bluuebunny/crossref_metadata_2025 huggingface dataset:
On the Phase Transition of Cyclic Tris(ethylene terephthalate)
Authors: Kitano Yukishige , Kashiwagi Michio , Ebata Yasuyuki
Published: July 2006

The crystal data of the Type B modification of the cyclic tris(ethylene terephthalate) showed it to be hexagonal, with the unit-cell dimensions of a=15.42±0.03 and c=20.78±0.05 Å (space group, P61 or P65). The effects of some organic reagents on the stability of Type B were studied qualitatively, and some information about the phase changes was obtained by the X-ray-diffraction and thermal-analysis techniques.
The Regioselective Addition of Alcohols to Isoprene with Rhodium Trichloride Hydrates
Authors: Kawazura Hiroshi , Takagaki Toshihisa , Ishii Yoshio
Published: July 2006

Rhodium trichloride hydrates gave predominantly the 1,2-addition product, 2-alkoxy-2-methylbut-3-ene, in the addition reaction of alcohols to isoprene. The regioselective path was established by assuming the formation of the π-(2-methylbut-3-en-2-yl)rhodium complex.
Sucrose Chemistry. 6. Synthesis of Amino Derivatives of Sucrose
Authors: Suami Tetsuo , Ikeda Toshihide , Nishiyama Shigeru , Adaghi Ryoichi
Published: July 2006

6′-Amino-6′-deoxy- and 1′,6′-diamino-1′,-6′-dideoxysucrose have been prepared by azidolysis of the corresponding tosylates, followed by catalytic hydrogenation.
The Formation of 1,1′-Oligomeric Ferrocenes from Chloromercuriferrocene and Bis(chloromercuri)ferrocene
Authors: Izumi Taeko , Kasahara Akira
Published: July 2006

A series of 1,1′-oligomeric ferrocenes, including biferrocene, 1,1′-biferrocenylene, 1,1 ′-terferrocene, 1,1′-quaterferrocene, 1,1′-quinqueferrocene, and 1,1′-sexiferrocene, was formed by the reaction between chloromercuriferrocene and 1,1′-bis(chloromercuri)ferrocene in the presence of palladium(II) salt.
Hydrogen Bonding Interactions of Carboxylic Acids with N,N-Dimethylacetamide and Pyrazine as Studied by Means of NMR Dilution Shifts
Authors: Fujiwara Hideaki , Yoshida Nobuyuki , Ikenoue Tsuneo
Published: July 2006

The NMR dilution shifts of OH proton in several carboxylic acids have been studied for mixtures with N,N-dimethylacetamide (DMA) or pyrazine. The acids treated were acetic, propionic isobutyric, and trifluoroacetic acids. The dilution shifts curve of OH proton in each acid–DMA system showed a characteristic ν-type curve with the minimum value at 0.65–0.75 mol fraction of the acid. The curve for the isobutyric acid-pyrazine system was linear below 0.45 mol fraction of the acid, taking the minimum at 0.75 mol fraction. These curves were explained by assuming the formation of both 1: 1 and 2 (acids): 1(base) complexes in the chemical equilibrium. The formation constants of the complexes and the shifts of OH proton in the 2: 1 complex were estimated for each system. Liability of the complex formation and the structure possible for the 2: 1 complex were discussed.
The Crystal and Molecular Structure of the p-Bromobenzoate of Sterigmatocystin
Authors: Fukuyama Keiichi , Tsukihara Tomitake , Katsube Yukiteru , Tanaka Nobuo , Hamasaki Takashi , Hatsuda Yuichi
Published: July 2006

The crystals of the p-bromobenzoate of sterigmatocystin, C25H15O7Br, are monoclinic, with the space group of P21 and with two molecules per unit cell with the dimensions of a=13.062(7), b=9.029(4), c=8.942(4) Å, and β=102.25(5)°. The structure was refined by a least-squares method to R=0.055 for 1292 non-zero reflections. The absolute configuration of the molecule was determined by using the anomalous dispersion effect of the bromine atom. The absolute configuration of the bisdihydrofuran ring agrees with that in aflatoxin B1.
Theoretical Determination of the Principal Axes of 13C Chemical Shielding Tensors and their Relationship to the Anisotropies in Some Organic Compounds
Authors: Ando Isao , Nishioka Atsuo , Kondo Masahiro
Published: July 2006

The principal axes and values for the 13C chemical shielding tensors of carbonyl compounds (formaldehyde, acetaldehyde, acetone, and formic acid), methanol, and n-paraffins (propane and n-butane) have been determined theoretically by the LCGI–MO theory using the MINDO/2 method. Further, their anisotropies have been estimated. These results have then been discussed by comparing them with the observation of Pines et al. and in part compared with the anisotropies in the literature calculated by using other theoretical methods.
Inhibition Effects of Some Polymers on Electroreduction of Anions at the Mercury/Solution Interface
Authors: Ohsaka Tetsuya , Iida Yasuo , Yoshida Tadashi
Published: July 2006

The present work was conducted to investigate the electroreduction of anions (typically S2O82− and BrO3−) under the influence of the adsorption of polymers (polyethyleneglycol, alkylphenoxy polyethoxy ethanols and polyvinylpyrrolidone) on the electrode surface. The limiting current of S2O82− reduction was depressed by the polymers in the region from nearly the zero-charge potential to the more negative potential. The half-wave potential of BrO3− reduction shifted towards more negative potential by adding the polymers. In the potential range where the cathodic current was mainly controlled by mass transfer of the anions, the time (tm) needed to complete the formation of a monolayer was obtainable conveniently from the instantaneous current vs. time (I–t) curve as reported previously for the inhibited reduction of Cd2+ or Cu2+. In the potential range where the current was mainly controlled by charge transfer, an exact determination of tm, by which the maximum surface concentration of polymer was given, was possible only when the instantaneous current density (i) was plotted against t1⁄2. In such a potential range, i was expressed as follows.

