bluuebunny/crossref_metadata_2025 huggingface dataset:
Efficient Synthesis of (±)-Solavetivone and (±)-[8,8-2H2]Solavetivone
Authors: Murai Akio , Sato Shingo , Masamune Tadashi
Published: July 2006

An alternative and efficient synthesis of the title compounds is described. The synthesis involves cycloaddition of 2-methylene-4-methoxy-6-methyl-4-cyclohexenylacetonitrile with methyl vinyl ketone as a key step.
Total Synthesis of (±)-Lubimin and (±)-Oxylubimin. I. Synthesis of (±)-15-Norsolavetivone and Related Compounds
Authors: Murai Akio , Sato Shingo , Masamune Tadashi
Published: July 2006

The total synthesis of (±)-15-norsolavetivone, a key intermediate in the synthesis of oxygenated spirovetivane stress metabolites, is described.
Total Synthesis of (±)-Lubimin and (±)-Oxylubimin. II. Transformation of (±)-15-Norsolavetivanes into (±)-Lubimin, (±)-Oxylubimin, and Related Compounds
Authors: Murai Akio , Sato Shingo , Masamune Tadashi
Published: July 2006

The transformation of (±)-15-norsolavetivone and related compounds, into (±)-lubimin and (±)-oxylubimin, which constitutes the total synthesis of these highly oxygenated spirovetivane phytoalexins, is described.
Synthesis of 3-(Substituted Methyl)-2-phenyl-4H-1-benzothiopyran-4-ones
Authors: Nakazumi Hiroyuki , Ueyama Tamio , Sonoda Hikaru , Kitao Teijiro
Published: July 2006

Reaction of 2-phenyl-4H-1-benzothiopyran-4-ones and related compounds with chloromethyl methyl ether and fuming sulfuric acid gave mainly 3-chloromethyl compound, whereas chloromethylation of methoxy-substituted thioflavones took place at another position or gave tris(chloromethyl) compound. 3-(Chloromethyl)thioflavone could be easily converted into various 3-(substituted methyl)thioflavones which showed significant antimicrobial activity against Trichophytons.
Convenient and Improved Synthesis of Tricarbonyl(1,2-dihydropyridine)iron Complex
Authors: Yamaguchi Ryohei , Nakazono Yutaka , Kawanisi Mituyosi
Published: July 2006

(N-Alkoxycarbonyl-1,2-dihydropyridine)tricarbonylirons are conveniently prepared in good yields by photo-irradiation in the presence of excess pentacarbonyliron without any solvent. 13C NMR spectra of the complexes are also described.
Ultrasounds in Synthetic Reactions. II. Convenient Methylenation of Carbonyl Compounds with Zinc–Diiodomethane
Authors: Yamashita Junzo , Inoue Yoshio , Kondo Takashi , Hashimoto Harukichi
Published: July 2006

Ultrasonic irradiation facilitates the methylenation of carbonyl compounds with zinc–diiodomethane reagent in tetrahydrofuran at room temperature.
Single Step Synthesis of 4H-1,4-Benzothiazines
Authors: Gupta Radha Raman , Kalwania Gopal Singh , Kumar Rakesh
Published: July 2006

Single step synthesis of substituted 4H-1,4-benzothiazines is reported by the condensation and oxidative cyclization of substituted 2-aminobenzenethiol with β-dicarbonyl compounds in DMSO. The structures of the synthesized compounds have been confirmed by their elemental analyses and spectral studies.
Kinetic Studies of the Base Equilibrium of Secondary Amines on the Surface of Sodium Dodecyl Sulfate Micelle by Means of the Ultrasonic Absorption Method
Authors: Yamashita Teruyo , Sumino Minako , Yano Hiroshige , Harada Shoji , Yasunaga Tatsuya
Published: July 2006

The ultrasonic relaxation absorption has been measured in aqueous solution of dipentylamine, dihexylamine, dioctylamine, N-methylphenethylamine, and N-ethylbenzylamine in the presence of the sodium dodecyl sulfate(SDS) micelle. The relaxation absorption has been ascribed to the base equilibrium of the amines on the surface of the micelle: RR′NH2++OH−\oversetkf\undersetkb\ightleftharpoonsRR′NH+H2O. The rate constants γ±2kf, kb, the apparent base dissociation constant Kb (=kb⁄γ±2kf), and the volume change in the base equilibrium ΔV were obtained, where γ± is the mean activity coefficient for RR′NH2+ and OH−. The dependence of the rate constants on Kb revealed that, in the detailed mechanism of the base equilibrium of the amines, RR′\underset(I)NH2++OH−\oversetk12\undersetk21\ightleftharpoons(RR′NH\underset(II)2+···OH−)\oversetk23\undersetk32\ightleftharpoonsRR′N\underset(III)H+H2O, the rate-determining step is the proton-transfer process, (II) \ightleftharpoons (III). The pKb values of the secondary amines on the surface of the SDS micelle were 0.94–1.26 smaller than the corresponding values in the aqueous solution, and the micellar effect on pKb was smaller than that of the primary amines. From the standpoint of the micellar effect, the structures of the amines solubilized in the micelle were discussed.
Studies on the Phase Transition near the Melting Point in Acetylferrocene
Authors: Sato Kumiko , Katada Motomi , Sano Hirotoshi , Konno Michiko
Published: July 2006

The entitled compound shows an anomalous temperature dependence of the mean-square amplitude of iron atoms derived from the Lamb-Mössbauer factor near the melting point. To clarify the anomaly, the crystal structure of this compound was determined at room temperature by X-ray diffraction. The crystal is monoclinic with space group P21/c, a=20.595(2), b=5.7909(4), c=18.840(2) Å, β=116.870(7)°, U=2004.4(3) Å3, and Z=8. Weissenberg and oscillation photographs taken at a high temperature lead us to propose a model in which the acetylferrocene molecules rotate around the central iron atoms.
New Transport Phenomenon. Enhanced Transport into a Membrane Due to the Presence of Polyelectrolyte
Authors: Nango Mamoru , Ohta Shozo , Maekawa Masako , Katayama Akira , Kuroki Nobuhiko
Published: July 2006

