, while another γ-CyD derivative, 2, which has no spacer alkyl chain, takes various conformations. The host–guest binding constants of 1—4 for several guests revealed that the ferrocene moiety of 1—4 depresses the guest binding, acting as an intramolecular inhibitor in guest binding. In particular, the depression was remarkable for 3 and 4 and the spacer alkyl chain was suggested to stabilize the intramolecular complexes. The ferrocene modified CyDs exhibit similar trends in guest selectivity to those of native CyDs. The effects of EG content on the binding constants of 1 and 2 revealed that hydrophobic effect operated in the guest accommodation. Thermodynamic parameters for the binding processes of 1 and 2 for 1-adamantanol were obtained from the temperature variations in binding constants, the values being −21.9 kJ mol−1 for ΔH° and 2.76 J mol−1 K−1 for ΔS° for 1 and −25.1 kJ mol−1 for ΔH° and −36.1 J mol−1 K−1 for ΔS° for 2. These values indicated that the complexation of 1 and 2 for 1-adamantanol was governed both by hydrophobic effect and van der Waals interaction, and the latter was especially important in the case of 1 and 1-adamantanol.
A Practical O2-Oxidation of Functionalized Alcohols Producing Carboxylic Acids Catalyzed by the Pd–C/Pb(OAc)2 System
Authors: Akada Mitsuo , Nakano Shinji , Sugiyama Toshiyuki , Ichitoh Kazumoto , Nakao Hiroki , Akita Munetaka , Moro-oka Yoshihiko
Published: August 2006

The Pd–C/Pb(OAc)2 system catalyzes selective O2-oxidation of ArCH(R)CH2OH to ArCH(R)COOH (useful intermediates for drug synthesis) in high yields without contamination of ArCOOH. The turnover number (substrate/Pd) is improved to 85 and >1800 by recycling the catalyst and using a special reactor, respectively. Alkanols are also efficiently oxidized to alkanoic acids by the title catalyst system.
Extraction Spectrophotometric Determination of Molybdenum(V) with N1-(o-Chlorophenyl)-N1-hydroxy-N2-(o-methylphenyl)benzamidine Hydrochloride and Thiocyanate
Authors: Mishra Indumati , Mohabey Hemlata
Published: August 2006

A highly selective method has been developed for the extraction and spectrophotometric determination of molybdenum(V) using N1-(o-chlorophenyl)-N1-hydroxy-N2-(o-methylphenyl)benzamidine hydrochloride and thiocyanate. The reagent reacts with molybdenum(V) in the presence of thiocyanate ion and forms orange red complex in strongly acidic medium. Which can be extracted with benzene. The extract shows a sharp maximum at 470 nm, having molar absorption coefficient 3770 cm3 mol−1 cm−1. The system obeys Beer’s law from 3 to 22 ppm. A large number of metal ions associated with matrix of Mo, such as Ni, Co, Cu, V, Nb, Ti, Zn, etc. do not interfere with the determination. The applicability of the method has been tested with various alloys. The stoichiometry of mixed complex is found to be 1 : 2 : 2 (metal : reagent : thiocyanate).
A Convenient Synthesis and Structural Assessment of [Sn(CH3)2(L2)](ClO4)2
Authors: Dey D , Basu Baul T S , Rivarola E
Published: August 2006

A general synthesis for a novel class of complexes of the type, [Sn(CH3)2(L2)](ClO4)2 (L = 2-(substituted arylazo) pyridine) is reported. The structure of the complexes have been investigated by 119tin Mössbauer spectroscopy and NMR coupling constant 2J (117/119 Sn–CH). Further, the extent of distortion of tin–methyl groups in octahedral complexes have been calculated from the quadrupole shift (Q.S.) values using Parish’s relationship.
Photo-Redox Catalytic Behavior of Water-Soluble Copolymers of the 5,10,15,20-Tetra-p-tolylporphyrins Bearing a Vinyl Group in a Substituent at the Pyrrole Moiety and Their Zn-Complexes
Authors: Kamogawa Hiroyoshi , Kato Koichiro
Published: August 2006