2& i=i_0-(i_0-i_1)(t/t_m)^1/2 & & for t≤t_m

or & i=i_1 & & for t>t_m

Moreover,

2& \barI_ads/\barI_0=1-\frac1013\fraci_0-i_1i_0(t_d/t_m)^1/2 & & for t_d≤t_m

& \barI_ads/\barI_0=1-\frac1013\fraci_0-i_1i_0-\frac313\fraci_0-i_1i_0{1-(t_d/t_m)^-5/3} & & for t_d>t_m

where i0 and i1 are the instantaneous current densities at θ=0 and 1, \barIads and \barI0 the polarographic currents with and without polymers, td the drop time, tm the time required to attain the saturated adsorption. The relationship between the shift of half-wave potential and (td⁄tm)1⁄2 (for td≤tm) or (td⁄tm)−5⁄3 (for td>tm), was introduced and the results were verified for the inhibition effects of polymer on the electroreduction of BrO3− as well as for that on VO2+ reduction.
Microwave Spectrum of 2-Pyridinecarbaldehyde
Authors: Kawashima Yoshiyuki , Suzuki Masao , Kozima Kunio
Published: July 2006

The microwave spectrum of 2-pyridinecarbaldehyde has been observed in the region 8–22 GHz. The rotational constants of the ground state are A=5362.52±2.19 MHz, B=1620.07±0.03 MHz, and C=1244.42±0.03 MHz and the inertia defect is −0.075 amu·Å2. This value demonstrates that the molecule is planar in its equilibrium position. The total dipole moment is 3.56±0.07 D, the components of which are μa=3.48±0.05 D and μb=0.76±0.08 D. From these facts it is concluded that the conformation of the molecule is of the O–N s-trans form. The rotational constants of the five vibrationally-excited states have also been determined.
The Thermodynamic Properties of C9H18 Naphthenes. I. The Determination of the Equilibrium Constants for the Hydrogenation of Propyl- and Isopropylbenzene and Ethyltoluenes
Authors: Miki Yasuo
Published: July 2006

The equilibria for the hydrogenation of n-propylbenzene, isopropylbenzene, 1-methyl-2-ethylbenzene, 1-methyl-3-ethylbenzene, and 1-methyl-4-ethylbenzene were determined experimentally over the temperature range of 250 to 450°C and under hydrogen pressures ranging from 5 to 50 atm. The data were then used to calculate the values of the free energy and the equilibrium constant of the above reactions and the values of standard free energy of formation from the elements for n-propylcyclohexane, isopropylcyclohexane, 1-methyl-cis-2-ethyl-cyclohexane, 1-methyl-trans-2-ethylcyclohexane, 1-methyl-cis-3-ethylcyclohexane, 1-methyl-trans-3-ethylcyclohexane, 1-methyl-cis-4-ethylcyclohexane, and 1-methyWrawj-trans-ethylcyclohexane.
The Steric Requirements of N,N′-Bis(salicylidene)-2-aminobenzylamines on Metal Chelate Formation
Authors: Kanatomi Hajime , Demura Yoichi , Murase Ichiro
Published: July 2006

Copper(II), Ni(II), Co(II), Zn(II), and Be(II) chelates of N,N′-bis(salicylidene)-2-aminobenzylamine and its methyl and dimethyl salicylidene derivatives have been prepared and characterized. According to the molecular models, the ligands are favorable to tetrahedral arrangement on complex formation. The spectral and magnetic properties revealed that all the Co(II) and some of the Cu(II) chelates were pseudo-tetrahedral, while the Ni(II) and other Cu(II) chelates were square-planar, with a considerable angle strain. This ligand property is somewhat inconsistent with the conclusion derived from N,N′-bis (salicylidene) polymethylenediamine chelates, in which the trimethylene analogue could not take a pseudotetrahedral arrangement around a metal ion. The difference in stereochemistry between the two ligands with the same number of bridging carbon atoms will be discussed on the basis of the flexibility and the steric requirement of the central chelate ring.
Iminophosphorane Complexes of Palladium(II)
Authors: Fukui Mitsuyo , Itoh Kenji , Ishii Yoshio
Published: July 2006

Iminophosphorane complexes of palladium [(C6H5)3P=N–C6H4–X-p]PdCl2(CH3CN) (X=NO2, 1A; COO-C2H5, 2A; Cl, 3A; H, 4A; CH3, 5A) have been prepared by ligand-substitution reaction between (C6H5CN)2PdCl2 and the parent iminophosphoranes, followed by recrystallization from acetonitrile-ethyl acetate. Other iminophosphoranes (X=OCH3, and (C6H5)2(CH3)P=N–Si(CH3)3), however, gave only dimeric complexes with the [(Iminophosphorane)PdCl2]2 composition. Complexes 1A–5A and {[(C6H5)3P=N–C6H4–X-p]PdCl2}2 (X=NO2, 1B; COOC2H5, 2B; Cl, 3B; H, 4B; CH3, 5B) are also discussed. The ligand-exchange reaction of 2B and 5B with α,α′-bipyridine, (C6H5)3P, and (CH3O)3P took place, liberating the parent iminophosphorane.
Carboxymethylation of Organic Halides by Palladium Complexes under Mild Conditions
Authors: Hidai Masanobu , Hikita Tomoji , Wada Yoshimasa , Fujikura Yuzo , Uchida Yasuzo
Published: July 2006

Palladium complexes, Pd(CO)(PPh3)3, Pd3(CO)3(PPh3)4, Pd3(CO)3(PPh3)3, and PdCl2(PPh3)2 were found to be excellent catalysts for the carboxymethylation of various organic halides under very mild conditions. The carboxymethylation reaction is considered to proceed via acyl complexes as the intermediates.
Reaction of Tetrachloroxylenes with Fuming Nitric Acid. Side-chain Nitrooxylation and Quinol Nitrate Formation
Authors: Suzuki Hitomi , Ishizaki Katsuro , Maruyama Shigeru , Hanafusa Terukiyo
Published: July 2006

Direct action of fuming nitric acid upon tetrachloro-o- and -m-xylenes at room temperatur led to the formation of 3,5,6-trichloro-1,2-dimethyl-4-oxocyclohexa-2,5-dienyl nitrate and 2,5,6-trichloro-1,3-dimethyl-4-oxocyclohexa-2,5-dienyl nitrate, respectively, as the major products. In contrast, tetrachloro-p-xylene was simply converted into 2,3,5,6-tetrachloro-4-methylbenzyl nitrate. Plausible reaction sequences as well as criteria as a basis for predicting the propensity of polysubstituted alkylaromatics towards unusual nitration have been discussed.
Nitration of 9,10-Dialkylphenanthrenes. Side-chain Nitrooxylation in Competition with Side-chain Nitration
Authors: Suzuki Hitomi , Yoneda Hajime , Hanafusa Terukiyo
Published: July 2006