The transport of chromophore into a membrane in the presence of polyelectrolyte is enhanced much as it is in the presence of simple salt. The presence of polyelectrolyte with different kinds of counterions seem to modify this observed enhancement. The differences in enhanced transport into the cellulose membrane in the presence of polyelectrolyte may suggest a new model for reinterpretation of the transport phenomenon in a biological system.
Electron Paramagnetic Resonance and Optical Detection of Magnetic Resonance Studies of the Lowest Excited Triplet States of Purine, Benzimidazole, and Indazole in Benzoic Acid Host Crystals
Authors: Noda Masayo , Nagaoka Shin-ichi , Hirota Noboru
Published: July 2006

The triplet states (3ππ*) of purine, benzimidazole, and indazole are investigated in benzoic acid crystals by electron paramagnetic resonance (EPR) and optical detection of magnetic resonance (ODMR) techniques. Well resolved phosphorescence spectra were obtained at 4.2 K. The T1 states of purine and benzimidazole are located at 26409 and 26536 cm−1, respectively. The zero field splittings (ZFS) are D=0.1042 cm−1, |E|=0.0608 cm−1 for purine, and D=0.1123 cm−1, |E|=0.0270 cm−1 for benzimidazole. The decay rate constants of the triplet sublevels are determined at 1.5 K and are compared with those of indole. From the angular dependence of the EPR signals, the probable orientations of purine and benzimidazole in benzoic acid hosts are determined. From the observed hyperfine splittings (hfs) spin distribution of the T1 state of purine is estimated. (ρ6=0.20, ρ8=0.27, and ρ2=0.12). The effects of the nitrogen substitution in the pyrole ring of indole on the ZFS and spin distribution are discussed.
Analysis of Rotation-Vibration Bands of Sulfine, (CH2SO), by FT-IR and Microwave Spectroscopy
Authors: Koga Yoshinori , Takeo Harutoshi , Kondo Shigeo , Matsumura Chi , Saeki Shinnosuke
Published: July 2006

The rotation-vibration bands of a transient molecule, sulfine, (methanethial S-oxide), have been observed by FT-IR and analyzed with the aid of microwave data, a part of which has been newly obtained in this study. The band center frequencies for ν5 and ν9 are determined to be 1175.75 cm−1 and 762.07 cm−1, respectively. The good agreement between the observed and simulated band contours clarifies that the origin of these bands is sulfine.
The Synthesis of Green Rust II(FeIII1–FeII2) and Its Spontaneous Transformation into Fe3O4
Authors: Tamaura Yutaka , Yoshida Takashi , Katsura Takashi
Published: July 2006

Conditions for the synthesis of a pure green rust II with a definite chemical composition and its transformation reaction to Fe3O4 under a nitrogen atmosphere were studied. A pure green rust II with the composition of (Fe3+)1(Fe2+)2(SO42−)(OH−)5−2n(O2−)n was obtained by the air oxidation of an aqueous solution containing (0.05 mol dm−3) FeII and (0.3 mol dm−3) SO42− ions at pH 6.8 and 25 °C. This iron composition differs from those estimated previously; therefore, the green rust II synthesized here is designated as green rust II(FeIII1–FeII2). This green rust II is spontaneously transformed into Fe3O4 under a nitrogen atmosphere at 50–75 °C. It has been accepted that green rust II is transformed to Fe3O4 by oxidation. The above evidence suggests that the green rust II can be transformed into Fe3O4 not only by oxidation but also spontaneously without oxidants.
Arylation and 1-Alkenylation on α-Position of Ketones via Tributyltin Enolates Catalyzed by Palladium Complex
Authors: Kosugi Masanori , Hagiwara Isao , Sumiya Takao , Migita Toshihiko
Published: July 2006

The reaction of tributyltin enolates, prepared from tributyltin methoxide and enol acetates in situ, with aryl and 1-alkenyl bromides in the presence of dichlorobis(tri-o-tolylphosphine)palladium was found to give α-aryl and α-(1-alkenyl) ketones, respectively, in good yields with essentially complete retention of the enol acetate regiochemistry.
The Base-Catalyzed Isomerization of the (Iminodiacetato)-(N-methyliminodiacetato)cobaltate(III) and Bis(iminodiacetato)cobaltate(III) Ions
Authors: Kawaguchi Hiroshi , Ama Tomoharu , Yasui Takaji
Published: July 2006

The isomerization reaction among three geometrical isomers of [Co(ida)(mida)]− was studied in a basic aqueous solution. It has been found that the reaction scheme is u-fac\ightleftharpoonsmer\ightleftharpoonss-fac. The rates of these isomerization paths have been determined as the functions of pH and temperature. The rate of the u-fac\ightleftharpoonsmer change is considerably faster than that of the mer\ightleftharpoonss-fac change. The CD loss of the optically active u-fac isomer is caused by the isomerization process of u-fac\ightleftharpoonsmer. The isomerization of the [Co(ida)2]− system has also been measured, and the rate data analysed according to the same scheme as that used for the [Co(ida)(mida)]− system. It is suggested that the isomerizations of the [Co(ida)(mida)]− and [Co(ida)2]− systems proceed through a conjugatebase intermediate.
Synthesis and Cation-Complexing Ability of Oxo Crown Ethers Containing a Ferrocene Nucleus
Authors: Izumi Taeko , Tezuka Takeshi , Yusa Sachiko , Kasahara Akira
Published: July 2006

Fifteen new oxo crown ethers having a ferrocene unit as an integral part of the ring member are reported. These oxo crown ethers were synthesized by the reaction of 1,1′-bis(chloroformyl)ferrocene with oligoethylene glycols or heterocyclic dialcohol compounds such as 2,6-bis(hydroxymethyl)pyridine by the high dilution method. Complexing ability of these compounds with alkali, alkaline earth, and transition metal cations was measured by the solvent extraction method.
Effect of the Base Stacking Association on the Phosphate Ionization of 2′-Deoxyguanosine 5′-Monophosphate
Authors: Hirota Kazumi , Inoue Yoshio , Chûjô Riichirô
Published: July 2006

