bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photoinduced Intramolecular Aromatic Nucleophilic Substitution (the Photo-Smiles Rearrangement) in Amino Ethers
Authors: Mutai Kiyoshi , Kobayashi Keiji 
Published: July 2006

Abstract
Intramolecular rearrangement was induced by light as well as base in a homologous series of 1-(p-nitrophenoxy)-ω-anilinoalkanes, p-O2NC6H4O(CH2)nNHPh(n=2–5), yielding N-(p-nitrophenyl)-ω-anilino-1-alkanols, p-O2NC6H4N(Ph)(CH2)nOH. The reaction rate in acetonitrile showed abnormal order, n=4&gt;5&gt;3&gt;2, which was reversed by the addition of triethylamine. The mechanism of this photorearrangement through a radical ion pair and a spiro type Meisenheimer complex was proposed. The anomaly in the reaction rate order was discussed on the basis of this mechanism.
Hydration of Aza-aromatic Aldehydes. II. Solvent Effect on the Equilibrium Constants of the Hydration
Authors: Abe Kazuhisa , Endo Hiroko , Hirota Minoru 
Published: July 2006

Abstract
The equilibrium constants for the hydration reaction of 4-pyridinecarbaldehyde were determined in several solvents by 1H-NMR spectroscopic measurements. The hydration reactions were sensitive to the nature of the solvents. In strong donor solvents such as hexamethylphosphoric triamide, pyridine, and dimethyl sulfoxide, formation of the hydrate is far more favorable than in water or other poor donor solvents. Thus the stabilization of the product by hydrogen bond formation is assumed to favor the reaction. Polarity of the solvent alone does not explain the solvent effect, even if it is supposed to affect the equilibria secondarily.
Effect of Cationic Micelles on the pKa Values of Disulfones
Authors: Yano Yumihiko , Kawada Shuji , Tagaki Waichiro 
Published: July 2006

Abstract
The acid dissociation constants of carbon acids activated by two sulfonyl groups were determined spectrophotometrically in aqueous solution with and without GTAB micelles. The results indicate that a cationic micelle causes larger pKa decrease for more hydrophobic disulfones. Hydrophobic properties of cyclic and acyclic disulfones are discussed.
The Determination of the “Flat-band” Potential of Nitrogen-stabilized n-TiO2 Photoanode
Authors: Hirai Taketsugu , Tari Isao , Ohzuku Tsutomu 
Published: July 2006

Abstract
The differential capacitance (C) and the photocurrent onset voltage (Ep) of nitrogen-stabilized n-TiO2 semiconductor electrodes were measured in buffered Na3PO4 solutions. The C−2 vs. E plots did not show the Mott-Schottky (MS) behavior. In order to explain the nonlinearity in MS plots, the distribution in donor density (Nd) at the solid side and the contribution of the electrical double layer at the solution side to the total capacitance were considered. The characterized flat-band potential (Efb) and the zero-charge potential (Ezc) were defined from the derived equations. The roles of the defined Efb and Ezc in the photocurrent onset voltage (Ep) were also considered, and the reason why Ep differed from Efb was explained using the “Gate” model.
Shock Tube Studies of the Acetylene and Ethylene Pyrolysis by UV Absorption
Authors: Koike Tohru , Morinaga Kihei 
Published: July 2006

Abstract
Absorption measurements at 216 and 230 nm of shock heated C2H2, C2H2+H2, and C2H4 diluted in Ar were made over the temperature range 1800 K to 2600 K at half of atmospheric pressure. Absorptivities were evaluated for C4H2, which is the main product of C2H2 pyrolysis, as well as for C2H2 and C2H4. The relative value of C4H2 absorption was confirmed to decrease with the presence of H2 in accordance with a computer modeling result using a 25-reaction mechanism. The time profile of C4H2 absorption could be modeled well with k=1012.4 cm3 mol−1 s−1 for the reaction H2+C2H=C2H2+H.
Adsorption of d-, l-, and Dl-Phenylalanines at the Mercury–Aqueous Solution Interface
Authors: Kakiuchi Takashi , Senda Mitsugi 
Published: July 2006