9,10-Dimethylphenanthrene and 9-methyl-10-ethylphenanthrene gave 9-methyl-10-nitromethylphenanthrene and 9-ethyl-10-nitromethylphenanthrene, respectively, as major product, when treated with fuming nitric acid in dichloromethane at low temperatures. In contrast, 9,10-diethylphenanthrene yielded a comparable mixture of products arising from side-chain nitration and side-chain nitrooxylation, which on chromatography over deactivated alumina gave 9-ethyl-10-(α-nitroethyl)phenanthrene and 9-ethyl-10-(α-hydroxyethyl)phenanthrene as main isolable products. 9-Methylphenanthrene and 9-ethylphenanthrene were both simply nitrated at the ring position to give the corresponding 9-alkyl-10-nitrophenanthrenes in good yields. No side-chain attack was observed. Factors responsible for determining which one of the competitive pathways will be followed have been discussed.
The Radiation-induced Decoloration of Azo Dye in Aqueous Solutions
Authors: Suzuki Nobutake , Nagai Takeshi , Hotta Hiroshi , Washino Masamitsu
Published: July 2006

The decoloration yield of an Acid Red 265 neutral aqueous solution, G(-Dye), equaled 1.00±0.04, regardless of the dose rate and the initial dye concentration in the early stage. The G(-Dye) increased to 1.46 in the presence of nitrous oxide, but was independent of the presence of oxygen and acetone. In nitrogen-saturated solutions, the G(–Dye) increased markedly upon the addition of alcohols—for example, up to 1.83 upon the addition of 2 mM n-butyl alcohol. On the other hand, in oxygen-saturated solutions, the G(-Dye) decreased markedly upon the addition of even a small amount of alcohols. The effects of alcohols, namely, the G(-Dye) in both the solutions were in the order of their reactivity with OH radicals. The decoloration is attributable to the attack of the OH radicals formed by the radiolysis of water to the dye. The increase in the G(-Dye) for the nitrogen-saturated solutions containing alcohols is attributable to the attack of the alcohol radicals (R\dotCHOH) formed by the reactions of alcohols with OH radicals. In the oxygen-saturated solutions, the R\dotCHOH radicals are converted to the peroxides, which do not react with the dye. The rate constant for the reaction of the OH radical with Acid Red 265, obtained by using various additives from the competition reaction method, is 9.3±1.4×109 M−1 s−1. The effects of CNS−, glucose, and phenol were also examined.
ENDOR Studies in the Conformation of 3,3′- or 3,4′-Polymethylenebiphenyl Anion Radicals.
Authors: Ishizu Kazuhiko , Nemoto Fujito , Yamamoto Koji , Nakazaki Masao
Published: July 2006

The ENDOR spectra have been observed for the anion radicals of 3,3′- and 3,4′-polymethylenebiphenyl with various chain lengths. The hyperfine coupling constants of the ring protons of the 3,3′-derivatives are comparable with those of the reference derivative, m,m′-bitolyl, and the biphenyl ring is considered to take the planar conformation. When the chain length is shortened and the polymethylene chain increases its probability of being held on the biphenyl aromatic plane, strong through-space interactions are observed between the aromatic π and the polymethylene pseudo-π orbital. In 3,4′-polymethylenebiphenyl with shorter chain lengths, the coplanar phenyl rings are twisted out by the polymethylene span and the magnitudes of the spin densities at the ortho-position are reduced by the resonance inhibition between two phenyls. McLachaln’s MO calculations predict that the twisting angles between the two phenyls are similar to the value reported for 2,2′-bitolyl anion radical. In contrast to the case of the 2,2′-bitolyl anion radical, however, a conformational change in biphenyl resulting from the delocalization of the unpaired electron is suppressed by a tight lock of the rotation of the phenyl groups in the polymethylene derivatives.
The Cadmium-photosensitized Reaction of Water, Alcohols, and Ethers. The Quenching of the Resonance Radiation at 326.1 nm and the Photosensitized Luminescence
Authors: Yamamoto Shunzo , Tanaka Kazuyuki , Sato Shin
Published: July 2006

A luminescence similar to the photosensitized luminescence of ammonia was observed in the cadmium-photosensitized reaction of water, alcohols, and ethers. The quantum yields of the luminescence with these compounds were much smaller than that with ammonia. The rate constants for the formation of the excited complexes between the excited cadmium atoms and the substrates generally increased with a decrease in the ionization potentials of the substrates. This shows that the complex has the characteristics of a charge-transfer type. On the other hand, the efficiencies of the quenching of the resonance radiation at 326.1 nm by ethers were smaller than those of alcohols. It is concluded that the quenching through the formation of the complex is a minor process in the quenching of the resonance radiation by water, alcohols, and ethers.
Studies on Xanthenyl and Thioxanthenyl Derivatives. Reactions of Xanthenyl and Thioxanthenyl Halides with Substituted-Ethylenes
Authors: Awad Sami Bassili , Abdul-Malik Nadia Fouad , Abdou Sadek Elsayed
Published: July 2006

Xanthenyl and thioxanthenyl chlorides (1) were added to 1,1-bis-(p-alkoxyphenyl)-2-substituted-ethylenes (2) to give 1,1-bis-(p-alkoxyphenyl)-2-substituted-2-[xanthen(or thioxanthen)-9-yl]ethylenes (3). The 2-nitroderivatives (3) were converted in boiling methanolic potassium hydroxide into the allenes, 1,1-bis-(p-alkoxyphenyl)-2-[xanthen(or thioxanthen)-9-ylidene]ethylenes (4). The 2-methyl(or chloro)-derivatives (3) reacted with bromine in the presence of hydrogen bromide, to yield xanthylium or thioxanthylium tribromide (5) and the corresponding 2,2-disubstituted-ethylene (6). The tribromides (5) reacted with the ethylene (2, Z=H to give, after spontaneous dehydrobromination, the corresponding 2-bromo-derivatives (3, Z=Br).
Charge Transfer Interactions between Oxygen and the Anion Radicals of Tetracyanoquinodimethane and Tetracyanoethylene
Authors: Sakata Tadayoshi , Okai Toshihiro , Tsubomura Hiroshi
Published: July 2006

