bluuebunny/crossref_metadata_2025_split huggingface dataset:
Kinetic Parameters of Thermal Dehydration and Decomposition of Zeise’s Salt Hydrates
Authors: Sen\={o} Manabu , Iwamoto Kazutoshi , Asahara Teruzo 
Published: July 2006

Abstract
The kinetic parameters of the dehydration of Zeise’s salt hydrates, K[PtCl3 (olefin)]·H2O, (olefin; CH2=CH2, CH3CH=CH2, C2H5CH=CH2, n-C3H7CH=CH2 and n-C4H9CH=CH2) and the thermal decomposition of Zeise’s dimers were determined by using DTA and TG. By comparing the kinetic parameters with the data of IR and the enthalpy change of dehydration, it was shown that the important factor in determining the kinetic behavior of the dehydration is an extent of deformation of lattice at the transition state. Similarly, it was suggested that the bulkiness of ligand olefin is an important factor in governing the kinetics of the thermal decomposition reactions.
Conductivity, Emf, and Spectrophotometric Study on the Participation of Na+ and Cl− into Acridine Orange-Poly(α,l-Glutamic Acid) Complex
Authors: Watanabe Fumiyuki 
Published: July 2006

Abstract
Conductivity, emf and spectroscopic investigations were made for the dimerization process of Acridine Orange (AO) and for the complex formation of AO with poly(α,l-glutamic acid) (PLG) in water. The increase of the dimer species of AO by adding the neutral salt was quantitatively explained, taking the ionic strength into account. From the emf measurements, the inclusions of Cl− into PLG–AO complex were concluded to be negligible, whereas Na+ was included into this complex to a fairly appreciable extent. The association of Na+ with carboxylate groups in the PLG–AO complex was described on the basis of the ordinary law of mass actions. The association constant Ki was unaffected by the presence of AO even in the helical region of PLG. These results strongly support Schwarz’s theory on cooperative binding.
Coulomb Interactions and Optically-active Vibrations of Calcite-type Carbonates
Authors: Yamamoto Akio 
Published: July 2006

Abstract
Polarizable-ion model calculations are made for optically-active vibrations of five carbonates with calcite structures: calcite, magnesite, dolomite, rhodochrosite, and smithsonite. The fit to the experimental TO-LO splittings of the internal modes is found to be greatly improved by the introduction of ionic polarizabilities. It is also ascertained that the electronic polarizabilities of constituent atoms must be regarded as anisotropic in order to interpret the optical anisotropy. The resulting force constants for non-bonded oxygen-oxygen interactions can give the correct orders of magnitude for the Lennard-Jones potential constants.
X-Ray Photoelectron Spectroscopy of the Molecules Containing the C≡N Group
Authors: Fujikawa Takashi , Ohta Toshiaki , Kuroda Haruo 
Published: July 2006

Abstract
The gas-phase X-ray photoelectron spectra (with MgKα radiation) were observed on acetonitrile, propionitrile, acrylonitrile and fumaronitrile. The ionization potentials were determined for all valence-electron levels of the above molecules by using the data derived from the observed valence-electron bands of X-ray photoelectron spectra and the reported data of ultraviolet photoelectron spectroscopy. It is shown that there is a linear relation between the observed ionization potential (IP) and the CNDO/2 orbital energy (ε): IP=0.61(−ε)+3.2[eV], for σ-orbitals; IP=0.38(−ε)+6.0[eV], for π-orbitals. The observed binding energies of the C ls levels were analyzed by means of the electrostatic potential model and the charge densities calculated by CNDO/2 method. Discussion is given also on the shake-up satellite of core-electron peak.
Predictions of Molecular Geometries and Electronic Spectra of Complex Unsaturated Molecules from MC-LCAO-MO Method. II. 1,3-Butadiene and Cyclobutadiene
Authors: Nakayama Mitsunobu , Nishihira Moriyuki , I’Haya Yasumasa J 
Published: July 2006