Abstract
The adsorption of d-, l-, and Dl-phenylalanines at the mercury-aqueous sodium fluoride solution interface has been studied by measuring differential capacities, potentials of zero charge, pzc, and surface tensions at the pzc. The racemate of phenylalanine showed higher surface activity than the enantiomers. This difference has been interpreted in terms of the intermolecular interactions, orientation and re-orientation of adsorbed molecules at the interface.
Interaction between Aromatics and Zinc Chloride. III. The Dissociation of Triphenylmethane and 9,10-Dihydroanthracene into Ions
Authors: Morita Mikio , Hirosawa Kunio , Sato Toshio , Ouchi Koji 
Published: July 2006

Abstract
Triphenylmethane and 9,10-dihydroanthracene were found to produce colored complexes when placed in contact with molten zinc chloride or with solid zinc chloride pulverized or supported on porous Vycor glass. The triphenylmethane complex gave the same electronic absorption spectrum as that of the triphenylmethyl cation generated by contact with silica-alumina and BF3 on silica. The 9,10-dihydroanthracene complex exhibited the same electronic absorption band as that of the 9-anthracenium ion produced by the reaction of anthracene with concd H2SO4. The reaction of the triphenylmethane complex with deuterium gas provided HD gas and (C6H5)3CD. Similarly, the 9,10-dihydroanthracene complex and deuterium gas produced HD gas and 9,10-dihydroanthracene-9-d. Furthermore, their colored complexes on the supported zinc chloride gave a very weak IR absorption band at about 1720 cm−1, which is interpreted as corresponding to the formation of a Zn–H bond. These observations led us to conclude that triphenylmethane and 9,10-dihydroanthracene dissociate into ions . upon contact with zinc chloride:
(C6H5)3CH+nZnCl2 \ightleftarrows (C6H5)3C+(ZnCl2)n−H
(Remark: Graphics omitted.)
The Optical Absorption Spectra of Ferrocene and Biferrocene Anions Produced in the γ-Ray Irradiation by the Matrix-protection Method
Authors: Ikuta Shigeru , Kira Akira , Imamura Masashi , Motoyama Izumi , Sano Hirotoshi 
Published: July 2006

Abstract
The absorption spectra of the transient species produced through the one-electron reduction of ferrocene and biferrocene were determined by applying a radiation-chemical method in frozen glass matrices. The spectral shapes were assigned to ferrocene- and biferrocene-anionic species on the basis of the experimental results. In the biferrocene anion, the “intervalence transfer” band was observed at about 2050 nm.
Preparation of an Ideal Thin Mercury Film Electrode and Its Electrochemical Property
Authors: Yoshida Zenko 
Published: July 2006

Abstract
In order to get an ideal thin mercury film electrode, the structure of mercury film electrodeposited on foreign metals was investigated with the aid of the thermal-evaporation behavior of mercury and correlated to the electrode properties of the mercury-deposited surfaces. A mercury layer deposited on gold, copper, nickel, or platinum consists of stable mercury compounds with the base metal at their interface and a uniform metallic mercury layer on them. The hydrogen(H)-overpotential at the mercury-coated surface increases with the increase in the amount of mercury deposited. Mercury on molybdenum or stainless steel forms island-like metallic mercury droplets by electrodeposition. The H-overpotential at the surface is identical with that at molybdenum or stainless steel without mercury. Mercury deposited on lead or zinc easily forms a stable amalgam with the base metal, and no metallic mercury is present. The H-overpotential at the surface is slightly less than that at a base metal without mercury. A nickel-based thin mercury film electrode is recommended for such electroanalytical uses as anodic stripping voltammetry.
Metal-semiconductor Transition with Anomalous Thermal Hysteresis Observed in Hexagonal (Ni1−xFex)1−yS, (0≤x≤0.30, 0≤y≤0.035)
Authors: Ohtani Tsukio , Kosuge Koji , Kachi Sukeji 
Published: July 2006