Water-soluble copolymers of the 5,10,15,20-tetra-p-tolylporphyrins bearing a N-(p-vinylphenyl)carbamoyl group in a substituent at the pyrrole moiety or their Zn complexes with N-vinyl-2-pyrrolidone have been effective as photo-redox catalysts for the FRA–l-ascorbic acid and the viologen–triethanolamine in aqueous solutions or in the copolymer films.
Solvent Extraction of Europium(III) Anionic Complexes with Several β-Diketones as Ion-Pairs with Tetrabutylammonium into Chloroform
Authors: Noro Junji , Sekine Tatsuya
Published: August 2006

The solvent extractions of europium(III) in 0.1 mol dm−3 sodium nitrate solutions with acetylacetone (Hacac), benzoylacetone (Hbza), benzoyltrifluoroacetone (Hbfa), trifluoroacetylacetone (Htfa), and hexafluoroacetylacetone (Hhfa) into chloroform were measured in both the absence and presence of tetrabutylammonium (tba+). From the results and those with 2-thenoyltrifluoroacetone (Htta) in a previous study it was concluded that extractions with the CF3– containing β-diketones, Hbfa, Htfa, Hhfa, and Htta are greatly enhanced by the addition of tba+. This could be explained in terms of the extraction of a ternary complex, EuA4− tba+ (A− is a β-diketonate ion). However, extractions with Hacac and Hbza were nearly the same when tba+ was added. The enhancement of extraction was statistically treated by assuming an association of EuA3 and A−tba+ in the organic phase. The equilibrium constants for an association with different β-diketones were compared, and the reasons for the difference in the association equilibrium as well as the enhancement of extraction are described.
Synthesis and Characterization of Mononuclear (Mn(II) and Mn(III)) and Dinuclear (Mn(II)Mn(II) and Mn(II)Mn(III)) Complexes with 2,6-Bis[N-(2-pyridylethyl)iminomethyl]-4-methylphenol
Authors: Mikuriya Masahiro , Fujii Toshinori , Tokii Tadashi , Kawamori Asako
Published: August 2006

Mononuclear and dinuclear manganese complexes with2,6-bis[N-(2-pyridylethyl)iminomethyl]-4-methylphenol (HL), [MnII2(L)(CH3COO)2(CH3OH)](ClO4) (1), [MnII2(L)(CH3COO)2(NCS)] (2), [MnII(HL)(NCS)2(H2O)] (3), [MnIIMnIII(L)(CH3COO)2(CH3OH)2](ClO4)2 (4), [MnIIMnIII(L)(CH3COO)2(NCS)2] (5), [MnIIMnIII(L)(CH3COO)2(N3)2]·2CH3OH (6), and [MnIII(HL)(N3)3] (7), have been prepared and characterized by infrared, electronic, and ESR spectra, as well as the temperature dependence of the magnetic susceptibilities (80—300 K). The molecular structures of 1, 2, 3, 6, and 7 were determined by single-crystal X-ray structure analyses. Complexes 1 and 2 have a μ-phenoxo-di-μ-acetato-bridged dinuclear structure, in which one manganese atom is five-coordinated and the other six-coordinated. Complex 6 is a μ-phenoxo-di-μ-acetato-bridged dinuclear molecule comprising an octahedral Mn(II) atom and an elongated-octahedral Mn(III) atom. The manganese atoms of 3 and 7 are six-coordinated in a distorted octahedral environment. The spectral and magnetic properties are discussed in relation to the crystal structures.
Side Chain Liquid Crystalline Polyoxetanes with a Spacer-Separated Azobenzene Moiety. I. Preparation and Characterization
Authors: Motoi Masatoshi , Noguchi Kunimasa , Arano Akio , Kanoh Shigeyoshi , Ueyama Akihiko
Published: August 2006

Several oxetane derivatives carrying the azobenzene moiety at the C-3 position of the oxetane ring through the spacer arms of differing lengths were prepared by a substitution reaction of the corresponding bromide or p-toluenesulfonate residue of the oxetane with 4-hydroxyazobenzenes. The polymers of these oxetane derivatives were readily obtained by cationic ring-opening polymerization using the adequately increased amount of a THF· BF3 complex as an initiator at 20—30 °C. The liquid crystalline property of the polymers thus obtained were examined by differential scanning calorimetry and by optical polarized microscopy. From these measurements the influences of the p′-substituted azobenzene and of the spacer arm on the liquid crystalline property were found.
Characterization of Isomers Which Are Produced by Reactions of (1R,3S-Cyclohexanediamine)platinum(II) with Nucleotide d(GpG)
Authors: Inagaki Kenji , Sawaki Kimie
Published: August 2006

