bluuebunny/crossref_metadata_2025_split huggingface dataset:
Rotatory Dispersion and Stereochemistry of Organic Compounds. XVI. Carbonylphenyl Glucosides
Authors: Tsuzuki Yojiro , Kataoka Shintaro , Funayama Minako , Satsumabayashi Koko 
Published: July 2006

Abstract
Rotatory dispersion, circular dichroism and ultraviolet absorption of six kinds of carbonylphenyl tetraacetyl glucoside (carbonyl=o- and p-CHO, o- and p-COCH3, o- and p-COC2H5) and their deacetylation products were measured, and the optical rotatory contributions of carbonyl groups were investigated, especially with respect to the effect of the bulk and position of the substituent. This led to the conclusion that all the absorption bands due to the n→π* and π→π* transitions are optically active. Anomaly was also observed in the o-substitution products, thus making the general effect of electrophilic substituents on optical rotation definite, viz., that all the Cotton effects of the longer wavelength (due to the n→π* transition) are negative in p-carbonylphenyl β-glucosides, and in good accordance with the optical contribution of C1-configuration, but optical anomaly was invariably observed with the o-isomers which displayed positive Cotton effects. This rule in rotatory dispersion holds with the deacetylated compounds, in contrast to the deacetylated o-nitrophenyl glucosides (in this sense o-nitro group is anomalous). Some regularities were found with the Cotton effects due to the π→π* transition and the effect of the bulk of the carbonyl groups was discussed.
Condensation Reactions of Sulfonylcarbanion
Authors: Yamamoto Yasusi , Nisimura Tetuya , Nozaki Hitosi 
Published: July 2006

Abstract
Phenylsulfonylcarbanion PhSO2CH2− reacts with anthracene and acridine in HMPA to afford methylated products much as does methylsulfinylcarbanion MeSOCH2− in DMSO. The reaction mechanism is examined by following the change in the D-content during the reaction of 9-deuterioanthracene. The transformation of the negatively-charged σ-complex into the methylated product involves the concerted occurrence of a hydride shift and the elimination of the sulfinate anion. Meanwhile, the reaction of this carbanion with anthracene at a higher temperature yields the ethylated products of 9-ethyl-10-methyl- and 9,10-diethylanthracene besides 9,10-dimethylanthracene. Other condensation reactions of the carbanion investigated are those with (a) Ph2C=CH2, (b) PhC≡Cph, (c) Ph2CO, (d) PhCOCOPh, and (e) 2-aminobenzophenone, the main products being (a) (Remark: Graphics omitted.), (b) Ph2C=C(Ph)Me, (c) Ph2C(OH)CH2CH2SO2Ph and Ph2C=CHCH2SO2Ph, (d) PhCOCH2SO2Ph and PhCOOH, and (e) 3-phenylindole respectively.
The Crystal Structure and Nonstoichiometry of Rare Earth Oxyfluoride
Authors: Niihara Koichi , Yajima Seishi 
Published: July 2006

Abstract
Oxyfluoride phases for the rare earth Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Y have been prepared by heating a mixture of lanthanon fluorides, LnF3, and lanthanon oxides, Ln2O3. Three phases were identified. The rhombohedral phases, LnOF, have a stoichiometric composition, and the tetragonal phases, Ln4O3F6, have a comparatively large nonstoichiometric composition range. The third cubic phase, with a fluorite-type structure, was observed in the SmOF-Sm4O3F6 region after quenching from a high temperature. This establishes that both the rhombohedral SmOF and the tetragonal Sm4O3F6 transform to the cubic phase and form a complete solid solution in the high-temperature range. It is postulated that the rhombohedral and tetragonal phases are pseudo-cubic from the fact that the diffraction patterns of these two phases are closely similar to that of the fluorite type.
The Effect of Pressure on the Electronic Absorption Spectra of Alkali Metal Cation-Chloranil and -Bromanil Anion Radical Salts, and the Dimerization of the Chloranil Anion Radical in Solution
Authors: Sakai Nobuko , Shirotani Ichimin , Minomura Shigeru 
Published: July 2006