Abstract
The phase relation of (Ni1−xFex)1−yS system was determined by the X-ray powder diffraction method. Fe1−yS can be dissolved in Ni1−yS in ca. 30 at.%. Transition temperature (Tt) was measured mainly by the DSC method. Tt increases with increase in Fe contents. Tt in the forward direction, however, shows a significant increase as high as 50 degrees, when specimens are aged at a temperature below Tt. The reverse transformation is not affected by thermal hystory at all. This is explained by the relaxation process in which the strain energy stored in the low temperature phase is relieved by aging.
Studies on the Uptake of Some Complex Cations of Copper by Molecular Sieves 4A and 5A
Authors: Thantry S S , Iyer K Veeramoni , Ramanathan P S 
Published: July 2006

Abstract
Studies on the uptake of Cu2+ and a few of its complex cations (i.e., [Cu(NH3)4]2+, [Cu(en)]2+, [Cu(en)2]2+, [Cu(pn)]2+, [Cu(pn)2]2+, and [Cu(tea)]2+, where en, pn, and tea represent ethylenediamine, propylenediamine, and triethanolamine respectively) by molecular sieves 4A and 5A were undertaken using batch equilibration procedure. [Cu(pn)]2+, [Cu(en)2]2+, [Cu(pn)2]2+, and [Cu(tea)]2+ showed very little affinity for the zeolite phases, while the uptake of Cu2+ and [Cu(en)]2+ was comparatively higher. [Cu(NH3)4]2+ occupied a position in between these two sets. During the equilibration of [Cu(en)]2+ and [Cu(pn)]2+ some side reactions could be observed leading to the conclusion that the 1:1 complex species underwent disproportionation, generating Cu2+ and an equivalent amount of [Cu(en)2]2+ or [Cu(pn)2]2+. These conclusions drawn from the batch equilibration studies were confirmed by appropriate column experiments.
Exchange Kinetics of Rubidium and Caesium Ions on Pyridinium Tungstoarsenate Exchanger
Authors: Jain Ajay K , Singh Raj P , Agrawal Sushma 
Published: July 2006

Abstract
The Kinetics of exchange of Rb+ and Cs+ has been investigated on pyridinium tungstoarsenate ion exchanger using limited bath technique. The exchange rate was studied as a function of concentration, temperature and particle size of exchanger to determine the slowest step. It was found that Rb+ exchange is particle diffusion controlled whereas Cs+ exchange shows dual behaviour at low concentration level. However, at higher concentrations, particle diffusion controls Cs+ exchange but the rate is concentration dependent. This anomalous behaviour has been explained by assuming that Cs+ exchange approaches closely to a chemical reaction. Thermodynamic parameters of exchange such as effective diffusion coefficient (D), activation energy (Ea) and entropy of activation (ΔS*) were calculated. The D and Ea values were found in the same order as that of ionic size, ΔS* value being positive for Cs+ exchange and negative for Rb+ exchange. A negative ΔS* value is usual but a positive value for Cs+ exchange might be due to dehydration of the cation while passing through the channels of the exchanger. This explanation is in line with that of interaction energy for the exchange of Cs+ on pyridinium tungstoarsenate.
Chemistry at Hydrocarbon–Water Phase Boundaries. Biphase Hydrolysis of Organic Halides
Authors: Ohtani Noritaka , Besse Jacques J , Regen Steven L 
Published: July 2006

Abstract
The kinetics of the biphase hydrolysis of 1-bromoadamantane and 1-phenylethyl chloride in toluene–water and decane–water systems have been investigated. Evidence has been obtained for the first examples of ratelimiting SN1 reactions occurring at a hydrocarbon–water phase boundary, based on (1) the influence of temperature, mild stirring, interfacial area, reaction volume, and pH on the observed first-order rate constants, (2) comparison of absolute rates and activation energies with analogous homogeneous hydrolysis reactions, (3) the temperature dependence of the initial rate of diffusion of tritiated 1-methoxyadamantane from toluene into water, and (4) the initial rate of diffusion of 3H2O into toluene.
The Crystal Structure of Bis(acetylacetonato)platinum(II) Benzene Solvate
Authors: Katoh Mitsunori , Miki Kunio , Kai Yasushi , Tanaka Nobuo , Kasai Nobutami 
Published: July 2006