The spectra of the anion radicals of tetracyanoquinodimethane and tetracyanoethylene formed on porous Vycor glass change by introducing O2 at 77 K. The main features are broadening and slight energy shift of the bands and appearance of a new band. These changes are explained by assuming the charge transfer interactions between O2 and the anion radicals.
The Syntheses and Properties of Mixed Cobalt(III) Complexes Containing 2-Mercaptoacetic Acid or 3-Mercaptopropionic Acid
Authors: Hori Kiichi
Published: July 2006

The following mixed cobalt(III) complexes were prepared and characterized: [Co(SCH2COO)en2]X and [Co(SCH2CH2COO)en2]X, where X is a chloride or iodide ion. Those complexes are common mononuclear complexes, in which the mercaptocarboxylic acids of the ligands function as bidentate ligands.
Rearrangement of Tetramethyl-trans-decalin Derivatives
Authors: Tatee Tochiro , Tsuyuki Takahiko , Takahashi Takeyoshi
Published: July 2006

The dihydroxydecalin (6) was treated with iodine at 140 °C to give the octalins (13 and 14). Treatment of the β-epoxide (8) with boron trifluoride etherate gave the octalins [17 and 18 (or 19)] and the oxide (20).
Effect of Alkylation on the Iodine 6s Rydberg States of Iodoalkanes
Authors: Katsumata Shunji , Wakabayashi Hidechika , Kimura Katsumi
Published: July 2006

In a series of alkyl iodides far UV absorption and photoelectron spectra indicate that, unlike higher Rydberg members, the lowest Rydberg states are rather sensitive to the alkyl groups, linearity holding between the term values and the first ionization potentials.
Studies on Ferrocene and Its Derivatives. I. Reactions of Formylferrocene with α-Amino Acids
Authors: Osman A M , El-Maghraby M A , Hassan Kh M
Published: July 2006

The condensation reactions of formyl-ferrocene (I) with various α-amino acids and their esters were studied. The products are new Schiff bases (II) which may be of medicinal value.
Formulation of Stokes’ Radii in DMF, DMSO and Propylene Carbonate with Solvent Structure Cavity Size as Parameter
Authors: Matsuura Niro , Umemoto Kisaburo , Takeda Yasuyuki
Published: July 2006

Conductance of univalent ions in DMSO (dimethyl sulfoxide), DMF (dimethylformamide) and PC (propylene carbonate) was determined by use of tetrabutylammonium-tetrabutylborate as standard electrolyte of equal cationic and anionic conductance. Empirical formulation of Stokes’ radius was attempted on the assumption of a structure-cavity affecting the ionic transport in a medium of aprotic and polar solvent as well as water. By application of classical fluid dynamics Stokes’ radius rs is given in terms of −(2⁄3)rc+(1⁄σs) (rc–ro)2, where rc is crystal ionic radius, ro and σs are parameters characteristic of the cavity and molecular sizes, respectively, with respect the solvent.
Solvent Effects on the Absolute Intensities of Infrared Absorption Bands and the Dipole-Dipole Interaction
Authors: Kakimoto Masao , Fujiyama Tsunetake
Published: July 2006

The absolute intensities of the infrared absorption bands, ν3 of methyl iodide, ν2 of methyl cyanide, and ν8 of methyl cyanide, were measured in various solvents at various concentrations. Even after the effect of the internal field is eliminated, very large solvent effects remain in the absorption intensities due to the intermolecular interactions. An equation based on the model of the dipole-dipole interaction is proposed to interpret the experimental results. Comparison with the experimental data confirms the validity of the model.
The Raman Spectra of Surfactants and The Concentration Dependence of Their Molecular Conformations in Aqueous Solutions
Authors: Okabayashi Hirofumi , Okuyama Masataka , Kitagawa Teizo
Published: July 2006

The laser Raman scattering by potassium n-alkyl carboxylates and sodium n-alkyl sulfates was measured in the solid state and aqueous solutions, and the concentration dependence of molecular conformations of these molecules was studied. For aqueous solutions of potassium n-hexanoate and potassium n-pentanoate, the Raman intensities of the accordion vibrations of the all-trans form relative to the skeletal deformation vibrations of the gauche isomers were found to increase with an increase in the concentration. This intensity change is remarkable at the critical micelle concentration. A concentration dependence of the intensity of the Raman lines was also observed in the frequency region of 1600–600 cm−1. These observations revealed that the percentage of the all-trans form of the surfactant molecules increases with an increase in the concentration above the critical micelle concentration.
Semiempirical Relations in Molecular Liquids. I. Molecular Structure, Melting Temperature, and Effective Hard Core Diameter of Molecules
Authors: Oono Yoshitsugu
Published: July 2006

A simple method for the estimation of the effective hard core diameter of a molecule (at melting point), which is the only parameter in the application of the scaled particle theory to molecular liquids, is proposed. For a nearly spherical molecule, the effective hard core diameter a in Å can be given by

a=1.072 P^2/5T_m^-1/10,

where P is the parachor of the molecule in cgs unit and Tm is the melting temperature in K. The factor 1.072 is equal to that predicted by the scaled particle theory.
Synthesis and Thermochromic Properties of New Five-coordinate Copper Chelates
Authors: Iwasaki Noriko , Sone Kozo , Ojima Heijiro
Published: July 2006

Two new five-coordinate copper(II) chelates [Cu(PCdien)] and [Cu(PCenpn)] were prepared, and the thermochromism of the former in methanolic solution was studied. When this violet-blue solution (νmax: 16500 cm−1) was heated nearly to the boiling point of methanol, the color of the solution became gradually yellowish (νmax: 21000 cm−1). The absorption spectra of these cold and hot solutions were compared with those of similar four-coordinate Cu(II) complexes in various solvents, and the yellow color was ascribed to a tetracoordinated species of [Cu(PCdien)], which is formed by the partial rupture of the pentacoordinated structure caused by the intramolecular steric strains. No thermochromic property of the PCenpn chelate was observed.
Studies of Ruthenium Complexes. VIII. Kinetic Studies of the Thermal Substitution Reaction of Hexaammine and cis-Dihalogenotetraammineruthenium(III) Complexes in the Solid State
Authors: Ohyoshi Akira , Hiraki Shunichi , Odate Tomio , Kohata Susumu , Oda Junko
Published: July 2006