Two adducts obtained from reactions of dinucleotide (d(GpG)) with 1R,3S-cyclohexanediamineplatinum(II) have been investigated on the basis of NMR spectroscopy. They were assigned as interbase cross-linked adducts being platinated at the N7 positions of the adjacent guanine bases. Both isomers differ with respect to the orientation of the cyclohexane ring toward the carbonyl group at the 6 position of the adjacent guanine bases. A conformational analysis of the cyclohexane ring is also described.
Fritsch–Wiechell Rearrangement of 1-Chlorovinyl Sulfoxides: A New Method for Synthesizing Acetylenes from Aldehydes with One-Carbon Homologation
Authors: Satoh Tsuyoshi , Hayashi Yasumasa , Yamakawa Koji
Published: August 2006

1-Chlorovinyl sulfoxides, easily prepared from aldehydes and chloromethyl phenyl sulfoxides, were treated with t-butyllithium to afford one-carbon homologated acetylenes via alkylidene carbenoids in high yields.
Acidity and Dynamic Structure of the Potent Uncoupler SF6847 (2,6-Di-t-butyl-4-(2,2-dicyanovinyl)phenol) and Its Derivatives
Authors: Miyoshi Hideto , Guo Ze-jian , Fujita Toshio , Iwamura Hajime
Published: August 2006

The acid dissociation constant (Ka) of a series of 2,6-di-t-butyl-4-(disubstituted vinyl)phenols was measured in water spectrophotometrically at 25 °C. The electronic substituent effects of the substituted vinyl moiety on the pKa value were examined by dual-electronic-parameter analyses. The electronic effects of the two substituents at the end of the vinyl moiety were found to be not equal in the acid-base dissociation equilibrium. The inductive and resonance effects of the X-substituents trans to the benzene ring and the inductive effect of the Y-substituents cis to the benzene ring were significant factors governing the pKa value. These results and the molecular orbital calculation studies suggest that although the π-bonded X-substituents are coplanar to the vinyl plane, the π-bonded Y-substituent are twisted by a steric repulsion with the benzene ring. The variations in the pKa value of variously substituted analogs were related with the ease of intramolecular rotational motion around the bond connecting the vinyl group and the benzene ring, based on 1H NMR studies.
Synthesis of 1-(2,2-Dicyanovinyl)-, 1-(2,4,4-Tricyano-1,3-butadienyl)-, 1,6-Bis(2,2-dicyanovinyl)-1,3,5-cycloheptatriene and Their Vinylogs
Authors: Higuchi Hiroyuki , Kondo Masao , Yonehara Hiroko , Ojima Juro , Iyoda Masahiko
Published: August 2006

The 1-(2,2-dicyanovinyl)-, 1-(2,4,4-tricyano-1,3-butadienyl)-, 1,6-bis(dicyanovinyl)-substituted 1,3,5-cycloheptatriene, and their vinylogs have been synthesized by condensation of 1-formyl-, 1-(2-cyano-2-formylvinyl)-, 1,6-diformyl-1,3,5-cycloheptatriene, and their vinylogs, respectively, with malononitrile mediated with TiCl4 as a Lewis acid.
Photochromism of Heterocyclic Fulgides. IV. Relationship between Chemical Structure and Photochromic Performance
Authors: Tomoda Akihiko , Kaneko Akira , Tsuboi Hideki , Matsushima Ryoka
Published: August 2006

The absorption spectra and quantum yields of various heterocyclic fulgides were measured. The absorption maxima of the colored photocyclization products of fulgides were dependant upon the structure of heterocyclic rings and the substituent; and increase of the electron-donating ability of the heterocyclic ring caused a red shift of λmax. A quantum yield measurement of the photochromic reaction of fulgides revealed that not only the steric effect, but also the electronic effect of substituent (e.g. p-(dimethylamino)phenyl, cyano, acetyl) introduced into the heterocycles, changed the reactivity for both coloration and bleaching.
The Structures of M2X93− (M = Bi ; X = Cl, Br) Ions Determined by Rietveld Analysis of X-Ray Powder Diffraction Data
Authors: Ishihara Hideta , Yamada Koji , Okuda Tsutomu , Weiss Alarich
Published: August 2006