The concentration dependence of 31P chemical shifts at neutral pH has been measured for 2′-deoxyguanosine 5′-monophosphate and deoxyribose 5-monophosphate. The chemical shifts are sensitive to the variation of concentration, and are affected by the presence or absence of the base. The variations of 31P chemical shifts correspond to those of pKa′ values. The concentration dependence of 31P chemical shift of deoxyribose 5-monophosphate can be explained by the ionic strength change accompanied by the concentration change, whereas that of the nucleotide can not be interpreted with the aid of it alone. The phosphate group of the nucleotide ionizes more readily at higher concentration. There is an additional effect other than ionic strength on the pKa′ eand it is caused by the presence of the base. The appearance of the concentration effect owing to the base is attributable to the base stacking association. The measurements at different temperatures support this conclusion.
Acid-catalyzed Backbone Rearrangement of 5,6-Epoxyalnusanes and Preparation of Daturadiol
Authors: Tori Motoo , Takai Masaki , Matsumoto Yuzo , Moriyama Yoshihiko , Tsuyuki Takahiko , Takahashi Takeyoshi , Ohnishi Hiraku , Itai Akiko , Iitaka Yoichi
Published: July 2006

Epoxidation of alnus-5-en-3β-yl acetate with m-chloroperbenzoic acid gave a 5β,6β-epoxide as a main product together with a 5α,6α-epoxide as a minor product. Treatment of the α-epoxide with BF3·OEt2 afforded a 1(10),5-diene and a mixture of 6α-hydroxy-12- and -18-ene derivatives. The 12-ene was converted into daturadiol (=olean-12-ene-3β,6β-diol).
Branched-chain Sugars. XXXV. The Synthesis of l-Rubranitrose (2,3,6-trideoxy-3-C-methyl-4-O-methyl-3-nitro-l-xylo-hexopyranose)
Authors: Yoshimura Juji , Yasumori Toshio , Kondo Tatsuya , Sato Ken-ichi
Published: July 2006

The title compound was stereoselectively synthesized from methyl 2,6-dideoxy-4-O-methyl-β-l-thero-hexopyranosid-3-ulose (11) through the successive conversions; cyanomesylation, reductive spiro aziridine formation, reductive ring-opening to the methyl-branched amino sugar, oxidation to the corresponding nitro sugar.
Branched-chain Sugars. XXXVI. A New Synthesis of Methyl 4-O-Benzoyl-3-benzoylamino-2,3,6-trideoxy-3-C-methyl-α-l-xylo-hexopyranoside, a Derivative of the Branched-chain Amino Sugar of Antibiotic A35512B
Authors: Yasumori Toshio , Sato Ken-ichi , Hashimoto Hironobu , Yoshimura Juji
Published: July 2006

The title compound was synthesized from methyl 4-O-benzyl-2,6-dideoxy-β-l-threo-hexopyranosid-3-ulose (19) through cyanomesylation, reductive spiro aziridine formation, and reductive ring-opening. When (2-methoxyethoxymethyl) group was used as the protecting group at O-4 of the above intermediate, it could not be removed at the final stage.
Synthesis of a Heat-stable Enterotoxin (STh) Produced by a Human Strain SK-1 of Enterotoxigenic Escherichia coli
Authors: Ikemura Haruo , Yoshimura Shoko , Aimoto Saburo , Shimonishi Yasutsugu , Hara Saburo , Takeda Tae , Takeda Yoshifumi , Miwatani Toshio
Published: July 2006

A peptide with the amino acid sequence proposed for a heat-stable enterotoxin (STh) produced by a human strain SK-1 of enterotoxigenic Escherichia coli was synthesized by a conventional method. Synthetic STh evoked fluid secretion in suckling mice at a dose of 0.8 ng, which is similar to the effective dose of native STh. The fluid secretion was completely inhibited by antisera raised against the native toxin. Furthermore, synthetic STh showed the same 1H-NMR spectrum and heat-stability as native STh.
Sensitization of Polycrystalline SrTiO3 Photoanodes by Lanthanum Doping
Authors: Chang Byong-Tae , Campet Guy , Claverie Jean , Hagenmuller Paul
Published: July 2006

The behaviors of polycrystalline LaxSr1−xTiO3(x≤0.05) electrodes in a photoelectrochemical cell for water decomposition have been investigated in aqueous NaOH electrolyte. The lanthanum substitution for strontium resulted in impressive visible photosensitization of the corresponding electrodes under anodic polarization. This visible photoresponse is based on the relatively deep subband gap states introduced into the forbidden band by lanthanum doping, in analogy with the polished undoped SrTiO3 electrodes reported previously.
The Crystal and Molecular Structure of 3,4-Dimethyl-2,5-diphenyl-3,4-dihydro-3a-thia-1,3,4,6-tetraazapentalene
Authors: Iwasaki Fujiko , Akiba Kin-ya
Published: July 2006

The crystal structure of 3,4-dimethyl-2,5-diphenyl-3,4-dihydro-3a-thia-1,3,4,6-tetraazapentalene has been determined by the X-ray method. The crystals are orthorhombic, space group Pbcn, a=14.533(4), b=9.285(3), c=11.305(2) Å, V=1525.4(6) Å3, Z=4, Dx=1.343 Mg m−3. The final R value is 0.060 for 1107 reflections. The molecule has an exact C2 symmetry, with the central S–C bond coincident with the 2-fold axis of the crystal symmetry. The length of 1.904 Å of the two equivalent S–N bonds indicates that the molecule is a tetraaza analogue of the thiathiophthenes. The length of this S–N bond is 9% longer than the N–S single bond and significantly less than the sum of the van der Waals radii.
Structure and Properties of Thallium(I) Formate Solutions
Authors: Ozutsumi Kazuhiko , Ohtaki Hitoshi , Kusumegi Asao
Published: July 2006

The structure of thallium(I) formate aggregates in concentrated aqueous thallium(I) formate solutions was investigated by the X-ray diffraction method at 25 °C for solutions A (10.77 mol dm−3) and B (3.493 mol dm−3). The former solution had the density of 3.189 g cm−3 and the CH2O⁄CTl mole ratio of 2.59, where Ci represents the total concentration of species i, and was an almost saturated solution at room temperature. From the analysis of the X-ray diffraction data of solution A, thallium(I) formate was found to be present as a tetramer Tl4(O2CH)4. The nearest interatomic distances between thallium(I) and atoms within the formate ions in the tetramer were determined as Tl–O: 2.79(1) Å and Tl···C: 3.33(2) Å. The nonbonding Tl···Tl distances within the aggregate were estimated to be 3.92(1) Å, 4.34(1) Å, and 4.79(1) Å. The Tl–OH2 bond length was also determined to be 3.22(3) Å, which was much larger than the distance expected from the sum of the ionic radius of thallium(I) ion (≈1.4 Å) and size of a water molecule (≈1.4 Å). A comparison of the radial distribution function of solution A with that of solution B, which had the CH2O⁄CTl mole ratio of 13.5, indicated that the aggregate decomposed by dilution. Raman spectra of four different thallium(I) formate aqueous solutions of 3.493 to 10.77 mol dm−3 were measured and the frequencies of the C–O and C=O stretchings of formate ions in the solutions were compared with those of free formate ion. Band shifts of the two frequencies observed for concentrated thallium(I) formate solutions indicated the existence of bridge-type formate ions coordinated to thallium(I) ions, and the result agreed with that observed by the X-ray diffraction analysis. Densities, refractive indices, viscosities and conductivities were measured for thallium(I) formate aqueous solutions with varying concentrations.
Cobalt(III) Complexes with [N6−nXn] type Ligands. IV. The Preparation and Properties of Tetraammine(salicylideneaminato)cobalt(III) and Diamminebis(salicylideneaminato)cobalt(III) Complexes
Authors: Yamamoto Yoshihisa , Toyota Eiko
Published: July 2006