The Kinetics of the thermal substitution reaction of hexaammineruthenium(III) halides and cis-dihalogenotetraammineruthenium(III) halides have been studied in the solid state. The reaction rates and kinetic parameters were determined for these two reactions; [Ru(NH3)6]X3→[RuX(NH3)5]X2+NH3, (X=Br, I) and cis-[RuX2(NH3)4]X→[RuX3(NH3)3]+NH3, (X=Cl, Br). The values of the rate constant, the activation energy, and the activation entropy were 2.10×10−5 s−1 (at 161°C), 23.3 kcal mol−1, and −29.3 e.u. for the hexaammine bromide, and 2.92×10−5s−1 (at 162 °C), 31.3 kcal mol−1, and −10.1 e.u. for the cis-dibromotetraammine bromide. The Sn2 mechanism is more probable for the former reaction, while the SN1 mechanism is more probable for the latter reaction.
Synthesis of 6′-Amino-1-N-[(S)-4-Amino-2-Hydroxybutyryl]-6′-Deoxylividomycin A
Authors: Watanabe Isamu , Ejima Akio , Tsuchiya Tsutomu , Umezawa Sumio , Umezawa Hamao
Published: July 2006

The titled compound (11) was prepared from lividomycin A. A partially protected cyclic 1,6-carbamate derivative (6), which has free hydroxyl groups at C-4′ and C-6′, was prepared, and the 6′-hydroxyl group was selectively tosylated. Replacement of the tosyl group by azido group, followed by partial hydrolysis of the carbamate ring gave the aminol (9). Acylation of the free C-1-amino group with (S)-4-amino-2-hydroxybutyric acid and hydrogenation of the azido group led to 11 Preparation of 4′,6′-di-O-methyllividomycin A (13) was also described.
The Rearrangement of 10-Bromo-10,11-dihydrodibenzo[b,f]thiepin-11-one and Related Compounds in an Alkaline Solution
Authors: Ueda Ikuo
Published: July 2006

The reaction of 10-bromo-10,11-dihydrodibenzo[b,f]thiepin-11-one (1) with sodium methoxide in methanol has been shown to lead to thioxanthone (4) and 10-hydroxy-10,11-dihydrodibenzo[b,f]thiepin-11-one (5). If the reaction of 1 in an aqueous sodium hydroxide solution is carried out, six products, 4, 5, 9-hydroxy-thioxanthene-9-carboxylic acid (6), thioxanthene-9-carboxylic acid (7), thioxanthene (8), and 10,11-dihydrodibenzo [b,f]thiepin-10-one (9), are formed. The structures of the products were established by elementary analysis, by an examination of the spectral data, by gas chromatography, and by an independent synthesis. The results were discussed in terms of the mechanism proposed.
The Formation of Ethers from Nerol and l-Linalool in the Presence of Boron Trifluoride Etherate
Authors: Nagai Kimiko
Published: July 2006

Upon treatment with boron trifluoride etherate at room temperature, dl-linaloyl neryl, dl-geranyl linaloyl, dl-neryl α-terpenyl, and dineryl ethers were obtained from nerol and linaloyl neryl, l-geranyl linaloyl, dl-neryl α-terpenyl, and l-linaloyl piperityl ethers, from l-linalool. Of these ethers, linaloyl piperityl ether was thought to be formed by the cyclization of linaloyl neryl and geranyl linaloyl ethers.
The Reaction of 2,4-Dehydrohomoadamantane: The Synthesis of Several 2-Mono- and 2,4-Di-substituted Homoadamantanes
Authors: Yamaguchi Ryohei , Katsushima Takeo , Kawanisi Mituyosi
Published: July 2006

The synthesis of several 2-mono- and 2,4-di-substituted homoadamantane derivatives is described. The photobromination of 2,4-dehydrohomoadamantane (I) at −78 °C gave e,a- and e,e-2,4-dibromohomoadamantanes (IIa and IIb). The treatment of a mixture of IIa and IIb with t-BuOK in HMPT gave e-2-bromohomoadamant-4-ene (IV) in an 84% yield. The methanolysis and hydrolysis of IV gave e-2-methoxyhomoadamant-4-ene (V) and e-2-hydroxyhomoadamant-4-ene (VI), with a retention of the configuration, in 90 and 99% yields respectively. The oxidation of VI with the CrO3-pyridine complex gave homoadamant-4-en-2-one (VII) in a 94% yield. The reduction of VII with LiAlH4 gave a-2-hydroxyhomoadamant-4-ene (VIII). The catalytic hydrogenations of VI, VII, and VIII gave e-2-hydroxyhomoadamantane (IX), homoadamantan-2-one (X), and a-2-hydroxyhomo-adamantane (XI) respectively. The possibility that a homoallylic cation (XII) intervenes in the solvolysis of IV is proposed.
The Photoreactions of 2,3-Dicyanobarrelene
Authors: Saito Katsuhiro , Mukai Toshio
Published: July 2006

The direct irradiation of 2,3-dicyanobarrelene (II) provided 1,2-dicyanocyclooctatetraene (III). On the other hand, the acetone-sensitized photoreaction of II afforded semibullvalene derivatives (IV and V). Investigations of their NMR spectra clarified that IV completely degenerates, whereas V inclines to the favorable form of the valence isomers.
The Molecular and Crystal Structure of Dl-3-Chloro-2,4-pentanediol
Authors: Kuribayashi Shunsuke
Published: July 2006

The crystal structure of Dl-3-chloro-2,4-pentanediol has been determined by X-ray analysis. The crystal is triclinic, with dimensions of a=6.573, b=8.991, c=6.243 Å, α=80.18°, β=94.25°, and γ=102.87°. The five carbon atoms have a TT conformation, and the two OH groups have intermolecular hydrogen bondings, whose distances are 2.75 Å and 2.80 Å respectively.
A Study of the Molecular Compound between Inosine and Tryptophan
Authors: Suzuki Yoshihisa , Hara Kentaro , Hirahara Tsuneo
Published: July 2006

Equilibria have been determined at 30 °C for the inosine-l-tryptophan–water and inosine–d-tryptophan–water systems. They show the formation of a molecular compound, which was demonstrated in U.S. Patent 3532684, over a wide range of variable ratios of the two components, inosine and tryptophan. The influence of some organic solvents on the formation of the molecular compound was examined, and it was shown that the water molecule is significantly involved in the formation of the crystalline molecular compound, and that solvent interactions play an important role. Similar crystalline molecular compounds were not formed by chemically closely related substances; the high specificity of the interaction between inosine and tryptophan was confirmed.
Radiation Chemical Studies with Cyclotron Beams. IV. The Effect of Water in the Heavy-ion Radiolysis of Liquid Acetone
Authors: Matsui Masao , Imamura Masashi
Published: July 2006