The results of the Rietveld analysis of X-ray powder diffraction data for title compounds show that the space group for (CH3NH3)3Bi2Cl9 is Pnma with Z = 4 and its lattice constants are a = 2040.6, b = 770.0, c = 1324.6 pm. It consists of one–dimensional double chains of Bi2Cl93− polyanions. The space group for [N(CH3)4]3Bi2X9 (X = Cl, Br) is P63/mmc with Z = 2 and its lattice constants are a = 926.2, c = 2192.2 pm for X = Cl and a = 951.8, c = 2245.9 pm for X = Br. It contains ioslated Bi2X93− anions with a triple bridged bioctahedral structure.
Study of Polarographic Anodic Current in the Presence of Selenate Ion
Authors: Kikuchi Kenji , Murayama Teisuke
Published: August 2006

The polarographic anodic current observed in the presence of selenate ion has been studied using a numerical method previously proposed by us. Though there is no current plateau in the current-potential curve, the current increases with an increase in the concentration of selenate. The logarithmic plots of the current against the electrode potential give a straight line with a slope of 39—40 mV/unit. With the aid of the numerical method, it is concluded that the anodic current is controlled by the rate of precipitation, and that the rate can be expressed by a formula which is derived by assuming a reaction sequence for precipitation and represents the rate controlled by the nucleation step.
Intercalation of Ferrocene and (Ferrocenylalkyl)ammonium Halides into the Gel-V2O5 Interlayer Space
Authors: Okuno Shoji , Matsubayashi Gen-etsu
Published: August 2006

Ferrocene, FcH, 1,1′-dimethylferrocene, FcMe2, some (ferrocenylalkyl)ammonium iodides, Fc(CH2)nNR2R′+I−, chlorides, Fc(CH2)nNR2R′+Cl− [Fc = (C5H5)Fe(C5H4); n = 1 and 2; R, R′ = H and Me], benzyldimethyl-, benzyltrimethylammonium and octylammonium iodides reacted with powdered gel-V2O5 suspended in ethanol to afford intercalation compounds; V2O5·(H2O)0.6·[Fc+H]0.27, V2O5·(H2O)0.6·[Fc+Me2]0.22, V2O5·(H2O)0.6·[Fc+CH2NHMe2+]0.16, V2O5·(H2O)0.6·[Fc+CH2NMe3+]0.15, V2O5·(H2O)0.8·[Fc+CH2CH2NH3+]0.21, V2O5·(H2O)0.8·[Fc+CH2CH2NMe3+]0.14, V2O5·(H2O)0.6·[Fc+CH2NHMe2+]0.18, V2O5·(H2O)0.6·[Fc+CH2CH2NH3+]0.22, V2O5·(H2O)0.6·[PhCH2NHMe2+]0.29, V2O5·(H2O)0.6·[PhCH2NMe3+]0.24, and V2O5·(H2O)0.6·[n-C8H17NH3+]0.33. The intercalation compounds are constructed with layered V2O5 moieties in both V(IV) and V(V) states and the ferrocenium, the ferrocenium derivatives, the benzyldimethyl-, the benzyltrimethylammonium or the octylammonium cation in the interlayer space, producing the single V2O5-interlayer spacings. Molecular arrangements of these (ferrocenylalkyl)ammonium species in the interlayer space and electronic states of the guest and the host moieties are discussed on the basis of powder X-ray diffraction patterns as well as powder reflectance, ESR and X-ray photoelectron spectra.
The Classification of Twenty Common Amino Acid Residues in Protected Peptides by Their β-Sheet-Structure-Stabilizing Potentials, SPβ, and Its Application to Peptide Synthesis
Authors: Narita Mitsuaki , Lee Jin-Shik , Murakawa Yuka , Kojima Yoshihisa
Published: August 2006