Abstract
A multi-configuration (MC)-LCAO-MO method is applied to 1,3-butadiene and cyclobutadiene, predicting their molecular geometries and electronic spectra. The molecular ground state geometry, electronic spectrum and stabilization energy of the trans- to the cis-isomer of 1,3-butadiene are predicted to be in good accord with experiments and with those derived from the ordinary semi-empirical SCF-CI method. The results obtained for cyclobutadiene indicate that (a) the Jahn-Teller distortion occurs to favor a rectangular (D2h) form, the stabilization energy being 0.3–0.9 eV depending on approximations, and (b) even in a square (D4h) form a singlet (ground) state is more stable than a triplet state by ca. 0.3 eV. It is also shown that the lowest excited singlet and triplet states (3A2g and 1B1g) in the square form are not subjected to the Jahn-Teller effect. A discussion is given on a possible error in a CI treatment arising when degenerate molecular orbitals are expressed by real coefficients of atomic orbitals.
Interactions of Calcium Ions with Carbohydrates: Crystal Structure of Calcium d-Glucarate Tetrahydrate
Authors: Taga Tooru , Osaki Kenji 
Published: July 2006

Abstract
The crystal structure of calcium d-glucarate tetrahydrate has been determined from three dimensional X-ray data, and refined by the least squares method including an anisotropic temperature factor. The crystals are orthorhombic, space group P212121 with a=16.09, b=11.36 and c=6.68Å. The calcium ion is bound to two glucarate molecules and three water molecules. The eight oxygen atoms form the calcium coordination shell of a distorted square-antiprism geometry. The carboxyl group including C(1) of d-glucarate has an eclipsed conformation relative to C(2) and O(2), and is coordinated with one calcium ion through the carboxyl oxygen O(1) and the α-hydroxyl oxygen O(2), and with the other calcium ion through the carboxyl oxygen O′(1) and the hydroxyl oxygens O(3) and O(4). The other carboxyl group including C(6) has an unusual staggered conformation relative to C(5) and O(5), and is not coordinated with calcium ions. However the oxygen atoms of the latter carboxyl group are attached by hydrogen bonds to a number of hydroxyl groups and water molecules, all of which are coordinated with calcium ions.
Electronic Population Analysis Based on the Electron Pair Concept
Authors: Okada Takashi , Fueno Takayuki 
Published: July 2006

Abstract
The electronic population in molecular systems is analyzed on the basis of the spin coupling matrix. A proposal is made to define the pair-coupling population which is directly related to the electron pair concept. The theory is applied to the examinations of various types of wave functions used for three-centered two-, three-, and four-electron systems. The results permit clear comparisons of the characteristics of the various wave functions examined.
The Crystal and Molecular Structure of (Acetylacetonato)(carboxymethyl)(triphenylphosphine)palladium(II)
Authors: Zenitani Yukio , Inoue Kaoru , Kai Yasushi , Yasuoka Noritake , Kasai Nobutami 
Published: July 2006

Abstract
The molecular structure of (acetylacetonato)(carboxymethyl)(triphenylphosphine)palladium(II) [(acac)-(PPh3)PdCH2COOH] has been determined by means of X-ray diffraction. The crystal belongs to the triclinic system, space group P\bar1, with two formula units in a cell with dimensions of a=10.433(2), b=12.746(2), c=10.224(2) Å, α=106.62(1), β=112.41(2), and γ=75.13(2)°. R=0.032 for 4972 non-zero reflections. The palladium atom, σ-bonded to the methylene group of the acetic acid moiety (Pd–C=2.063(4) Å), has a square-planar geometry. The molecule forms a dimer with the adjacent molecule related by a center of symmetry through an inter-molecular hydrogen bonding between acetic acid moieties, O–H···O=2.621(4) Å.
Bivalent Metal Complexes of N,N-Bis(2-hydroxyethyl)glycine
Authors: Inomata Yoshie , Takeuchi Toshio , Moriwaki Takao 
Published: July 2006