A study was made of the effect of water on the LET dependence of the product yields for liquid acetone. Acetone containing 2 wt% water was subjected to irradiation by energetic 4He, 12C, and 14N ions as well as by 60Co γ rays at room temperature; the LET range was up to 80 eV Å−1. A significant effect of water was observed above 50 eV Å−1, where G(H2) and G(CO) showed continuous increases with an increase in LET. For pure acetone, G(H2) and G(GO) showed their peak values at 50 eV Å−1, indicating a saturation of decomposition in the ionization track, as has been reported previously. The present results may be interpreted in terms of the hydrogen-bonded network formed by the addition of water; this will expand the reaction zone outside the track and result in increases in the product yields without any waste of excessive energy in the high-LET region.
The Partial Molal Volumes of Normal Chain Alcohols in Water–Ethanol Mixtures at 25 °C
Authors: Manabe Masahiro , Koda Masaharu
Published: July 2006

The partial molal volumes (\barV0) of n-alcohols (RmOH, m=1–7) at an infinitely dilute concentration in water–ethanol mixtures of various compositions have been determined by means of dilatometry. The \barV0 value does not depend on the concentration of the solute alcohol within the region studied in any composition of the solvent mixtures. The excess volume, the difference between \barV0 and the molal volume (V0), is negative and is at a minimum in water-rich mixtures (<16 wt% ethanol) for all of the alcohols studied. On the other hand, in the moderate composition range the excess volumes for R4OH and higher alcohols are positive and reach a maximum distinct from the disappearance of the maximum for R3OH and lower alcohols. The volumetric contribution of a methylene group (\barVme) to \barV0 was separately evaluated. From the results, a linear relation was found between \barV0 and the alkyl chain length of the alcohols in the mixtures of 0–8 and 55–100 wt% ethanol, while in the mixtures the relationship was rather quadratic. Such volumetric behavior was discussed on the basis of the structural properties of the water–ethanol mixtures.
Dufour Effect in Gases
Authors: Boushehri A , Afrashtehfar S
Published: July 2006

A study of the Dufour effect was made for five different gas mixtures: H2–N2, H2–O2, H2–N2O, He–N2O and He–O2. Measurements were made at 25 °C under 700 Torr. The values of the thermal diffusion factor were calculated for the above mixtures from the experimental data on the basis of the thermodynamics of irreversible processes.
The γ-Radiolysis of Liquid Nitrogen Containing Methane
Authors: Siderer Yona , Sato Shin
Published: July 2006

The γ-radiolysis of the liquid nitrogen–methane system has been investigated. As products, hydrogen cyanide, ethane, and the basic compounds were observed. The G(HCN) attained was 0.08 at higher concentrations of methane, while the G(basic compounds) was found to be in the order of 0.5. In order to explain these results, different precursors for the HCN and the basic compounds are considered.
Effects of HMPA in the Kharasch Type Reaction of Allylic Halides
Authors: Ohbe Yoshihiro , Matsuda Tsutomu
Published: July 2006

Addition of HMPA was found to bring about an increase of cross-coupling products in the transition metal catalyzed reaction of allylic chlorides (allyl, crotyl, and methallyl) with Grignard reagents, the effect being most significant in copper (II) chloride catalyzed reactions.
Studies of Bivalent Metal Complexes of 2-Acetylpyridine
Authors: Kidani Yoshinori , Noji Masahide , Koike Hisashi
Published: July 2006

Bivalent metal complexes of 2-acetylpyridine (abbreviated as 2AP), M(2AP)2X2, M being copper, nickel, cobalt, and zinc ions and X being chloride, bromide, and iodide ions, were synthesized in ethanol solutions. The far-infrared analyses were discussed with reference to their structures, which were determined by means of the magnetic moments and the diffuse reflectance spectra. Except for Co(2AP)2Cl2 and Co(2AP)2I2, an octahedral structure was suggested for the M(2AP)2X2 complexes. A tetrahedral structure was assigned to Co(2AP)2Cl2 and Co(2AP)2I2 on the basis of their magnetic moments of 4.55 and 4.25 B.M. respectively and the diffuse reflectance spectra. The stretching vibrations of metal-nitrogen, metal-oxygen, and metal-halogen have been discussed.
N-Alkyldiarylamines from 3-Alkyl-3-aryl-1-(2-carboxyphenyl)triazenes
Authors: Nakayama Jyuzo , Yoshida Masayuki , Simamura Osamu
Published: July 2006

Heating 3-alkyl-3-aryl-1-(2-carboxyphenyl)triazenes in organic media afforded N-alkyldiarylamines in good yields, thus providing a useful synthetic route to this type of amines.
Light Induced Hydrogen Isotope Exchange between Terephthalonitrile and Thiols
Authors: Yoshida Masayuki , Sakuragi Hirochika , Tanaka Itaru , Tokumaru Katsumi , Morikawa Naotake
Published: July 2006

Interaction of an excited singlet state of terephthalonitrile with thiol is shown to be responsible for the title reaction on the basis of higher reactivity of terephthalonitrile relative to benzene and efficient quenching of fluorescene from terephthalonitrile by thiols.
Di-tert-butyl Thioketone
Authors: Ohno Atsuyoshi , Nakamura Kaoru , Nakazima Yukio , Oka Shinzaburo
Published: July 2006

Di-tert-butyl thioketone, a new aliphatic thioketone, has been prepared and its IR and UV spectral properties are studied.
The Structure of the Cyclodextrin Complex. I. The Crystal and Molecular Structure of the α-Cyclodextrin– p-Iodoaniline Complex
Authors: Harata Kazuaki
Published: July 2006