Abstract
The pressure dependence, up to 7 kbar, of the electronic absorption spectra of ion-radical salts composed of the alkali metal cation and the chloranil or bromanil anion radical in the crystalline state at room temperature, and the temperature dependence, down to 134°K, of the dimerization of chloranil anions in an ethanol solution at 1 bar have been studied. The absorption band in the visible region shows a blue shift with an increase in the pressure for Li+ and Na+ salts, while for K+ and Rb+ salts the spectra are insensitive to the pressure. The anion radicals seem to be in the dimeric electronic state for the former and to be in the monomeric state for the latter, in the crystalline state.
Study of Hydration and Association of Ions in Solution. I. Chromatographic and Electrophoretic Behaviors of Hexamminetype Cobalt(III) Complexes in Aqueous Solutions of Various Electrolytes
Authors: Yoneda Hayami , Muto Masayuki , Baba Tetsuo , Miura Takao 
Published: July 2006

Abstract
The dissolved state of ions in solution was investigated through the study of separation mechanism of a series of tervalent hexammine-type cobalt(III) complexes in thin-layer chromatography and in electrophoresis. The results obtained are summarized as follows. In the case of strongly hydrated complexes, a strongly hydrated anion has a greater tendency towards association than a weakly hydrated anion. On the contrary, in the weakly hydrated complexes, a weakly hydrated anion is associated more easily than a strongly hydrated anion. From these findings, ionic association was presumed to occur through direct contact of a complex cation and an anion.
A Proton Magnetic Resonance Study of Cobalt(III) Complexes Containing 1,10-Phenanthroline and Ethylenediamine
Authors: Ito Haruko , Fujita Junnosuke , Ito Tasuku 
Published: July 2006

Abstract
The proton magnetic resonance (PMR) spectra of the phenanthroline ligand in [Co(phen)3]Cl3, [Co(phen)2-(en)]Cl3 (new complex) and [Co(phen)(en)2]Cl3 were measured in deuterium oxide and analyzed as ABX systems. Significant up-field shifts of signals were observed only for the protons 2 and 9 of [Co(phen)3]3+ and the proton 2 of [Co(phen)2(en)]3+, not for the proton 9 of [Co(phen)2(en)]3+ nor the protons 2 and 9 of [Co(phen)(en)2]3+. The up-field shift was considered to be due to the effect of the ring current of the other phenanthroline ligands, since the protons 2 and 9 of [Co(phen)3]3+ and the proton 2 of [Co(phen)2(en)]3+ lies very close and to above the neighboring aromatic ligand.
Solvent Effects on ρ Values of the Hammett Equation. II.
Authors: Matsui Takeki , Tokura Niichiro 
Published: July 2006

Abstract
The rates of reactions of N,N-dimethylbenzylamine or its derivatives with methyl iodide in fourteen nonaqueous solvents at 30°C have been studied. The effects of the solvents on reactivities and Hammett’s ρ values have been examined. For establishing the relationship between ρ and solvent polarity, a unique solvent parameter for reactivity ξ0 was defined, which measures the relative solvent polarity in determining the order of reaction rate with respect to solvent. There is a linear relationship between ρ and ξ0, but protic and aromatic solvents show deviation from this relation in a particular way. The liner relationship provides a common basis for explaining both substituent and solvent effects. This suggests the importance of solvent reorientation accompanied by an activation process. It is argued that the hydrogen-bonded solvation of reactant amines and solvation of the leaving group are responsible for abnormal behaviors in protic and aromatic solvents.
Calorimetric Study of Polystyrenes of Low Molecular Weight
Authors: Morimoto Satoshi 
Published: July 2006