Tetraammine(salicylideneaminato)cobalt(III) complexes, (Remark: Graphics omitted.) (X: Cl, NO3, ClO4, and picrate) and diamminebis(salicylideneaminato)cobalt(III) complexes, (Remark: Graphics omitted.) (X: Cl, NO3, ClO4, and picrate), have been isolated from a reaction mixture of CoCl2·6H2O, 25% aqueous ammonia, 30% H2O2 and salicylaldehyde, and characterized. In the latter complexes, the three isomers of green, orange and brown color have been isolated by column chromatography on alumina and their configurations have been established by their NMR spectra, i.e., the configuration of the green complex is in the trans-trans-trans positions for two ammine ligands, and two phenoxyl groups and two CH=NH groups of the coordinated salicylideneaminato ligands, respectively, while those of the orange and brown complexes are in the trans-cis-cis and cis-cis-trans positions, respectively.
Formation Process of Aluminium Nitride by the Vapor-phase Reaction of Aluminium Trichloride with Ammonia
Authors: Saeki Yuzo , Park Suh Ho , Yajima Akimasa , Akiyama Masayo
Published: July 2006

The reaction products of gaseous AlCl3 with ammonia were AlCl3·3NH3 at 200–500 °C, AlN, AlCl3·3NH3, NH4Cl at 550–900 °C, and AlN, NH4Cl at 1000 °C. AlN is considered to be formed by the reaction of gaseous AlCl3·3NH3, formed by the reaction of gaseous AlCl3 with ammonia, with ammonia above ca.550 °C.
Temperature and Isotope Effects in the Reactions of Phenylcarbene with Acetone
Authors: Tomioka Hideo , Ozaki Yasuji , Nakamura Hiroyuki , Izawa Yasuji
Published: July 2006

Phenylcarbene generated in acetone solution gives oxirane, vinyl ether and 1,3-dioxolane presumably via initial attack of the singlet state on the lone pair electrons of carbonyl oxygen leading to a carbonyl ylide, whereas a C–H insertion product arising from the triplet markedly increases in matrix environments.
The Reaction of Diethyl Acyl Phosphites with α,β-Unsaturated Carbonyl Compounds
Authors: Okamoto Yoshiki , Azuhata Toshio
Published: July 2006

Diethyl acetyl and diethyl benzoyl phosphites reacted with propenal and 3-buten-2-one to give 1,4-addition products respectively. While the reaction of diethyl acetyl phosphite with 2-butenal and 2-methyl- and 3-phenylpropenals gave 1,2-addition products exclusively.
Preliminary Work on Orientation of Nematic Liquid-Crystalline Molecule by Electronic Spectra
Authors: Kobayashi Michio , Kasahara Toshiyuki , Nakajima Keihachiro , Maruyama Kazunori , Tanizaki Yoshie
Published: July 2006

Absorption spectra of a nematic liquid-crystalline molecule (4-butyl-4′-ethoxyazobenzene) were measured in sandwich-type cells with very thin gaps which ranged from 0.2 to 1.0 μm when the cells were empty. The intensity ratio of the first (354 nm) to second (240 nm) band in the liquid state (86 °C) decreases as the state changes into liquid-crystalline (LC) states (70 and 48 °C). According to results of dichroism analysis and MO calculation, the 354 nm and 240 nm bands are due to π-π* transitions polarized along the molecular long and short axes, respectively (with an angle of about 66°to each other). This finding coupled with an assumption that the molecular orientation of the liquid state is isotropic, allows a qualitative discussion on the orientation of molecule in the LC state, leading to a conclusion that the molecular long axis against the cell surface takes two kinds of orientation with respective tendencies to be parallel in the interface region and perpendicular in the bulk region.
Reversing-Pulse Electric Birefringence of Poly(γ-methyl l-glutamate) in Hexafluoro-2-propanol
Authors: Ueda Kazuyoshi
Published: July 2006

Reversing-pulse electric birefringence (RPEB) signals of poly(γ-methyl l-glutamate) (PMLG) were measured, for the first time, in hexafluoro-2-propanol at 25 °C and at 535 nm. Quantitative analyses were carried out on the steady-state birefringence and the field-free decay time (<τ>EB) in the wide field strength region and also on the rise, reverse, and decay portions in the low field strength region by taking into account the continuous molecular length distribution of a fractionated PMLG sample. The weight-average length (lw), permanent dipole moment (μw), polarizability anisotropy (Δαw), and the degree of polydispersity (lw/ln) were evaluated by two procedures: one from the analysis of the reverse-transient portion and the other from the field-free decay portion of RPEB signals. These two sets of the parameters should be identical with each other, if the electrooptical and hydrodynamic properties of PMLG do not change during the field-on and field-off processes. However, the length of the PMLG helix is shorter by about 18% in the presence of an electric field than that in the absence of the field. In order to explain this discrepancy, a new concept of reversible conformational transition under the external electric field is introduced.
The Two-phase Oxidation of Some Aromatic Compounds with Cerium Ammonium Nitrate in the Presence of Surfactants
Authors: Skr\.{z}ewski Jacek , Cichacz Ewa
Published: July 2006