Abstract
Complexes of N,N-bis(2-hydroxyethyl)glycine(BHEG) with a bivalent cation (Cu(II), Ni(II), Co(II), Zn(II), Fe(II), Cd(II), and Pb(II)) have been prepared and investigated by means of infrared absorption spectra, powder surface diffuse reflection spectra, electronic spectra, magnetic susceptibility, and thermal analysis. They can be classified into two types: (A) ML2·nH2O and (B) ML·X·nH2O, (M: metal, L: BHEG−, X: Cl− or NO3−). Ni(II), Co(II), Zn(II), and Fe(II) complexes are of type A, and those of Cd(II) and Pb(II) of type B. In the case of Cu(II) complexes, a blue A type complex (Cu(II)-A) has been prepared from a basic solution and a green B type one (Cu(II)-B) from an acidic solution. From detailed assignments of IR spectra, BHEG is found to have a zwitter ion structure. From magnetic moment data and reflection spectra, we presume that the A type complexes have a trans octahedral structure and the B type complexes a tetrahedral structure.
Photoreactions of Cyclic Benzylidene Acetals with Ketones in the Presence and Absence of Dissolved Oxygen
Authors: Suzuki Morio , Inai Toshimi , Matsushima Ryoka 
Published: July 2006

Abstract
Photoreactions of 2-phenyl-1,3-dioxane (1) and 4,6-O-benzylidene-1,2,3-tri-O-acetylglucopyranose (10) in the presence of benzophenone, acetophenone, or acetone have been studied in both deoxygenated and aerated benzene solutions at room temperature. Photolysis of 1 with ketone in deoxygenated solution gave a dimeric product of 1 (8), cross adduct, and pinacol, while in aerated solution an oxidative ring cleavage product, i.e., trimethyleneglycol monobenzoate (9), was obtained instead of 8, besides smaller amounts of pinacol and cross adduct. The yields of pinacol and cross adduct decreased with the change in ketone in the order benzophenone&gt;acetophenone&gt;acetone, while the yield of 8 or 9 was in the reverse order. Photolysis of 10 with ketone led to results parallel to those of 1: photolysis under nitrogen atomosphere gave pinacol, cross adduct, and a dimeric product of 10 (14), while under bubbling air 4-O-monobenzoate and 6-O-monobenzoate derivatives of 10 were obtained instead of 14, besides pinacol and cross adduct. The effects of temperature, oxygen, and structure on the course of the reaction, to produce dimeric or ring opening products, have been discussed.
A Study on the Photochemistry of α,β-Unsaturated γ-Lactones. III. Photodimerization of 2-Penten-4-olide
Authors: Ohga Kazuya , Matsuo Taku 
Published: July 2006

Abstract
Irradiation of 2-pentene-4-olide (I) with 254 nm light afforded three and dimers; two head-to-tail isomers and one head-to-head isomer. The photodimerization proceeds via the lowest triplet state. The quantum yields for the formation of the photodimers were determined as a function of the concentrations of I. Addition of I in the excited state to cyclopentene gave two isomeric cyclobutane derivatives. The photocycloaddition took place more rapidly than the photodimerization of I. The photodimerization was also quenched by anisole, probably through formation of an exciplex between I and anisole.
Stereochemistry of the C and D Rings of C-Nor-D-homosteroids. III. The Synthesis of Etiojervane Analogs of Androstan-3β-ol
Authors: Murai Akio , Nishimura Takeshi , Masamune Tadashi 
Published: July 2006

Abstract
The synthesis of C/D trans- and cis-fused C-nor-D-homoandrostan-3β-ol 3-acetates (11a and 34a) from jervine (1) is described. The configurations of both the compounds and the synthetic intermediates are defined clearly on the basis of the chemical and spectral evidence.
The Effect of Steric Condition in Cobalt(II), Nickel(II) and Copper(II) Complexes with Schiff Bases Obtained from Salicylaldehyde Derivatives and Diphenylmethylamine
Authors: Yamanouchi Kuniko , Yamada Shoichiro 
Published: July 2006