Abstract
Heats of mixing ΔHM at infinite dilution and integral heats of dilution ΔHd were directly measured for the systems of atactic polystyrenes (PSt: MW≤104, prepared by Pressure Chemical Co.) with benzene, toluene, and chloroform. The results are summarized as follows: (1) ΔHM and ΔHd decrease remarkably with the molecular weight of PSt in all solvents used. (2) The glass energies of the samples treated under the same thermal conditions were investigated and the large difference of heat capacities between liquid and glassy state of PSt was observed in the low molecular weight region. (3) Schulz’s theory of osmotic second virial coefficient of athermal polymer solutions was found to agree, to a good approximation, with the differential heat ‾ΔH1 of dilution in toluene in the molecular weight region between 103 and 104. (4) The NMR and the X-ray diffraction analyses were performed for the PSt oligomer liquid (MW 600). All alkyl end group of molecules and an order formation in the liquid were observed. They are discussed in terms of calorimetric data.
Brönsted and Lewis Acidity of Solid Nickel Sulfate
Authors: Hattori Hideshi , Miyashita Shun-itsu , Tanabe Kozo 
Published: July 2006

Abstract
The distribution of Brönsted and Lewis acidities of nickel sulfates heat-treated at various temperatures in air or in a vacuum has been determined by observing the infrared spectra of pyridine adsorbed on the sulfates in the range 1300–1600 cm−1. It has been found that the Brönsted acidity increases with the rise of temperature of heat treatment in air, attains a maximum value at 250°C and then decreases, while the maximum of the Lewis acidity appears at a higher temperature (about 400°C), the sum of both acidities giving the total acidity measured by n-butylamine titration method. An experiment in a vacuum showed that Lewis acid is converted into Brönsted acid by the addition of water. The structural nature and the catalytic activity of the Brönsted and Lewis acid sites on nickel sulfate are discussed.
The Effect of Pressure on the Association of Dye Molecules in an Aqueous Solution
Authors: Suzuki Keizo , Tsuchiya Masao 
Published: July 2006

Abstract
The effect of pressure on the association of rhodamine B (RB) and methylene blue (MB) in water has been investigated on the basis of their absorption spectra under hydrostatic pressures up to 4500 atm at room temperatures. Pressure increases the association of these dyes. The volume changes accompanying the 2 monomer\ightleftarrowsdimer process are calculated. The values are −10.4 cc/mol and −10.6 cc/mol in RB and MB respectively. These negative values are inconsistent with the suggestions by Rohatgi and Singhal and by Mukerjee and Ghosh that hydrophobic bonds are responsible for the associations of RB and MB. It is more plausible to assume that the hydrogen bond is the main binding force in the dye associations. London’s dispersion force and the increase in the dielectric constant of water with the increase in the pressure may also assist the dye associations.
Light-scattering Studies of the Interaction of Sodium Chondroitin Sulfate C with Bovine Serum Albumin
Authors: Nakagaki Masayuki , Sano Yoh 
Published: July 2006

Abstract
Angular light-scattering investigations were carried out in 0.01 m sodium chloride solutions at 25°C for various mixed solutions of bovine serum albumin (BSA) and chondroitin sulfate (Chs). The experimental values of molecular weight and of the molecular dimensions showed an entirely different tendency from the calculated values, and we may assume that there is no interaction between them. It has, therefore, been concluded that Chs interacts with BSA strongly and that a complex is formed between them. For the soluble complex thus formed, the number of the bound BSA molecules with one Chs molecule was expressed by a Langmuir-type equation as a function of the amount of excess BSA existing free in the solution. When the latter was sufficiently large, the number of bound BSA molecules per Chs molecule approached 20.6.
A Zimm plot of the complex was drawn, and the molecular weight, the radius of gyration, and the second virial coefficient of the complex were determined. It has been concluded from these results that the complex molecule has a long-like shape; the length was about 30% longer, but the diameter was about 6 times thicker, than the Chs molecule at the maximum binding of BSA.
The Reactions between a Rhenium Filament and Nitric Oxide at High Temperatures and Low Pressures
Authors: Tamura Teijiro 
Published: July 2006