The two-phase oxidations of 3,6-dimethoxydurene and xylenes in cyclohexane solutions with the aqueous solution of cerium ammonium nitrate were carried out in the presence of cationic, nonionic, and anionic surfactants. Both cationic (ammonium salt) and nonionic (Dipodand) surfactants inhibited the reaction. The anionic surfactant (sodium dodecyl sulfate, SDS) catalyzed these oxidations. From the product distribution it was concluded that the catalytic action of SDS is due to the binding of aromatic compounds and the Ce(IV) ions to the surface of the SDS micelles. The micellar oxidant has the high oxidation potential which should allow to oxidize the comparatively nonreactive substrates.
Molybdenum Peroxo Complex. Structure and Thermal Behavior
Authors: Segawa Koichi , Ooga Katsumi , Kurusu Yasuhiko
Published: July 2006

The molybdenum peroxide (Mo-y) prepared by oxidation of molybdenum metal with hydrogen peroxide has been studied to determine its structure and thermal behavior. Temperature programmed decomposition has been used to study the thermal stability of Mo-y. Two distinct peaks, I and II, of decomposition processes are discernible in Mo-y. Peak I corresponds to the elimination of water of crystallization and peak II to the decomposition of a peroxide ion of Mo-y. IR and UV examinations support the results of the thermal analysis. The IR band at 931 cm−1 and the UV band at 381 nm show the same thermal behavior. Both bands are attributable to the peroxide ion of Mo-y. Spectroscopic studies show that Mo-y has the tetrahedral coordination derived from the single molybdenum complex, which has double bond oxygens attached to Mo atom and has a symmetric type of peroxide ion with one water of crystallization.
Preparation of Ni- or Pt-Containing Cyclic Esters by Oxidative Addition of Cyclic Carboxylic Anhydrides and Their Properties
Authors: Sano Kenji , Yamamoto Takakazu , Yamamoto Akio
Published: July 2006

Metal containing cyclic ester complexes, (Remark: Graphics omitted.)(L=1,2-bis(diphenylphosphino)ethane (dpe) or 2,2′-bipyridine (bpy); R1, R2=H or CH3) and (Remark: Graphics omitted.) (L=tricyclohexylphosphine (PCy3) or dpe; n=1 or 2), have been prepared by oxidative addition of cyclic carboxylic anhydrides to zero-valent metal complexes. These complexes have been characterized by elemental analysis and spectroscopies (IR as well as 1H-, 13C{1H}-, and 31P{1H}-NMR) and chemical reactivities. Rate of the oxidative addition of succinic anhydride to Ni(bpy)(cod) (cod=1,5-cyclooctadiene) is expressed by a second order rate equation, R=k[Ni(bpy)(cod)][succinic anhydride], and temperature dependence of k gives the activation energy of 68 kJ mol−1. The reaction of methylsuccinic anhydride with Ni(cod)2 in the presence of tertiary phosphine or bpy affords two isomers, (Remark: Graphics omitted.) and (Remark: Graphics omitted.), corresponding to two modes of C–O bond cleavage in methylsuccinic anhydride promoted by Ni; dependence of the ratio between the two isomers on the kind of ligand added and reaction conditions has been examined.
The Crystal Structure of 4-Cyanoimino-3-methoxymethylperhydro-1,3,5-oxadiazine
Authors: Ebisuno Toichi , Takimoto Michiaki , Shiba Ryuichi
Published: July 2006

The structure of 4-cyanoimino-3-methoxymethylperhydro-1,3,5-oxadiazine in the crystalline state was determined by X-ray crystal analysis. The crystal is triclinic, space group P\={l}, a=10.307(3), b=8.166(2), c=5.082(1) Å, α=97.34(2), β=91.98(2), γ=107.13(2)°, Z=2. The final R value was 0.061 for 1651 reflections.
Preparation and Characterization of [S-(2-Aminoethyl)-l-homocysteinato]cobalt(III) Complexes with Bidentate Ligands
Authors: Suzuki Masutaro , Arisato Osamu , Okamoto Ken-ichi , Einaga Hisahiko , Hidaka Jinsai
Published: July 2006

Three kinds of cobalt(III) complexes with S-(2-aminoethyl)-l-homocysteinate (l-aehc) and a bidentate ligand (glycinate, oxalate, and ethylenediamine) were prepared and chromatographically separated into the quasi-enantiomeric isomers: ΔL-trans(O)·mer(N)-R(S), ΔL-cis(O)·mer(N)-R(S), ΛL-cis(O)·mer(N)-S(S), and ΛL-cis(O)·fac(N)-S(S) for the glycinato complex, ΔL-trans(N)-R(S) and ΛL-cis(N)-S(S) for the oxalato one, and ΔL-R(S) and ΛL-S(S) for the ethylenediamine one. These isomers were characterized from their electronic absorption, CD, and 13C NMR spectra. The conformations of the six-membered N–S chelate ring in the l-aehc, of the chair for ΔL-R(S) and of the chair or skew-boat for ΛL-S(S), were suggested on the basis of the 13C NMR spectra. The CD spectra of the isomers are discussed in relation to their geometrical and absolute configurations.
Formose Reactions. XXI. A Selective Formation of Dihydroxyacetone in the Formose Reaction in N,N-Dimethylformamide
Authors: Shigemasa Yoshihiro , Sasaki Yoshihiro , Ueda Nasuo , Nakashima Ruka
Published: July 2006

Dihydroxyacetone (DHA) was obtained in good yield from the selective formose reaction which was conducted with 2-(dimethylamino)ethanol and vitamin B1 in N,N-dimethylformamide (DMF). The major products were isolated from the formose and identified as dihydroxyacetone and 2-(1,2-dihydroxyethyl)-5-(2-hydroxyethyl)-4-methylthiazole by spectral data. Vitamin B1 suppressed the vaporization of formaldehyde from the reaction solution. Irrespective of the 2-(dimethylamino)ethanol concentration (above 0.1 M (1M=1 mol dm−3)), the maximum yield of DHA was 80–90 glc% at 1.0 M formaldehyde concentration, when the formaldehyde consumption was above 90%. Above 3.0 M formaldehyde concentration, selective formation of DHA (above 80 glc%) was obtained at the early stage of the reaction. The scheme for the formation of DHA in the formose reaction in the presence of vitamin B1 was also proposed.
Selective Condensation of [3-(Alkylthio)allyl]titanium Reagent with Carbonyl Compounds
Authors: Furuta Kyoji , Ikeda Yoshihiko , Meguriya Noriyuki , Ikeda Nobuo , Yamamoto Hisashi
Published: July 2006