Abstract
Cobalt(II), nickel(II) and copper(II) complexes with N-diphenylmethyl-ring-substituted salicylideneiminates (abbreviated as X–Sal–Dpm) have been synthesized, in order to examine the steric and electronic effect of a substituent diphenylmethyl group on the structure of the metal complexes. Compounds of the type M(X–Sal–Dpm)2 and their adducts of the type M(X–Sal–Dpm)2·nL have been isolated in crystals, n being 2 or 4 and L being benzene, acetone or pyridine. Both in the solid state and in non-donor solvents, the complexes Co(X–Sal–Dpm)2 have a tetrahedral configuration, and Ni(X–Sal–Dpm)2 and Cu(X–Sal–Dpm)2 have a square-planar configuration, irrespectively of substituents X. The results so far available seem to indicate that the steric hindrance caused by the substituent diphenylmethyl group against the square-planar configuration of the metal complexes may be smaller than that by isopropyl group.
Ring-opening Reactions of Cyclic Ethers. IX. Molecular Weight Distribution of Adducts in the Acid-catalyzed Reactions of Epichlorohydrin with Alcohols
Authors: Sekiguchi Shizen , Hasegawa Yasushi , Nakamura Kenji , Matsui Kohji , Nagahama Kensuke 
Published: July 2006

Abstract
It was found that the molecular weights of adducts in the acid-catalyzed reactions of epichlorohydrin with alcohols obey the Weibull-Nycander distribution but not the Flory distribution. The distribution constants (C=ki⁄k0) were found to be smaller than 1, indicating that the reaction rate of the initial stage (k0), i.e., the reaction of epichlorohydrin with a starting alcohol, is greater than the rates of the later stages (ki), i.e., the reactions of epichlorohydrin with its adducts. The results indicate that the reaction proceeds via an “borderline” A-2 mechanism.
Thermolysis of Phenyl 3-Guaiazulenecarboxylate and the p-Acetyl and p-Methoxy Derivatives
Authors: Kurokawa Shinji , Anderson Arthur G 
Published: July 2006

Abstract
Thermolysis of p-acetylphenyl 3-guaiazulenecarboxylate (1) results in loss of the ester group. In contrast, thermolysis of phenyl 3-guaiazulenecarboxylate (2) or p-methoxyphenyl 3-guaiazulenecarboxylate (3) gives (i) loss of the ester group, (ii) loss of the 1-methyl group with concomitant rearrangement of the ester group to the 1-position, (iii) interchange of the ester and 1-methyl groups, and (iv) cyclization to 5-isopropyl-7-methyl-1,2-dihydrocyclopenta[c,d]azulen-1-one (9).
Synthesis of Eriostoic Acid and Eriostemoic Acid
Authors: Tsukayama Masao 
Published: July 2006

Abstract
A 1,8-dioxaanthracenepropionic acid derivative (5), after being converted into methyl ester-methyl ether (6), was reduced with sodium borohydride to give methyl eriostate (7). Hydrolysis of the ester (7) with alkali afforded eriostoic acid (1). On the other hand, eriostemoic acid (2) was synthesized from methyl eriostemate (10), which was obtained from a 1,5-dioxaphenanthrenepropionic acid derivative (8) via four steps.
The Photoreaction of Benzyl 1-Cycloalkenyl Ketone in Acidic or Protic Media
Authors: Tada Masaru , Saiki Hiroshi , Miura Kyo , Shinozaki Hiraku 
Published: July 2006

Abstract
Three benzyl 1-cycloalkenyl ketones, I–III, were irradiated in the presence of boron trifluoride-diethyl ether (0.05 mol/1) in benzene to give the products V–VII, formed by the bonding between the β-position of αβ-unsaturated ketone and the ortho position of the benzene ring. Benzyl 1-cyclooctenyl ketone (IV) was inactive to the photocyclization because of the preferential geometrical isomerization of the olefin moiety. Trifluoro-acetic acid promotes the reaction exceedingly, but the reaction takes place also in methanol. The reaction in methanol was deduced from quenching experiments to be a triplet process. The reaction takes both singlet and triplet processes when irradiation is carried out in the presence of boron trifluoride–diethyl ether. The participation of the complex between benzyl 1-cycloalkenyl ketone and boron trifluoride is proposed for the singlet process.
Mixed Ligand Copper(II) Complexes of α-Amino Acids with Ligand-Ligand Interactions
Authors: Sakurai Takeshi , Yamauchi Osamu , Nakahara Akitsugu 
Published: July 2006