Abstract
The rates of the reaction of rhenium with nitric oxide under a filament temperature of (1300–1800)°K and a nitric oxide pressure of (3×10−5–1×10−3)Torr have been measured by a static method. The rate of the reaction increases with an increase in the temperature, and the apparent activation energy is 24 kcal/mol. The rate of the reaction is proportional to the nitric oxide pressure and independent of the nitrogen pressure. The apparent compositions of the rhenium oxide produced in the reaction have been determined from the weight change in the rhenium filament and from the amount of nitric oxide consumed in the temperature range of (1300–2100)°K. The ReO3 and Re2O7 were formed at lower temperatures and at higher temperatures respectively. The Re2O7 was presumed to be formed by the oxidation of the ReO3 deposited on the vessel wall with atomic oxygen evolved in a high-temperature range.
Effects of Chain Molecules on the Temperature of the Maximum Density of Water
Authors: Sakurai Masao , Komatsu Tsuyoshi , Nakagawa Tsurutaro 
Published: July 2006

Abstract
The shifts in the temperature of the maximum density of water produced by the addition of small amounts of oligomers of polyethylene glycol and polyethylenimine and other related compounds were determined by dilatometry. These effects were interpreted in terms of the change in the structure of water around the various solute molecules in connection with their chain length. It was found that, as the chain length increases, the extent of the modification of the water structure by the chain molecules decreases because of the hydrophobic contact between ethylene groups. The apparent specific expansibility of the solute in the neighbourhood of 4°C was also evaluated as a function of the concentration.
The Physical Properties of the Anion Radical Salts Derived from 3,5,3′,5′-Tetrachloro-4,4′-diphenoquinone and 3,5,3′,5′-Tetrabromo-4,4′-diphenoquinone
Authors: Iida Yôichi 
Published: July 2006

Abstract
The anion radical salts derived from 3,5,3′,5′-tetrachloro-4,4′-diphenoquinone and 3,5,3′,5′-tetrabromo-4,4′-diphenoquinone were prepared. The absorption spectra in solution and the solid-state spectra were examined in order to study the solid-state properties characteristic of the anion radical salts. The measurements of the static magnetic susceptibilities and the electrical resistivities were also useful for this purpose. These physical properties were found to be based on the charge-transfer interaction between the anion radical molecules. It was suggested that, in these solid anion radical salts, the anion radical molecules might be stacked by a unique face-to-face arrangement in groups of two or an infinite number of molecular systems.
The Chemical Structures of Glasses of the NaPO3-Sb2O3 and NaPO3-Sb2O5 Systems
Authors: Watanabe Makoto , Kato Mineo 
Published: July 2006

Abstract
Glassy substances of the NaPO3-Sb2O3 and NaPO3-Sb2O5 systems with P/Sb ratios in the range from 5.0 to 300 were prepared by heating NaPO3 and Sb2O3, or Sb2O5 at 1000°C, and by then quenching the melts of the mixtures. The condensed phosphates were separated by paper-chromatographic analysis and determined colorimetrically, and the average degree of polymerization of the phosphates was measured by the pH-titration method. From these results, it has been found that the degree of polymerization of the phosphates increased with the increase in the P/Sb ratio. When the glassy samples of both the systems were treated with water, antimony trioxide was deposited. The results show that, in the glassy samples of both the systems, the valency of antimony is three, assuming that the glasses have the P–O–P, P–O−, P–O–Sb, and Sb–O− linkages, a theoretical treatment of the degree of polymerization of condensed phosphates has been made and compared with the experimental data. It has been concluded that the glasses of both the systems with P/Sb ratios larger than 5.0 have P–O–P, P–O−, and P–O–Sb linkages.
Derivatographic Studies on Transition Metal Complexes. VII.Thermal cis, trans-to-trans, cis Isomerization of [CoCl2(NH3)2en]Br·H2O in Solid Phase
Authors: Tsuchiya Ryokichi , Suzuki Masatatsu , Kyuno Eishin 
Published: July 2006