Abstract
The crystal structure of bis(acetylacetonato)platinum(II) benzene solvate has been determined by means of X-ray diffraction. The geometry around the platinum atom is square-planar. Acetylacetonato ligands are bonded to the Pt atom by the O,O′-chelation, the Pt–O bond lengths being 2.008 (15) and 1.979 (14) Å.
X-Ray Photoelectron Spectra of Adsorbed Methyl Acetoacetate and Coordinated Tartaric Acid, Aspartic Acid and Alanine on the Nickel Surface
Authors: Inoue Yasunobu , Okabe Kiyomi , Yasumori Iwao 
Published: July 2006

Abstract
The adsorption of methyl acetoacetate and the coordination of tartaric acid, aspartic acid, and alanine on the nickel surface were studied by means of X-ray photoelectron spectroscopy. The adsorbed methyl acetoacetate was partly in the enol-form, and the amino acids were coordinated with the surface through COO− and NH2 groups in a manner similar to the corresponding nickel chelate complexes, whereas the interaction of OH groups of tartaric acid with the surface was rather weak.
Characterization of Intramolecular Charge-transfer Transitions. 1-Aryl-1,2,2-tricyanoethylenes and 7-Aryl-7,8,8-tricyanoquinodimethanes
Authors: Aihara Jun-ichi , Araya Kotaro , Matsunaga Yoshio 
Published: July 2006

Abstract
For the title compounds, the energy of the first electronic transition is linearly related to the vertical ionization potential of the aromatic nucleus (e.g., benzene in the case of 1-phenyl-1,2,2-tricyanoethylene). This relationship gives a definite experimental support to the chargetransfer character of the electronic transitions concerned.
Equilibria of Aluminium(III) Complexes with 3,3′-Bis[N,N′-bis(carboxymethyl)aminomethyl]-o-cresolsulfonphthalein
Authors: Murakami Sadaaki , Yoshino Takashi 
Published: July 2006

Abstract
A potentiometric and spectrophotometric study of aluminium(III) complexes with 3,3′-bis[N,N′-bis(carboxymethyl)aminomethyl]-o-cresolsulfonphthalein has been performed. Evidence was found for the formations of 1 : 1 and 2 : 1 (metal : ligand) complexes and it was assumed that protonated and hydroxo complexes are formed in addition to the simple complexes. The formation constants for these complexes were determined and suggestions are made concerning the probable structures of the complexes.
Enolate Anions. IV. The 13C NMR Spectra of Sodium Enolates of Ethyl Phenylacetates in DMSO
Authors: Kiyooka Syun-ichi , Suzuki Kojiro 
Published: July 2006

Abstract
The 13C NMR spectra of the sodium enolates of ethyl (p-substituted phenyl)acetates are presented. The polar interactions between the substituents and the anionic moiety in the sodium enolates are estimated by means of their 13C chemical shifts.
The Copyrolysis of 1,2,3-Trichloropropane and Methanol on Activated Alumina
Authors: Shinoda Kiyonori , Yasuda Kensei 
Published: July 2006

Abstract
The copyrolysis of 1,2,3-trichloropropane and methanol gave 1,2-dichloro-3-methoxypropane as well as dichloropropenes and their derivatives. The formation of 1,2-dichloro-3-methoxypropane is also described.
The Reduction of 2-Benzylidene-3(2H)-benzofuranones with Lithium Aluminium Hydride–Aluminium Chloride
Authors: Kurosawa Kazu , Morita Yasuhiro 
Published: July 2006

Abstract
The reduction of various 2-benzylidene-3(2H)-benzofuranones with lithium aluminium hydride-aluminium chloride in ether gave the corresponding 2-benzylbenzofurans in moderate yields. The reduction of 6-methoxy-2-(4-methoxybenzoyl)benzofuran also yielded 6-methoxy-2-(4-methoxybenzyl)benzofuran.
On Behaviors of a New Chemical Reaction Model Showing Hard Oscillations
Authors: Iwamoto Kazutoshi , Seno Manabu 
Published: July 2006

Abstract
The behavior of a new chemical reaction model was studied and the existence of hard oscillations was confirmed. This chemical reaction model is useful because it is easy to apply to investigations of the behavior of a chemically oscillating system surrounded by membranes or in a well-stirred continuous flow reactor. The latter was discussed relating to the chaotic oscillations due to the Belousov-Zhabotinskii reaction in a well-stirred continuous flow reactor reported by Schmitz et al.
Photodissociation Reaction from Higher Excited Triplet States of [2.2]Paracyclophane
Authors: Ishikawa Shun-ichi , Nakamura Junko , Nagakura Saburo 
Published: July 2006