Abstract
Synthetic and spectroscopic studies have been made on the ternary copper(II) complexes containing two optically active α-amino acids with charged groups in their side chains. Thus, for all combinations of ligands A and B, where A refers to aspartic or glutamic acid and B to arginine, lysine, or ornithine, the mixed ligand complexes, [Cu(l-A)(l-B)] and [Cu(d-A)(l-B)] except [Cu(l-aspartate)(l-ornithine)], were isolated as crystals. Infrared spectra of the isolated complexes suggested the presence of the geometrical isomers. By comparing the observed circular dichroism spectra of the ternary systems with the spectra estimated from those of the corresponding binary systems, the magnitude enhancements were detected for all the Gu(l-A)(l-B) systems, whereas no such enhancement was observed when one of the ligands was l-alanine or l-valine. The spectral behaviors as well as the solid complexes isolated have been interpreted as indicative of the existence of the intramolecular electrostatic bonding between the oppositely charged groups in the side chains of the ligands and their significance as an effective driving force leading to the ternary complex formation.
Mechanism for Light Induced Hydrogen Isotope Exchange in Benzonitrile
Authors: Yoshida Masayuki , Kaneko Hiroyuki , Kitamura Akihide , Ito Tomiyasu , Oohashi Kunio , Morikawa Naotake , Sakuragi Hirochika , Tokumaru Katsumi 
Published: July 2006

Abstract
Light induced tritiation of benzonitrile with diethylamine[N3H] or triethylamine-tritiated water was studied with respect to quenching of benzonitrile fluorescence by the amines and the tritium distribution in the nucleus. A mechanism involving an exciplex possessing charge transfer nature was proposed.
Preparation of Matsutake Alcohol (1-Octen-3-ol) from a Butadiene Telomer
Authors: Tsuji Jiro , Tsuruoka Katsuhiko , Yamamoto Keiji 
Published: July 2006

Abstract
A simple preparation of 1-octen-3-ol so called Matsutake alcohol using a butadiene telomer is described: selective hydrogenation of the terminal double bond of 2,7-octadienyl acetate gave 2-octenyl acetate which was converted via palladium-catalyzed allylic rearrangement and hydrolysis into 1-octen-3-ol.
The Catalytic Hydroboration of Ethylene with Diborane in the Gas Phase —The Acidity of Catalysts and the Reaction Activity—
Authors: Matsuda Tsuneo , Seto Isao , Tanaka Toyosuke 
Published: July 2006

Abstract
The catalytic hydroboration of ethylene with diborane to triethylborane in the gas phase was studied in the presence of various catalysts. The acidity of catalysts and the reaction activity were measured; the increase in the activity can be related to surface acidity of the catalysts.
The Reaction of a Stable Free Nitrogen-centered Radical, 3,4-Dihydro-2,4,6-triphenyl-2H-1,2,4,5-tetrazin-1-yl, with Organolithium Compounds
Authors: Miura Yozo , Morimoto Yuzo , Kinoshita Masayoshi 
Published: July 2006

Abstract
3,4-Dihydro-2,4,6-triphenyl-2H-1,2,4,5-tetrazin-1-yl (1) reacted with ethyl- and butyllithiums to give 1-ethyl- and 1-butyl-2,4,6-triphenyl-1,2,3,4-tetrahydro-1,2,4,5-tetrazines respectively. On the other hand, biphenyl and 1-benzyl-2,4,6-triphenyl-1,2,3,4-tetrahydro-1,2,4,5-tetrazine were given by the reaction of 1 with phenyllithium in toluene. Thus, the results indicate that these reactions proceed through a homolytic process.
The Thermal Decomposition of Cyanodiphenylmethyl t-Butyl Peroxide An Example of C–O Bond Scission
Authors: Okubo Masao , Iba-Imai Emiko , Mizuta Hiroko , Kawamoto Takumi 
Published: July 2006