Abstract
The cis, trans-to-trans, cis isomerization as well as dehydration of [CoCl2(NH3)2en]Br·H2O were investigated by using derivatographic, isothermal, and sealed tube methods. Isomerization in a solid phase proceeded regardless of whether its state was monohydrate or anhydride. Two distinct processes were found for isomerization, one being accompanied by the liberation of water of crystallization and the other taking place after complete liberation of water of crystallization. Both reactions were of the first order. The thermochemical functions were obtained to be ΔH=(12±2) kcal/mol, E\eweq=(28±3) kcal/mol and ΔS\eweq=(−10±4) e.u. for dehydration. The values E\eweq=(28±3) kcal/mol and S\eweq(−4±2) e.u. were estimated for isomerization in the first process, and E\eweq=(28±3) kcal/mol and ΔS\eweq=(−12±3) e.u. for that in the second process. As a possible reaction mechanism for isomerization, an “aquation-anation mechanism” was introduced for the first process and an “intramolecular mechanism” for the second.
Formation of Uranium Sesquicarbide by the Partial Decarburization of Uranium Dicarbide Using Magnesium Oxide
Authors: Tagawa Hiroaki 
Published: July 2006

Abstract
Formation of U2C3 by the reaction of UC2 with MgO has been studied by means of chemical and X-ray analyses at temperatures 1450–1700°C in vacuo. The reaction was found to proceed generating CO and Mg vapor and to produce U2C3. The decarburization is represented by
2UC2+MgO→U2C3+CO+Mg.
UO2 and UC were formed as the intermediate compounds. The amount of UO2 was nearly equal to that formed by the reaction: UC2+4MgO=UO2+2CO+4Mg. The lattice parameter of U2C3 was 8.0890 Å. The lattice parameters of UC2 and UC varied with the reaction time. The main reaction sequence was suggested to be:
1⁄4UC2+MgO=1⁄4UO2+1⁄2CO+Mg
7⁄4UC2+1⁄4UO2=U2C3+1⁄2CO.
The experimental results were in good agreement with those obtained by thermochemical calculation.
Stereochemical Studies of Metal Chelates. VII. The Preparation, Stereochemistry, and Circular Dichloism of Dinitrocobalt(III) Complexes with (3S, 8S)-Dimethyltriethylenetetramine and Related Tetramines
Authors: Saburi Masahiko , Sawai Tsutomu , Yoshikawa Sadao 
Published: July 2006

Abstract
Dinitrocobalt(III) complexes with (3S,8S)-dimethyltriethylenetetramine((3S,8S)-dimetrien) and related ligands were prepared and separated into the geometrical isomers. The cis-α and cis-β isomers of the (3S,8S)-dimetrien complex gave rise to the Λ and Δ isomers respectively. A similar stereospecificity could be observed for the other dissymmetric ligands employed in this study. The circular dichroism (CD) spectra of the cis-β isomers showed three kinds of patterns, which were related to the structural features of the complexes.
Behavior of Alkali Metals in the Hydrogen Flame Ionization Detector for Ultra-Micro Analysis of Alkali and Alkaline Earth Metals
Authors: Yamada Masaaki , Suzuki Shigetaka , Araki Shun 
Published: July 2006

Abstract
Behavior of alkali metals in the small hydrogen flame for ultra-micro analysis of alkali and alkaline earth metals were investigated. Distribution of free neutral atoms and formation of alkali hydroxides were studied by the photometric method, distribution of charged particles was determined by the Langmuir probe method, and confirmation of whether negative-charged particles are mostly electrons or negative ions by the sheath method. It was found that only lithium formed hydroxide in the flame, ionization chiefly occurred in the part 0–5 mm above the jet, and that most of negative-charged particles are not electrons but negative ions.
A MO-theoretical Study of the Catalytic Activity of Onium Compounds in the Liquid-phase Oxidation
Authors: Ohkubo Katsutoshi , Kanaeda Hirokazu 
Published: July 2006