A host-guest approach was devised to evaluate the β-sheet-structure-stabilizing potentials, SPβ, of the 20 common amino acid residues in protected peptides whose side-chain functional groups were protected by suitable groups commonly used in peptide synthesis. The β-sheet structure of host-guest pentapeptides, namely, Boc–X–Val–Asp(OBzl)–Ala–Gly–OPac and Boc–X–Ala–Glu(OBzl)–Leu–Gly–OPac in which X stands for guest amino acid residues, was easily disrupted in CH2Cl2 by increasing amounts of DMSO. The disrupted behaviors were strongly dependent on the nature of the guest amino acid residues and the 20 guest amino acid residues could be classified into six groups. Therefore, we arbitrarily defined SPβ as values of one to six. A method for estimating the β-sheet-structure stability of protected peptides by their arithmetic average  values was proposed, and it was applied to peptide synthesis. The significance of the estimation method in the design of synthetic routes for peptides and proteins is briefly discussed.
An Unusual Property of Benzyl Diphenylphosphinothiite in the Reactions with Various Electrophilic Reagents
Authors: Drozdova Yana A , Burilov Alexander R , Pudovik Michael A , Gainullin Rafinad M , Il’yasov Akhat V
Published: August 2006

Reactions of benzyl diphenylphosphinothiite with a number of electrophiles have been investigated. It has been proved that a kinetically controlled process affords the S-attacked product, which is further converted into the transalkylated product, whereas a thermodynamically controlled process results in the formation of a P-attacked product. An intramolecular S → P migration of the benzyl group is suggested for the reactions with reactive electrophiles.
Reductive Photoallylation of Dimethyl Naphthalenedicarboxylates by Allyltrimethylsilane via a Single Electron Transfer
Authors: Kubo Yasuo , Todani Toshiko , Inoue Takeo , Ando Hisanori , Fujiwara Takaji
Published: August 2006

The photoreaction of dimethyl 1,4-naphthalenedicarboxylate (4) with allyltrimethylsilane (7) in acetonitrile–methanol gave reductive allylation products. The formation of the products is rationalized by a mechanism involving a single electron transfer from 7 to the singlet excited state of 4, an attack of the allyl radical (16) generated by a C–Si bond cleavage in the radical cation of 7 toward the radical anion of 4 to give an anionic intermediate, and protonation of the intermediate. The photoreaction of dimethyl 1,2-naphthalenedicarboxylate (2) with 7 gave reductive allylation products along with a cyclobutane, possibly by the secondary photoreaction of another reductive allylation product. The photoreactions of dimethyl 1,3-, 2,3-, and 2,6-naphthalenedicarboxylates (3, 5, and 6) with 7 gave cyclobutanes, possibly by the photoreactions of reductive allylation products. The values of the free-energy changes (ΔGet) associated with the single-electron transfer from 7 to the singlet excited states of 2—6 and the fluorescence quenching rate constant (kq) support the photochemical single-electron transfer mechanism. The attacking position of 16 toward the radical anions of 2—6 and the position of the protonation of anions resulting from an attack of 16 are discussed on the basis of the values of the spin densities of the radical anions of 2—6 obtained by MNDO calculations and the net atomic charges of the model anions.
Preparation and Molecular Recognition Ability of Mono[6-deoxy-6-(l-tyrosylamino)]-β-cyclodextrin. Formation and Guest Binding Properties of Distorted Cavity Formed Outside the Parent Cyclodextrin
Authors: Takahashi Keiko
Published: August 2006

Mono[6-deoxy-6-(l-tyrosylamino)]-β-cyclodextrin (2) was prepared from N-(benzylcarbonyl)-l-tyrosine dicyclohexylamine salt (Z-Tyr DCHA salt) and mono(6-amino-6-deoxy)-β-cyclodextrin. 2 includes N-dansylphenylalanine enantioselectively (KL/KD = 2.13). From an NMR study, it was suggested that the hydroxyphenyl group attached to 2 was located at the outside of the cavity and that 2 had an expanded and distorted cavity enclosed by the hydroxyphenyl moiety and the parent cyclodextrin wall.
Studies on 5-8 Fused Ring Compounds. VI. Synthesis of Tricyclo[9.3.0.03,7]tetradec-3-ene-5,10-dione and Related Compounds
Authors: Umehara Misao , Honnami Hiromi , Hishida Shinzaburo , Kawata Takashi , Ohba Shigeru , Zen Shonosuke
Published: August 2006