Abstract
The thermal decomposition of cyanodiphenylmethyl t-butyl peroxide was investigated. The peroxide is abnormally stable and decomposes slowly at 130–135 °C, and the main reaction product is tetraphenylsuccinonitrile. A main reaction path including the C–O bond scission, in contrast to the case of triphenylmethyl t-butyl peroxide, is proposed.
The Photochemical Reaction of Iron Pentacarbonyl and 1,3-Butadiene-1,1,4,4-d4. The Lack of Secondary Isotope Effects
Authors: Noyori Ryoji , Yokoyama Keiichi 
Published: July 2006

Abstract
No significant deuterium isotope effects have been noticed in the formation of the 1,3-butadiene–iron tricarbonyl complex, in contrast to the olefin complexation of Ag+ or Rh(I) species.
The Catalytic Reduction of Nitrogen Oxide by Carbon Monoxide over Metal Oxide Catalysts —The Correlation of the Activities with the Surface States of Metal Oxides—
Authors: Sakurai Katsumi , Okamoto Yasuaki , Imanaka Toshinobu , Teranishi Shiichiro 
Published: July 2006

Abstract
In the catalytic NO–CO reaction over metal oxide catalysts, the surface states of reduced metal oxides were studied with ESCA, and the correlation of the activities of the reduced metal oxide catalysts for the NO–CO reaction with their surface states was investigated. The surfaces of the catalysts were studied with ESCA after treatments in situ. It was revealed that the surface states of the metal oxides did not always agree with their bulk constituents. For example, it was found that the oxygen in the surface layer of the cobalt oxide after a proper reduction treatment by CO was richer than in its bulk. Moreover, the correlation between the surface states and the activities of those oxides was successfully explained. It was also concluded that, in the NO–CO reaction, the metal states were most active for the cobalt, iron, and nickel oxides, while the Cu+ state was more active than the Gu metal state for the copper oxide.
Photolysis of Formaldehyde in the Presence of Nitric Oxide
Authors: Tadasa Kohji , Imai Naomi , Inaba Tetsuo 
Published: July 2006

Abstract
The photolysis of CH2O has been studied in the absence and presence of NO from room temperature to 300°C. In the photolysis of CH2O alone, the CO and H2 formation rates increase greatly with temperature. When NO is added, these rates vary and reach constant values with an increase in the amount of NO. These limiting rates are independent of the temperature to within the experimental error, in contrast to the rates observed for CH2O alone. It is suggested that the limiting rate of CO formation corresponds to the sum of the rates of the two primary processes, the molecular and radical reactions, and that that of H2 formation corresponds to the rate of the molecular process. For photolysis totally inhibited by NO, the rates of formation of CO, H2, N2, and N2O were examined and a reaction mechanism is proposed which is consistent with that for the photosensitized reaction between hydrogen and nitric oxide previously studied in this laboratory.
Heat of Adsorption from Solution. II. The Heat of Adsorption of Pyridine on Silica–Alumina from the Hexane Solution
Authors: Naono Hiromitu , Moori Kazuko , Morimoto Tetsuo 
Published: July 2006

Abstract
The amounts of physisorbed and chemisorbed pyridine on silica–alumina in the hexane solution were measured at 30°C, and found to be 1.25 and 0.25 molecules/100 Å2 respectively. The number of strong acid sites determined by Benesi’s method are in good agreement with the chemisorbed molecules, which indicates that the ratio of the number of chemisorbed pyridine molecules to that of the strong acid sites on the surface of silica–alumina is equal. The adsorption calorimetry was carried out on the same system by means of a flow microcalorimeter which permits us to differentiate the heats of physisorption and chemisorption: the results showed that the heats of physisorption and chemisorption of pyridine are 11.3±0.3 and 22±4 kcal/mol respectively.