[3-(Ethylthio)allyl]titanium reagent generated easily from allyl ethyl sulfides condensed with aldehydes to give erythro-β-hydroxy sulfides in highly regio- and stereoselective manner. In contrast, crotyl ethyl sulfide reacted with aldehydes affording δ-hydroxy vinyl sulfide exclusively. The substitution pattern of the starting sulfide can have a pronounced effect on the selectivity in this condensation reaction. erythro-β-Hydroxy sulfide obtained was transformed stereoselectively to the trans-vinyloxirane or 1,3-alkadiene.
Ab Initio Self-consistent Field MO Calculations of Ethanethiol and Ethanol
Authors: Ohsaku Masaru , Ichiishi Takehiro , Imamura Akira , Hayashi Michiro
Published: July 2006

Ab initio self-consistent field MO calculations were performed on EtSH and EtOH, and the optimized geometries were obtained by the use of the STO-3G and STO-3G* basis sets. It was found that ab initio MO calculations reproduced the observed geometries of these molecules sufficiently well. The variation in the observed bond angle, α(CCX) (X=S and O), from the trans to the gauche rotamers, which was observed by means of microwave spectroscopy, was very reasonably reproduced from the results of these calculations. The total energy calculated gives a reasonable explanation of the stability between the rotational isomers.
1H NMR and Differential Scanning Calorimetry Studies on Molecular Motions and Phase Transitions in Butylammonium Bromide
Authors: Fukada Shin-ichi , Ikeda Ryuichi , Nakamura Daiyu
Published: July 2006

The temperature dependences of the 1H NMR spin-lattice relaxation time and of the second moment of 1H NMR absorptions in the temperature ranges of 90–400 K and 77–456 K, respectively, were studied for butylammonium bromide and its N-deuterated analog. There are three known crystalline phases in butylammonium bromide as a result of two phase transitions which are confirmed by the present differential thermal analysis (DTA) experiments. The transition temperatures determined in this study are 200 and 249 K for butylammonium bromide. In the low temperature phase of this salt, CH3 groups perform the C3 reorientation with a relatively low activation energy of 11.0 kJ mol−1. The asymmetric T1 curves observed suggest the existence of some kind of disorder in the crystal structure of this phase. In the intermediate phase, the C3 reorientation of NH3+ groups and the 180 ° flip motion of butylammonium chains are activated with the activation energies of 23 and 14 kJ mol−1, respectively. The present NMR results for the high temperature phase indicate the occurrence of the conformational melting of the cation chains. The mechanism of the phase transitions is discussed.
Cadmium(II)-, Magnesium(II)-, and Zinc(II)-bearing Ferrites Formed from γ-FeOOH at Various Reaction pH’s
Authors: Ito Kazuo , Tamaura Yutaka , Katsura Takashi
Published: July 2006

The reaction of γ-FeOOH with the metal (Cd(II), Mg(II), or Zn(II)) and Fe(II) ions in solution gave the metal ion-bearing ferrites without oxidation. The ferrites obtained were the stoichiometric Mg(II)- and Zn(II)-bearing ferrites [Mg0.27Fe2.73O4.00 (pH 10.6), Zn0.38Fe2.61O4.00 (pH 10.5)] at pH 7.5–11.4, and the nonstoichiometric Cd(II)-bearing ferrites [Cd0.19Fe2.68O4.00 (pH 10.2)] at pH 7.5–10.5 (25 °C). The Cd(II)- and Mg(II)-ion content in the ferrites increases with an increase in the reaction pH, but the Zn(II)-ion content is almost constant at pH 7.5–10.5. This pH dependence of the metal-ion content in the ferrites agrees with that of the fractional adsorption of these metals on γ-FeOOH. This suggests that only the adsorbed metal ions are incorporated into the ferrites. The pH dependence of these metal-ion contents in the air-oxidation reaction is also similar to that in the transformation reaction from γ-FeOOH. This transformation reaction seems to be one process in the air-oxidation reaction.
Ylide-Metal Complexes. IX. The Preparation and Properties of Metal (Be, Mg, Zn, Cd, Hg, Al, In, Sn, and Pb) Complexes with Methylenetriphenylarsorane
Authors: Yamamoto Yoshihisa
Published: July 2006

The reactions of methylenetriphenylarsorane, (C6H5)3As=CH2 (L), with ZnCl2 or HgCl2 in the mole ratio 2:1 yield new monomeric compounds of bis(methylenetriphenylarsorane)metal dichloride, [(C6H5)3AsCH2–M–CH2As(C6H5)3]Cl2. The reactions of L with BeCl2 or MgCl2 in the mole ratio 2:2 yield dimeric trigonal compounds of di-μ-chloro-bis[(methylenetriphenylarsorane)metal] dichloride, (Remark: Graphics omitted.). The reactions of L with AlCl3 or InCl3 in the mole ratio 4:2 yield dimeric tetrahedral compounds of di-μ-chloro-bis[bis(methylenetriphenylarsorane)metal] tetrachloride, (Remark: Graphics omitted.). The reactions of L with (C6H5)3MCl (M: Sn and Pb) in the mole ratio 1:1 yield new monomeric compounds of (methylenetriphenylarsorane)triphenyl-metal chloride, [(C6H5)3AsCH2–M(C6H5)3]Cl. They are thermally stable complexes and their properties are compared with those of the methylenetriphenylphosphorane metal compounds.
Solvent Effects on Dimerization of Copper(II) Decanoate in Ketone Solvents
Authors: Yamada Hiromichi , Takahashi Kaoru , Fujii Yukio , Mizuta Masateru
Published: July 2006

The extraction of copper(II) with decanoic acid in some ketone solvents was carried out at 25 °C and at 0.1 mol/dm3 (NaClO4) aqueous ionic strength. Organic solvents used are 2-pentanone, 3-pentanone, 2-hexanone, 4-methyl-2-pentanone, 5-methyl-2-hexanone, and 2-octanone. For all solvents, the extracted species are CuA2, CuA2HA, Cu2A4, and Cu2A4(HA)2 (HA: decanoic acid). The dimerization and adduct formation of copper(II) decanoates in each organic phase can be formulated as:

CuA2+HA\oversetKad,monomer\ightleftharpoonsCuA2HA,

Cu2A4+2HA\oversetβad,dimer\ightleftharpoonsCu2A4(HA)2,

2CuA2\oversetKdim–1\ightleftharpoonsCu2A4,

2CuA2HA\oversetKdim–2\ightleftharpoonsCu2A4(HA)2.