Abstract
A theoretical study with the extended Hückel method augmented by d-orbitals was undertaken in order to elucidate the relation between the electronic structures of various onium compounds and their catalytic activities in the liquid-phase oxidation of hydrocarbons. There were several findings. Firstly, the differences in the catalytic activities of the carbonium, ammonium, and oxonium compounds are ascribed to those in the AO populations of the pz-orbitals on their central atoms. Secondly, the distinguished activities of sulfonium and phosphonium compounds were well explained by the partially-occupied sulfur or phosphorus 3d-orbitals, in which the dxz (or dyz) orbital is utilized most effectively for the interaction with the (1πg)z orbital of O2. Finally, the relatively low activities of arsonium and telluronium compounds are ascribed to the vacant and diffused 4d or 5d orbitals, while the appreciable activity of the selenonium compound is caused by the partial electron-occupancy of the 4dxz (or 4dyz) orbital of the central selenium.
Synthesis of 5,5-Dimethyl-4-acetoxy-2-cyclopentenone and 5-Methyl-t-5-acetoxymethyl-r-4-acetoxy-2-cyclopentenone Intermediates for Illudin M and S
Authors: Matsumoto Takeshi , Shirahama Haruhisa , Ichihara Akitami , Shin Hyonsobb , Kagawa Shohei , Sakan Fujio , Nishida Shuji , Matsumoto Sojiro , Saito Kenichi , Hashimoto Hisanobu 
Published: July 2006

Abstract
5,5-Dimethyl-4-acetoxy-2-cyclopentenone and 5-methyl-t-5-acetoxymethyl-r-4-acetoxy-2-cyclopentenone, intermediates for illudin M and S respectively, have been synthesized from ethyl adipate.
Photochemical Reactions of Aromatic Compounds. IX. Photochemical Reactions of Dimethylaniline with Halobenzenes
Authors: Pac Chyongjin , Tosa Takafumi , Sakurai Hiroshi 
Published: July 2006

Abstract
Irradiation of methanolic solutions of DMA containing halobenzenes (chlorobenzene, bromobenzene and iodobenzene) and triethylamine (TEA) gave TEA hydrohalides in quantitative yields along with benzene (II), di-phenyl, N-methylaniline, o- and p-dimethylaminodiphenyls (IV and V). From the properties of the products and spectroscopic and kinetic data, it was suggested that the reactions took place by way of electron transfer from DMA to halobenzenes. The electron transfer reactions were classified into a short range type (chlorobenzene and bromobenzene) and a long range type (iodobenzene) on the basis of the product ratio (IV+V)/II and the proportion of benzene-d1 in the benzene fraction obtained from the photoreactions of DMA-d6 with halobenzenes. From the kinetic and fluorescence data, an exciplex mechanism was suggested for the photoreactions with chlorobenzene and bromobenzene, and a direct electron transfer mechanism in the case of iodobenzene.
The Photochemical Reaction of Some Ketoximes and Their Derivatives
Authors: Sato Tadashi , Inoue Takeshi , Yamamoto Koichi 
Published: July 2006

Abstract
The photochemical reaction of mesityl oxide oxime was investigated. In protic solvents, the reaction via oxaziridine proceeded, while in aprotic solvents, syn-anti isomerization was the main reaction pattern. A cyclobutanol formation, which is a new type of reaction in the oxime system, was observed. The photochemical reactions on some other ketoximes and their derivatives were also investigated.
Palladium-catalyzed Reactions of 1,3-Dienes with Active Methylene Compounds. IV. Palladium-diphosphine Complex Catalysts
Authors: Takahashi Kuniyuki , Miyake Akihisa , Hata Go 
Published: July 2006

Abstract
Active methylene compounds, such as acetylacetone and ethyl acetoacetate, reacted with 1,3-butadiene in the presence of palladium-diphosphine complex catalysts to yield two 1 : 1 adducts, 1 and 2. Primary and secondary amines also afforded two 1 : 1 adducts, 10 and 11. Isoprene, 1,3-pentadiene, and 2,4-hexadiene also reacted with the active methylene compounds and the amines in a manner similar to that of 1,3-butadiene. The most effective and easily available catalyst is the combination of PdBr2(Ph2PCH2CH2PPh2)2 and sodium phenoxide.