Abstract
The mechanism of photodissociation of [2.2]paracyclophane in glassy solvent at 77 K was studied. It is concluded that the dissociation of the CH2–CH2 bridge occurs from higher triplet states (Tn) via the lowest triplet state as an intermediate. The efficiency of the reaction depends on the characters of Tn states; high from the locally excited state, and low from the charge-transfer state.
Pressure-induced Phase Transition and Compressive Behavior of Substituted Adamantanes
Authors: Hara Kimihiko , Katou Yoshikazu , Osugi Jiro 
Published: July 2006

Abstract
The compressive behavior of adamantane and its secondary monosubstituted derivatives; adamantanone, 2-methyladamantane, and 2-bromoadamantane was measured at various temperatures in a piston-cylinder apparatus. A first-order solid-solid phase transition was found under pressure in each system. The transition pressures, the equilibrium pressures, the volume changes, and the entropy changes for the transition were determined. The compression data for the low pressure phases were fitted to an equation of the form −ΔV⁄V0=a0+a1P+a2P2. The effects of substituent groups on the entropy changes of the transitions of these molecular crystals were discussed.
Nuclear Magnetic Resonance and Circular Dichroism Spectra of 2-(Aminomethyl)cyclohexylamine Platinum(II) Complexes
Authors: Okamoto Koji , Noji Masahide , Kidani Yoshinori 
Published: July 2006

Abstract
Six-membered platinum(II) complexes of 2-(aminomethyl)cyclohexylamine (=amcha), whose four isomers are (1R,2R)-, (1S,2S)-, (1R,2S)-, and (lS,2R)-amcha, were synthesized. The conformations of [Pt(en)(lS,2S-amcha)]Cl2, [Pt(NH3)2(1S,2R-amcha)]Cl2, [Pt(en)(1R,2R-amcha)]Cl2, and [Pt(NH3)2(1R,2R-amcha)]Cl2 were determined by 1H-NMR, 13C-NMR, and CD spectra. It is proposed that [Pt(en)1S,2S-amcha)]Cl2 and [Pt(NH3)2(1S,2S-amcha)]Cl2 take a fixed chair form with a dihedral angle (Pt–N–C(1)–C(6)) of 180°, while [Pt(en)(1S,2S-amcha)]Cl2 and [Pt(NH3)2(1S,2S-amcha)]Cl2 are interconverting between two chair forms.
A Kinetic Study of the Base Hydrolysis of (2-Aminoethanol)bis-(ethylenediamine)halogenocobalt(III) Complexes
Authors: Ogino Kazuko , Seki Hitoshi 
Published: July 2006

Abstract
The base hydrolysis of cis-[CoX(etaH)(en)2]2+(X=Cl or Br, etaH=2-aminoethanol, en=ethylenediamine) has been studied. The hydrolysis results in the formation of [Co(eta)(en)2]2+ (≈35%) and [Co(OH)(etaH)(en)2]2+ (≈65%) at I=1.0 (KNO3), 25 °C, the product ratio being independent of the pH. The base hydrolysis has also been studied in the presence of sodium azide.
Chiral Mesophases of 12-Hydroxyoctadecanoic Acid in Jelly and in the Solid State. II. A New Type of Mesomorphic Solid State
Authors: Tachibana Taro , Mori Tomoko , Hori Kayako 
Published: July 2006

Abstract
A new type of chiral solid mesophase was obtained by evaporating the solvents from solutions or jellies of chiral 12-hydroxyoctadecanoic acid (12HOA). The mesomorphic solids exhibited some optical properties characteristic of a helicoidal mesophase: (1) spherulitic or Schlieren texture under a polarizing microscope, (2) reflective circular dichroic band, and (3) induced circular dichroic spectra with a single sign due to achiral molecules added to the solid. From the circular dichroic and X-ray studies, it was concluded that the helicoidal mesophase structure exists locally as small domains with a chiral smectic structure within the mesomorphic solids. Microscopic observation revealed that, upon heating, the transition of the mesomorphic solid to the crystalline solid occurred. This process was studied by differential scanning calorimetry. Formation of a variety of helicoidal systems from chiral molecules such as 12HOA and polypeptides was regarded as a phenomenon characteristic of chiral assemblies of amphiphilic molecules.
Kinetics of the Catalytic Decomposition of Hydrogen Iodide in the Magnesium–Iodine Thermochemical Cycle
Authors: Oosawa Yoshinao , Kumagai Toshiya , Mizuta Susumu , Kondo Wakichi , Takemori Yoshio , Fujii Kinjiro 
Published: July 2006