The solvent effects on the dimerization of copper(II) decanoate can be interpreted in terms of the regular solution theory. It was proved that the number of solvent molecules liberated in the formation of the dimeric copper(II) decanoate in ketones was less than that in alcohols.
The Synthesis and Thermal Decomposition of Calcium Phosphoramidate
Authors: Watanabe Makoto , Morii Yoshio , Sato Shoji
Published: July 2006

Calcium phosphoramidate monohydrate was made by adding an aqueous calcium chloride solution to an aqueous potassium hydrogenphosphoramidate solution at pH 9.0–9.5 below 5 °C. The product was stable at room temperature, but it was decomposed by heating. When the product was heated at 150 °C in air, the phosphoramidate decomposed to produce anhydrous calcium phosphoramide and also ortho- and diphosphates. The elimination of ammonia from amino groups to form a P–N(H)–P linkage was not observed at this temperature. The phosphoramidate decomposed in air to form ortho-, imidodi-, di-, and a small amount of higher polyphosphates at a temperature higher than 150 °C. Imidodiphosphate was decomposed to diphosphate by moisture in air. β-Calcium diphosphate was formed by heating the phosphoramidate at a temperature higher than 750 °C in air. When the phosphoramidate was heated in dried N2, it showed the same thermal reaction as that in air below 250 °C, while the amount of imidodiphosphate in the thermal product was larger than that in air at a temperature higher than 400 °C.
The Syntheses, Properties, and Crystal and Molecular Structures of Bis(benzamide)tris(O,O′-diisopropyl dithiophosphato)neodymium(III), [Nd{(C3H7O)2PS2}3(C6H5CONH2)2], and Its Isomorphous Complexes of La, Ce, Pr, Sm, Eu, and Gd
Authors: Nakamura Reiko , Nagai Kiyofumi , Shimoi Mamoru , Ouchi Akira
Published: July 2006

The new complexes indicated in the title have been synthesized, and the crystal and molecular structure of the neodymium(III) complex has been determined by the X-ray diffraction method. The crystal is monoclinic, with the space group C2/c, Z=16, a=28.887(4), b=28.913(5), c=24.814(5)Å, β=106.72(1)°. The final R value for 7761 reflections is 0.066. The central neodymium(III) atom of the complex is octa-coordinated and is in a dodecahedron geometry; three O,O′-diisopropyl dithiophosphato ligands, chelating by both of the sulfur atoms, span the two m edges of a trapezium as well as one a edge of the other trapezium, and two oxygen atoms of both the benzamide ligate at both tips of the base edge of the latter trapezium. The solid and the acetonitrile solution of the europium(III) complex are orange in color, and they show a charge-transfer band in their near-ultraviolet absorption spectra.
Theory of Time-resolved Photon Absorption by Molecules after Radiationless Transition. Application to Benzene after S2\ightsquigarrowS0
Authors: Fujimura Yuichi , Arai Minoru , Nakashima Nobuaki , Yoshihara Keitaro
Published: July 2006

Expressions for the intensity of the time-resolved absorption (TRA) by molecules after radiationless transition have been derived. It is assumed that a non-equilibrium vibronic distribution is realized after the radiationless transition and relaxes to the equilibrium one. Two types of non-equilibrium distributions, Poisson distribution and canonical distribution with temperature higher than that of the heat bath are taken into account. The theory developed is applied to the TRA spectra (S3←S0) of benzene after the internal conversion S2\ightsquigarrowS0 (N. Nakashima and K. Yoshihara, J. Chem. Phys. 79, 2727, (1983)). It is shown that the expression for the intensity in the Sulzer-Wieland model is involved in the expression derived using the canonical distribution.
Studies of the Interaction of Isocyanides with Transition-metal Complexes. XXVI. The Preparation of Octakis(aryl isocyanide)dirhodium
Authors: Yamamoto Yasuhiro , Yamazaki Hiroshi
Published: July 2006

The treatment of a mixture of [Rh(cod)Cl]2 and aryl isocyanide with sodium amalgam afforded octakis(aryl isocyanide)dirhodium. A structure with two bridging and six terminal isocyanide ligands was deduced from the IR spectrum in comparison with that of the known cobalt analog. The temperature-dependent 1H NMR spectrum of this complex suggested harder intramolecular and easier intermolecular ligand exchanges than those of the corresponding cobalt analog.
400 MHz Proton Nuclear Magnetic Resonance Study of Magydardienediol, a Diterpene from Magydaris panacifolia
Authors: Nagano Hajime , Tori Motoo , Shiota Michio , de Pascual Teresa Joaquín
Published: July 2006

A detailed analysis of the 400 MHz 1H-NMR spectrum of magydardienediol (1), a diterpene isolated from Magydaris panacifolia (Vahl) Lange, has been performed by use of a combination of proton homonuclear spin decoupling, COSY, NOE difference, and NOESY techniques. This 1H-NMR spectral analysis, in conjunction with the mass spectral analysis of some derivatives of 1, revealed that the structure of 1 should be revised to t-6-hydroxymethyl-1,t-3-dimethyl-t-2-(3-methyl-2-butenyl)-3-(4-methyl-3-pentenyl)-γ-1-cyclohexanol.
A Rapid Pulse Nebulization Technique for Flame Atomic Fluorescence Spectrometry
Authors: Ekanem Edet Joseph
Published: July 2006

A simple and rapid pulse nebulization technique in which 200 μl sample volume is injected and aspirated into a flame-nebulizer is described for the determination of cadmium by line source atomic fluorescence spectrometry (AFS) and for magnesium and other elements by continuum source AFS. The volume of blood and serum samples required for replicate analysis is reduced below 1 ml; nebulizer clogging by heavy sample matrices is reduced; small volumes of rare samples can be analysed in the same batch as bulky samples using this technique. The technique is also applicable to flame AES which can also be performed with the instrumentation used in this work.
The Self-condensation of Methyl Iodide. The Intermediacy of Methylium Ions in C–C Bond Formation
Authors: Ono Yoshio , Kogai Masahiko
Published: July 2006

Hydrocarbons are formed by the reaction of methyl iodide vapor with solid-silver dodecatungstophosphate. The self-condensation is plausibly initiated by the attack of the methylium ion on the C–H bond of methyl iodide. It is suggested that the methylium ion is a key intermediate also in the conversion of methanol into hydrocarbons.
Theoretical Interpretation of the Mössbauer Parameter in [1]Ferrocenophanes
Authors: Ikuta Shigeru , Motoyama Izumi , Sano Hirotoshi
Published: July 2006