The crystal structure of the α-cyclodextrin–p-iodoaniline complex [(C6H10O5)6·C6H6NI·3H2O] has been determined by the X-ray method. The space group is P212121 with unit cell dimensions of a=13.659(2), b=15.413(3), and c=24.486(5) Å. The structure was solved by the heavy-atom method and refined by least-squares techniques. The final R-value was 0.072. The p-iodoaniline molecule is included in the cavity with its axis coincident with the axis of α-cyclodextrin; the iodobenzene group is situated in the cavity, while the amino group sticks out from the cavity. The shortest contact between the α-cyclodextrin molecule and the “guest” p-iodoaniline molecule is 3.25 Å, indicating that the latter is rigidly fixed in the cavity of the former. The distances between the amino group and the hydroxyl group are greater than 4.0 Å; this fact well explains why the catalytic ability of α-cyclodextrin is low in the hydrolysis of para-substituted phenyl esters.
The Crystal Structure of a Hofmann-en Type Pyrrole Clathrate, catena-μ-Ethylenediaminecadmium(II) catena-Tetra-μ-cyanonickelate(II)-Pyrrole (1/2)
Authors: Iwamoto Toschitake , Kiyoki Mamoru
Published: July 2006

The crystal structure of the titled pyrrole clathrate Cd(NH2CH2CH2NH2)Ni(CN)4·2C4H5N has been determined from three-dimensional X-ray data collected by counter techniques. The clathrate crystallizes in the orthorhombic space group Pmmm with a=7.618(3), b=7.641(10), c=7.861(4)Å, Z=1, Dm=1.69g cm−3, and Dx=1.70 g cm−3. The structure has been refined by the full-matrix least-squares procedure to a conventional R index (on F) of 0.057 for 462 observed reflections. The metal complex host-framework has a three-dimensional infinite cage structure where the ambident ethylenediamine molecules span Cd atoms at the corners of unit cell along the [001] direction and the ambident cyanide ions make infinite two-dimensional networks parallel to (001) by spanning the Cd atoms with the Ni atom at (1/2, 1/2, 0). The two crystallographically independent pyrrole molecules are enclathrated in the molecular spaces of the cages in the host-framework. The statistical dispositions observed for en and pyrrol molecules can be interpreted in terms of motional behavior of these molecules in the crystal.
The Infrared Dichroism and Molecular Orientation of Modifying Reagents, l-β-Phenyllactic Acid and l-β-Phenyl-α-alanine, in Thin Films on Nickel Metal Surfaces
Authors: Hatta Aritada , Suëtaka Wataru
Published: July 2006

The infrared absorption spectra of thin films of modifying reagents, l-β-phenyllactic acid and l-β-phenyl-α-alanine, formed on nickel metal plates were measured by the high-sensitivity reflection method. From the infrared dichroism in the reflection spectra, the molecular orientations in the thin films were deduced. The C=O and alcoholic O–H bonds of l-β-phenyllactic acid are oriented nearly vertical to the metal surface, whereas the carboxyl O–H bond and the benzene ring are parallel to the surface. The benzene ring and the C–N bond in l-β-phenyl-α-alanine are oriented nearly parallel to the metal surface, while the O···O axis of the carboxylate group is inclined to the surface.
Studies of Fragment Ion Distribution and Reaction by the Use of a Charge Spectrometer. VII. Fragmentation of Aliphatic Thiol Ions Produced by Charge Exchange with Positive Ions
Authors: Yoshihara Kenji , Kobayashi Masanao , Ikuta Shigeru , Shiokawa Takanobu
Published: July 2006

Fragmentation of molecular ions of methanethiol, ethanethiol, two kinds of propanethiols, and four kinds of butanethiols formed by charge exchange with positive ions has been studied using a tandem mass spectrometer. The results are compared with those of the corresponding alcohols obtained by Lindholm and coworkers, and similarities and differences between both series of ions are pointed out. The effect of the structure of the molecule on fragmentation is discussed. The fragment ions derived from primary scission are predicted on the basis of the EHMO calculation.
The Photo-oxygenation Reactions of Diethyl Ether, p-Phenylenediamine, and N,N-Dimethylaniline
Authors: Maeda Kojiro , Nakane Akihiro , Tsubomura Hiroshi
Published: July 2006

The products of photo-oxygenation reactions of ethyl–ether, p-phenylenediamine, and dimethylaniline were studied quantitatively and some radical intermediates were found by ESR measurements. The following quantum yields of the main products of these reactions were obtained: ethyl acetate (for ethyl ether), 0.49; p-benzoquinonediimine (for p-phenylenediamine), 0.01. As a possible reaction mechanism of the photo-oxygenation reactions of ethyl ether and p-phenylenediamine, it is proposed that at least part of the reaction is initiated by the charge transfer from the organic molecule to oxygen, followed by rapid proton detachment, yielding such radicals as EtO-\dotCHCH3 and \dotNHC6H4NH2 respectively.
Circular Dichroism Spectra of Unsym-cis(O) Isomers of (l-Alaninate-N-monoacetato) (diethylenetriamine)cobalt(III) Complexes
Authors: Okamoto Ken-ichi , Hidaka Jinsai , Shimura Yoichi
Published: July 2006

A couple of diastereomers, ΔΔΛ-R(N)–l(C) and ΔΛΛ-R(N)–l(C), of unsym-cis(O)-(l-alaninate-N-monoacetato)(diethylenetriamine)cobalt(III)(1+) complex was prepared and characterized from the circular dichroism spectra, which presented an example for the additivity between the circular dichroism contributions due to the configurational (ΔΔΛ and ΔΛΛ) and the vicinal (R(N)+l(C)) chiralities.
The Synthesis of 1,3-Thiazine-2,4-dithiones by the Reaction of Carbon Disulfide with Cyclic Ketones or Their Ketimines
Authors: Muraoka Motomu , Yamamoto Tatsuo , Takeshima Tatsuo
Published: July 2006

Cyclohexanone, 4-methylcyclohexanone, and phloroglucinol, when treated with carbon disulfide in the presence of triethylamine and aqueous ammonia, gave the respective 3,1-benzothiazine-2(1H),4-dithiones. Glutazines and 2-iminocyclopentanedithiocarboxylic acid underwent this reaction without ammonia.
Monomer–Isomerization Polymerization. XIV. Monomer–Isomerization Polymerization of 4-Methyl-2-pentene with Ziegler-Natta Catalyst
Authors: Otsu Takayuki , Endo Kiyoshi , Nagahama Hiroharu , Shimizu Akihiko
Published: July 2006