The C5–C8–C5 fused ring compounds (the title compound, 11) constituting the carbon skeletal ring of ophiobolane sesterterpenes have been synthesized from one of the photoadducts, 1-acetoxytricyclo[5.4.0.02,6] undecan-8-one (4a) of cyclopentene and 3-acetoxy-2-cyclohexen-1-one. The photoadduct 4a was converted via bromination and retro-aldol cleavage into 5-bromobicyclo[6.3.0]undecane-2,6-dione (8). The allylation of 8 with allyltributyltin and oxidation of the allyl group with palladium(II) chloride-copper(I) chloride yielded 5-acetonylbicyclo[6.3.0]undecane-2,6-dione (10a). Under basic conditions, the intramolecular cyclization of 10a afforded the title compound 11, and was accompanied by tetracyclo[9.3.01,5.05,8]tetradecane-2,7-dione (12). Under acidic conditions, 10a cyclized to 2-methyl-4,5,6a,7,8,9,9a,10-octahydro-6H-cyclopenta[6,7]cycloocta[1,2-b]furan-6-one (13). The structures of 8, 11, 12, and 13 were determined by X-ray analyses.
Preparation of Polytosylated γ-Cyclodextrins
Authors: Yamamura Hatsuo , Kawase Yoshitaka , Kawai Masao , Butsugan Yasuo
Published: August 2006

Practical preparation of polytosylated γ-cyclodextrins, octakis(6-O-tosyl)-2-O-tosyl-γ-cyclodextrin, octakis(6-O-tosyl)-γ-cyclodextrin, and heptakis(6-O-tosyl)-γ-cyclodextrin, has been established. The procedure involves reaction of γ-cyclodextrin with tosyl chloride in pyridine and column chromatographic separation using silica gel modified with 3-aminopropyl groups.
Regioselective Preparation of Allylgermanes
Authors: Yamaguchi Jun-ichi , Tamada Yoshitake , Takeda Takeshi
Published: August 2006

Allylgermanes were obtained by the reaction of allyl acetates with bis(triethylgermyl)cuprate(I) reagent in high yields. It was found that the present reaction proceeded with high regioselectivity, in which a triethylgermyl group was exclusively introduced to the less substituted side of an allylic system regardless of the original location of acetoxyl group. In the case of the allyl acetates possessing two secondary centers at the both ends of the allylic system, the formal SN2 product was preferentially produced (SN2 : SN2′ = ca. 9 : 1). The desulfurizative germylation of allyl phenyl sulfides utilizing bis(triethylgermyl)cuprate(I) reagent also proceeded to give allylgermanes in good yields with the same regioselectivity.
Photochemical Reactions of 4-Methyl-2-quinolinecarbonitrile with 2,2-Diphenylalkanoic Acids. The Magnetic-Field and Solvent Effects and Reaction Mechanism
Authors: Okumura Yoko , Hata Norisuke
Published: August 2006

Magnetic-field and solvent effects upon the photochemical reactions of 4-methyl-2-quinolinecarbonitrile with achiral carboxylic acids, such as diphenylacetic acid and 2,2-diphenylpropionic acid, were investigated. Consequently, the photoreactions were concluded to proceed by a radical-pair mechanism.
Pyrolysis of Di-n-Propylamine : Chromatographic Characterization of Hexane-Soluble Product and XPS Analysis of Insoluble Carbons
Authors: Murata Kazuhisa , Ushijima Hirobumi , Sugimoto Yoshikazu , Shimada Hiromichi , Imamura Motoyasu , Nishijima Akio
Published: August 2006

Characterizations of soluble and insoluble products prepared from di-n-propylamine by CVD method were carried out using GC-MS and XPS methods in addition to magnetic measurements. GC-MS analysis of hexane-soluble product showed the presence of a series of aromatics with aromatic nitrile and/or heterocyclic compounds. XPS spectra of insoluble carbon product exhibited little difference in the C1s binding energy between plasma-treated and -untreated samples. However, it is found that the amorphous-like carbon content, calculated from the C1 energy loss spectra, is dependent on the plasma power and attains a maximum at 120 W, in good accordance with a plasma dependence of the apparent saturation magnetization of the carbons.
N-Acyl-1-chloro-2,2,2-trifluoroethylamine as a 2,2,2-Trifluoroethylamine-Building Block
Authors: Tanaka Kiyoshi , Ishiguro Yoshiharu , Mitsuhashi Keiryo
Published: August 2006