The smaller quadrupole splitting values in [1]ferrocenophanes than that in ferrocene were accounted for by assuming a lesser quantity of the nuclear part in the electric-field gradient at the iron nucleus; smaller quadrupole splitting could not be explained by the electron distribution among Fe 3d orbitals.
Solvent Effects on the n→π* Absorption Intensities of Acetone and Cyclopentanone
Authors: Shibuya Tai-ichi
Published: July 2006

The recently proposed theory [J. Chem.  Phys.  78, 5175 (1983)] for the solvent effect on the absorption intensity has been successfully applied to the n→π* bands of acetone and cyclopentanone in various organic solvents observed by Nakashima, et al. [Bull.  Chem.  Soc.  Jpn.  55, 415 (1982)].
Fermi Resonance Effects on the ν1 Raman Bands of Liquid CH2Br2 and CH3Br
Authors: Fujita Kazuyoshi , Fukuda Takuya , Fukushi Kohji , Kimura Masao
Published: July 2006

Applying Fermi-resonance-band-shape functions to the isotropic Raman band profiles of liquid CH2Br2 and CH3Br in the ν1 region, the peak frequencies, band-widths, and coupling constants of the ν1 and combination vibrations have been determined.
On the Crystal-Structure Change of Manganese Dioxide (CMD) during the Acid Digestion in MnSO4-H2SO4 System
Authors: Ohzuku Tsutomu , Hirai Taketsugu
Published: July 2006

The wet method to convert chemically prepared manganese dioxides (MnO2s) into β-MnO2 was reported. Chemically prepared MnO2S, such as I. C. Sample Nos. 5, 8, 11, and 12, were converted into β-MnO2 by using a proton-assisted rearrangement reaction in a boiling dil. H2SO4 solution containing Mn2+ ion at 100±10°C.
A Convenient Method for the Preparation of Conjugated Olefins from Allylic Acetates and Aldehydes. Synthesis of Pellitorine
Authors: Tsukahara Yuhko , Kinoshita Hideki , Inomata Katsuhiko , Kotake Hiroshi
Published: July 2006

A variety of allylic acetates were treated with sodium bromide and triphenylphosphine in the presence of 5 mol% of [Pd(PPh3)4] to give the phosphonium salts, which were converted to the ylids in situ and allowed to react with various aldehydes to afford the corresponding conjugated olefins in good yields. Furthermore, this procedure was applied to the synthesis of an insecticidal substance, Pellitorine.
Second-order Rate Constants for the Decomposition of Methyl Iodide in Different Rare Gases
Authors: Saito Ko , Tahara Hiroyuki , Murakami Ichiro
Published: July 2006

The thermal gas-phase decompostion of methyl iodide was studied in He and Kr over the temperature range of 1025–1520 K and the total-density range of (0.96–2.3)×10−5 mol cm−3. The results showed that, at high temperatures, these inert gases act as “weak colliders.” From the low-pressure limit rate constants, the relative values of the collision efficiency, βc(M), were evaluted as;

βc(He):βc(Ar):βc(Kr)=1.7:1.0:0.46

by connecting them with the previously reported data for an Ar mixture.
Dynamic NMR as a Nondestructive Method for the Determination of Rates of Dissociation. VIII. Proton Affinities of Anions Derived from Strong Acids in Chloroform
Authors: Oki Michinori , Ohira Manabu
Published: July 2006

Dynamic NMR study of topomerization by dissociation of N,N-dibenzylanilinium salt was applied to the determination of proton affinities of anions derived from strong acids in chloroform-d. The total line shape analysis of the benzylic proton signals gave the following order of proton affinity:

Cl−>p-CH3C6H4SO3−>CH3SO3−>Br−.
The Crystal Structure of 13H-Dibenz[a,de]anthracen-13-one
Authors: Oonishi Isao , Fujisawa Shoji , Aoki Junji , Ohashi Yuji , Sasada Yoshio
Published: July 2006

Crystals of the title compound, C21H12O, are orthorhombic, belong to the space group Pn21a, have lattice constants of a=14.227(3), b=15.551(4), c=12.436(3) Å, and also have Z=8. The structure was determined using the direct method and was refined by using a full-matrix least-squares method to an R value of 0.106 on the basis of 1964 reflections with |Fo|>3σ(|Fo|). The molecules is slightly distorted from the planar conformation owing to a steric repulsion between the O and H atoms. The molecules are stacked in pairs and two pairs with different overlapping modes are randomly arranged with different populations. It has been qualitatively explained that the populations of disordered molecules reflect the difference in their lattice energies.
Thermochemical Studies on 3- and 4-Nitroanilines and Their N,N-Dimethyl Derivatives
Authors: Furukawa Junichi , Murata Shigeo , Sakiyama Minoru , Seki Syûzô
Published: July 2006

Standard enthalpies of combustion and of sublimation at 298.15 K were determined and standard enthalpies of formation in crystalline and gaseous states were derived for N,N-dimethyl-3- and N,N-dimethyl-4-nitroanilines by calorimetric measurements. Stabilization energies due to the intramolecular interaction between substituents were evaluated and discussed for these compounds and 3- and 4-nitroanilines.
The Dehydration of Ketohexoses into 5-Chloromethyl-2-furaldehyde. The Isolation of Diketohexose Dianhydrides
Authors: Hamada Kazuhiko , Yoshihara Hiroshi , Suzukamo Gohfu , Hiroaki Osamu
Published: July 2006

The isolation of diketohexose dianhydrides, produced during the dehydration of d(−)-fructose and l(−)-sorbose with concentrated hydrochloric acid, in a mixture containing water, an organic solvent and a catalytic amount of a surface-active agent is described.
The Formation and Solubility of Various Lead(II) Compounds Prepared by the Hydrolysis of Lead(II) Nitrate
Authors: Narita Eiichi , Okayasu Hiroshi , Naito Hiroyuki
Published: July 2006

Lead(II) nitrate was hydrolyzed by mixing with sodium hydroxide solutions at 25 and 50 °C. Four kinds of lead(II) hydroxide nitrates and two kinds of lead(II) oxides (massicot and litharge) were formed, depending on the pH, temperature, lead(II) nitrate concentration, and aging time of the suspension. The solubility of the products was also measured.