4-Methyl-2-pentene (4M2P) was found to polymerize in the presence of TiCl3–Al(C2H5)3 catalyst, and to yield a high molecular weight isotactic homopolymer of 4-methyl-1-pentene (4M1P). From the fact that the isomerizations from 4M2P to its positional isomers were also observed, it was concluded that this polymerization was induced by a monomer-isomerization polymerization mechanism, i.e. 4M2P isomerized first to 4M1P, which then homopolymerized. The rates of both polymerization and isomerization were affected by the Al/Ti molar ratio of catalyst system, and by the addition of transition metal compounds such as nickel acetylacetonate [Ni(acac)2]. It was concluded that the maximum rates were observed at Al/Ti=3 and Ni/Ti=0.2 in molar ratio.
The Facile Syntheses of Aldehydes and Aldehydic Acids from Carboxylic Acid Anhydrides Using Disodium Tetracarbonylferrate (–II)
Authors: Watanabe Yoshihisa , Yamashita Masakazu , Mitsudo Take-aki , Igami Mineo , Takegami Yoshinobu
Published: July 2006

Disodium tetracarbonylferrate reacts readily with aliphatic and aromatic carboxylic acid anhydrides under mild conditions; the corresponding aldehydes are formed in high yields by quenching the reaction solution with acetic acid. Intermolecular anhydrides give aldehydes and acids, and intramolecular ones give aldehydic acids. The reaction mechanism via acylcarbonylferrates is assumed.
Eine Ableitung aus der Hypothese über den Litheffekt
Authors: Suga Tsuneo
Published: July 2006

In früheren Arbeiten wurde der Mechanismus der Lithentwicklung und die Hypothese über die Entstehung des Litheffekts diskutiert. Nach dieser Hypothese ist für einen bildscharfen Litheffekt eine richtige Balance zwischen der Entwickelbarkeit der stärker belichteten Bildkeime und der Oxydierbarkeit der schwächer belichteten wichtig. Damit wurde der gute Litheffekt der Chlorbromsilber-Emulsion mit hohem Chloridanteil und der Litheffekt der Bromjodsilber-Emulsion mit niedrigem Jodidanteil gut erklärt. In der vorliegenden Arbeit wurde eine steile Gradation einer Bromjodsilber-Emulsion aus der Ableitung der Hypothese versucht. Die steile Gradation der Bromjodsilber-Emulsion, die man in Gegenwart von Rhodanid im Entwickler an Steile von Bromid erhielt, wurde der ,,Redox-Lith-Effekt“ der Bromjodsilber-Emulsion genannt.
Crystal and Molecular Structure of Potassium Acetylacetonate Hemihydrate
Authors: Shibata Shuzo , Onuma Shigeki , Matsui Yukinori , Motegi Shoichi
Published: July 2006

The crystal structure of potassium acetylacetonate hemihydrate, KC5H7O2· 1/2H2O, has been determined by X-ray diffraction method. Crystals are triclinic with space group P\barl, a=10.86, b=8.74, c=7.45 Å, α=90.5, β=95.8, γ=91.9°, and Z=4. The final R value was 0.109 for 1589 visually estimated reflection data. Each potassium ion is surrounded by seven oxygen atoms, at distances of 2.65 to 3.05 Å, six of which belong to four acetylacetone anions and the rest is a water molecule. The bond lengths and angles of the acetylacetone anion are very similar to those of acetylacetone groups in heavy metal chelates, but differ from those of the free molecule of acetylacetone.
The Spectroscopic Study on the Dimerization of Pyridine Derivatives on the Surfaces of MgO, CaO and SrO
Authors: Iizuka Tokio , Tanabe Kozo
Published: July 2006

The adsorption and dimerization of pyridine derivatives on MgO, CaO, and SrO were studied by ESR and visible absorption spectrometries. Adsorbed pyridine on the oxides was found to give an ESR signal of five lines and 580 nm absorption spectrum which were attributed to dipyridyl anion radical. The deuterium isotope effects for the formation of dipyridyl anion radicals were observed on MgO and CaO, but not on strong basic oxide, SrO. Methylpyridines adsorbed on MgO gave the same species as pyridine by the irradiation of light (λ>370 nm). From these facts, the surface intermediates for the dimerization reaction were discussed. When the adsorbed species were exposed to oxygen molecule, the dipyridyl anion radicals faded away and the ESR spectra attributed to the O2− ion were observed.
Studies of the Solvent Dyeing of Poly(ethylene terephthalate) with Disperse Dyes from Trichloroethylene and Isooctane
Authors: Morita Zenzo , Hiraoka Shinji , Yamamori Toshiyasu , Motomura Hiromi
Published: July 2006

The diffusion of 1,4-dihydroxyanthraquinone and C. I. Disperse Orange 3 in poly(ethylene terephthalate) (PET) from the trichloroethylene (TRI) and isooctance (ISO) dyebath was investigated by the method of the cylindrical film-roll. The stability of PET in TRI and ISO at high temperatures was also examined. The degradation of PET by solvents was in the following order: water>TRI>tetrachloroethylene (TCE) and ISO. The diffusion coefficients of Orange 3 from various solvents at 90°C were in the order: TRI>TCE>water>ISO. The activation energy of diffusion from ISO was much larger than that from TRI, the latter being nearly identical to that from TCE. The Arrhenius plots of the diffusion coefficients in PET indicated some transitions. The glass transition temperature of PET in TRI was lower than that in TCE. The diffusion coefficient and the surface concentration of Orange 3 from ISO were increased by the addition of water, while those from TRI were not changed within the range of experimental error.
A Photoconductivity Study of Trapped Ionic Species in γ-Irradiated Ethylcyclohexane Glass at 77 K
Authors: Kato Noriyuki , Fueki Kenji , Kuri Zen-ichiro
Published: July 2006

A photoconductivity study has been made of trapped ionic species in γ-irradiated ethylcyclohexane glass at 77 K. The photocurrent peak initially increases with an increase in the dose, reaches a maximum, and then decreases with a further increase in the dose. The experimental results indicate that the photocurrent vs. dose curve is probably affected by the radiolysis products. The photocurrents of γ-irradiated ethylcyclohexane–cyclopentane and 3-methylpentane glasses were also measured in the presence of biphenyl. It has been observed that electrons can be transferred almost reversibly between the biphenyl molecules and solvent traps. An analysis of the experimental data shows that only a very small fraction of the trapped electrons are responsible for the observed photoconductivity. A procedure is developed for estimating the lifetime of mobile electrons in glassy matrices.