The reactions of N-benzoyl- and N-acetyl-1-chloro-2,2,2-trifluoroethylamines with various carbon-nucleophiles gave the corresponding 1-substituted N-acyl-2,2,2-trifluoroethylamines in good yields and the efficient reactivity was applied on the synthesis of 2-acylamino-2-trifluoromethylethanol derivative.
Preparation of New Optically Active Germylmethylamine Derivatives
Authors: Terunuma Daiyo , Kizaki Hiroaki , Sato Takashi , Masuo Koujiro , Nohira Hiroyuki
Published: August 2006

New optically active organogermanium compounds, such as [methylphenyl(o-tolyl)-, benzylmethylphenyl-, benzylmethyl(o-tolyl)-, and benzyl(o-methoxyphenyl)methylgermyl]methylamine, were prepared in high optical purity.
Second-Order Optical Nonlinearities of Substituted Stilbenes and the Related Compounds Containing a Trifluoromethyl as the Electron-Withdrawing Group
Authors: Sugiyama Yoshio , Suzuki Yasushi , Mitamura Shuichi , Nishiyama Tatsuo
Published: August 2006

The second-order optical nonlinearities and transparencies of seventeen 4,4′-disubstituted stilbenes and ten related compounds containing a trifluoromethyl group at the para position, as the electron-withdrawing group, were examined. The introduction of a trifluoromethyl group produces a shorter-wavelength shift of the UV-vis absorption spectra without any decrease in the magnitude of the second-order molecular hyperpolarizability (β), as compared with the corresponding nitro-derivatives. The absorption cutoff (λcutoff) of 4-methoxy-4′-trifluoromethylstilbene (1) was observed at 375 nm, which is by ca. 90 nm shorter than that (463 nm) of p-nitroaniline (p-NA); the β value (12.2 × 10−30 esu) of 1, however, is almost equal to that (12.6 × 10−30 esu) of p-NA. The bromo- or methylthio-substituted stilbenes (12 and 16) with a cyano group on the central double bond show SHG activity. The relative intensities of SHG are 3.0 and 1.5, respectively.
Effect of Several Quarternary Ammoniums on the Solvent Extraction of Europium(III) 2-Thenoyltrifluoroacetonate Anionic Complex into Chloroform
Authors: Noro Junji , Sekine Tatsuya
Published: August 2006

The solvent extraction of europium(III) in aqueous 0.1 mol dm−3 sodium chloride or sodium nitrate solutions with 2-thenoyltrifluoroacetone (Htta) into chloroform was measured in the absence and presence of tetraethylammonium, tetrapropylammonium, tetrapentylammonium, or tetradecyldimethylbenzylammonium (base+). The addition of quarternary ammoniums enhanced the extraction, except for tetraethylammonium. This enhancement could be explained in terms of the extraction of the ternary complex, the Eu(tta)4−base+, in addition to the Eu(tta)3 complex. The difference in the enhancement of extraction with a different quarternary ammonium at a certain total concentration was much smaller than that expected from the difference in the size. This could be explained in terms that although the extraction of the anionic complex should be better when the size of the base+ is larger, its concentration in the aqueous phase at equilibrium is lower because it is extracted with the other anions in the aqueous phase better than a smaller base+. It was also found that the formation equilibrium of the ternary complex, the Eu(tta)4−base+, by association of the neutral complex, Eu(tta)3, with the ion-pair, tta−base+, in the organic phase is essentially not affected by the size of the base+.
Substituent Effect on the Enthalpies of Formation of CH/π Complexes of Aromatic π-Bases
Authors: Ehama Ritsuko , Tsushima Masaki , Yuzuri Tomoaki , Suezawa Hiroko , Sakakibara Kazuhisa , Hirota Minoru
Published: August 2006

The formation constants and the enthalpies of formation of CH/π complexes were determined for a series of ternary chloroform/aromatic π-base/carbon tetrachloride (solvent) systems. The enthalpies showed that the interaction is favored by the electron-releasing substituent on the aromatic ring. Electronegative substituents on the CH donor also strengthen the interaction. The fact renders a support on the hydrogen-bond-like nature of the CH/π interaction.
Coordination Environment and Redox Property of Co(II) in the Framework of CoAPO-36 Molecular Sieve
Authors: Nakashiro Katsumi , Ono Yoshio
Published: August 2006

The interaction of water, ammonia, methanol, and tetrahydrofuran molecules with Co(II) ions in CoAPO-36 was examined by means of diffuse reflectance UV-vis spectroscopy. The Co(II) ions in CoAPO-36 are in a tetrahedral environment. Upon adsorption of water or ammonia molecules, the coordination environment of a part of the Co(II) ions changes into octahedral, indicating the direct coordination of water or ammonia molecules to the Co(II) ions. The remainder of the Co(II) ions are slightly modified in their electronic state by the adsorption of these molecules in a close proximity. Adsorption of methanol and tetrahydrofuran molecules also causes a modification of the coordination environment, though they do not directly coordinate to the Co(II) ions.