Abstract
The decomposition of hydrogen iodide serves as the hydrogen-evolution step in several thermochemical water-splitting cycles, including the Magnesium–Iodine cycle. A kinetic analysis of the catalytic decomposition of hydrogen iodide has been carried out by the use of a flow method at 500–700 K. The platinum-supported active carbon catalyst (1 wt%) and the active carbon catalyst which have been found effective in the research reported previously, are used as the catalysts. The contact time-conversion relationships for both the catalysts are simulated successfully on the basis of an assumed reaction scheme. The influence of water vapor on the rate and the equilibrium of the decomposition of hydrogen iodide is negligibly small. The inhibition effect of iodine on the rate of the decomposition of hydrogen iodide over the platinum-supported active carbon catalyst is remarkable below 550 K.
Phase Relations in the System PbO–PbSiO3
Authors: Hirota Kazushi , Hasegawa Yasutoshi T 
Published: July 2006

Abstract
Phase relations in the system PbO–PbSiO3 were determined at temperatures above 650 °C. Two new lead silicate phases, Pb5SiO7 and Pb11Si3O17 were found to be stable. The former melts incongruently at 733±1 °C to solid PbO plus liquid, and decomposes below 702±1 °C. The latter melts congruently at 728±1 °C. The compound Pb4SiO6, which has been accepted as stable, could not be confirmed.
The Crystal and Molecular Structure of [trans-1,2-Bis(diphenyl-phosphinamino)cyclohexane](1,5-cyclooctadiene)rhodium(I) Perchlorate Dichloromethane Solvate
Authors: Onuma Ken-ichi , Nakamura Asao 
Published: July 2006

Abstract
The molecular structure of the title compound has been determined from three-dimensional X-ray diffraction data. The crystal belongs to the triclinic system: P\bar1, a=11.488(2), b=18.163(2), c=10.998(2)Å, α=101.70(2), β=118.29(1), γ=85.32(3)°, Z=2. The structure has been refined by block-diagonal least-squares techniques using 3749 non-zero reflections to the final R value of 0.067. The rhodium atom is coordinated in a slightly distorted square-planar geometry by the bisphosphine and the diene ligand, with average Rh–P and Rh–C distances of 2.301(2) and 2.26(1)Å, respectively. The seven-membered chelate ring takes a distorted boat conformation, and the two phenyl groups of diphenylphosphine are arranged in a face-edge manner and those of the other diphenylphosphine are in a helical arrangement like a propeller, viewed from cycloocta diene.
Nonbenzenoid Aromatic Compounds Containing an anti-Aromatic Four-membered Ring. Synthesis and Some Properties of 7-Hydroxy-6H-benzo[3,4]cyclobuta[1,2]cyclohepten-6-one (Benzo[3,4]cyclobuta[1,2-e]tropolone)
Authors: Sato Masaru , Ebine Seiji , Nishijima Kazumi , Tsunetsugu Josuke 
Published: July 2006

Abstract
Biphenylene-2,3-quinone reacts with diazomethane in the presence of boron trifluoride etherate to give 7-hydroxy-6H-benzo[3,4]cyclobuta[1,2]cyclohepten-6-one (5) and its boron difluoride chelate. The latter is convertible quantitatively into the former. Compound 5 has a reduced troponoid character due to fusion of the benzocyclobutadiene ring. Tautomerism of the tropolone ring in 5 seems to be imposed exclusively to one of the tautomers. Protonation of 5 gives a tropylium ion whose positive charge is partially localized. Bromination, nitration, and azo-coupling of 5 give only 7-substituted products. The reaction of 5 with maleic anhydride gives the Diels-Alder adduct in good yield.