The redox properties of Co(II) ions in CoAPO-36 were also studied. Heating CoAPO-36 in oxygen at 673 K brings about oxidation of a part of the Co(II) ions into Co(III) ions, which are reduced to Co(II) by a hydrogen-treatment at 573 K. In addition, a reduction of the Co(III) ions occurs upon adsorption of water or ammonia on the oxidized CoAPO-36, even at room temperature. The Co(III) ions react with toluene at room temperature and with methane at 673 K. The oxidation-reduction cycle of the Co ions in CoAPO-36 is also brought about by the adsorption-desorption cycle of NO.
Optical Properties and Molecular Orientation of Aggregates in Langmuir–Blodgett Films of a Long-Chain Spiropyran
Authors: Miyata Akio , Unuma Yutaka , Higashigaki Yoshiyuki
Published: August 2006

The aggregate formation was studied for Langmuir–Blodgett films of a spiropyran 5Me-SP1822 (1′-octadecyl-3′,3′-dimethyl-5′-methyl-6-nitro-8-(docosanoyloxymethyl)spiro[2H-1-benzopyran-2,2′-indoline]). Both a J-aggregate (λmax = 605 nm) and an H-aggregate (λmax = 493 nm) were formed, depending on the nature of the matrix molecule and the annealing temperature. The compound, having a substituent at the 5′-position, seems to prefer H-aggregation to J-aggregation by heat treatment at elevated temperatures. The molecular orientation in these aggregates was evaluated via analysis of the shifts in the first two absorption bands appearing after formation of the aggregates. Slip angles of 20—30° and 70—80° between the chromophore’s transition moment and the center-to-center line of the molecules, were found for the J- and H-aggregates, respectively, and a tilt angle of 20—30° between the chromophore’s plane and the film surface were obtained using the transition density model. These are in line with the results of Fourier-transform infrared (FT-IR) analysis.
Five Types of J-Aggregates in Single-Chain Merocyanine Langmuir Monolayers on an Aqueous Subphase
Authors: Miyata Akio , Heard David , Unuma Yutaka , Higashigaki Yoshiyuki
Published: August 2006

The formation of J-aggregates in Langmuir monolayers of a neat merocyanine dye (3-carboxymethyl-5-[2-(3-octadecyl-2-benzothiazolinyldene)ethylidene]-2-thioxo-4-thiazolidinone) has been examined by measuring the normal incidence absorption spectra. Five types of J-aggregates were found to be formed, depending on the temperature and the concentration and type of cations present in the subphase. The shift in the absorption peak wavelength on the J-aggregates formation is accounted for in terms of the number and the geometrical arrangement of the chromophores in each J-aggregate. The spectral shifts were analyzed numerically using both a point dipole model and a transition density model. These calculations indicate that the five different J-aggregates are linear ones with aggregation numbers ranging from 2 to 6.
Development of New Fast Oxide Ion Conductor and Application for Intermediate Temperature Solid Oxide Fuel Cells
Authors: Ishihara Tatsumi
Published: August 2006

Solid Oxide Fuel Cell (SOFC) show great promise as new power generators with high efficiency. Decreasing the operating temperature is critically required for the further development of SOFC. This review introduces that oxide ion conductivity in the perovskite oxide of LaGaO3, which was found by our group. LaGaO3 doped with La and Mg exhibits the high oxide ion conductivity over a wide PO2 range; the value is higher than that of Y2O3-stabilized ZrO2 by an order of magnitude. When LaGaO3-based oxide was used as the electrolyte of SOFC, the power density could be improved greatly, in particular over the low-temperature range. In this study, the power generating property of LSGM using a thin film of LaGaO3 is also introduced. The maximum power density of the cell using LaGaO3-based oxide is as high as 0.6 W cm−2 at 773 K. This suggests that SOFC could be operable at temperature lower than 773 K.