bluuebunny/crossref_metadata_2025 huggingface dataset:
Rotatory Dispersion and Stereochemistry of Organic Compounds. XVI. Carbonylphenyl Glucosides
Authors: Tsuzuki Yojiro , Kataoka Shintaro , Funayama Minako , Satsumabayashi Koko
Published: July 2006

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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.
Charge-transfer Interaction and Chemical Reaction. IV. Reactions of para-Substituted Derivatives of Aniline with Chloranil
Authors: Nogami Takashi , Yoshihara Keitaro , Nagakura Saburo
Published: July 2006

Interactions of chloranil with p-phenyIenediamine, N,N-dimethyl-p-phenyIenediamine, and N,N,N′,N′-tetramethyl-p-phenylenediamine were studied by measuring visible and ultraviolet absorption spectra at various temperatures between 77°K and 300°K. In an ether-isopropyl alcohol (3:1) mixed solvent, the p-phenylenediamine- and N,N-dimethyl-p-phenylenediamine-chloranil systems were led to the substitution reaction through the outer complex and the ionic species as reaction intermediates. In ethyl ether, the p-phenylenediamine- and N,N-dimethyl-p-phenylenediamine-chloranil systems were found to yield the inner complex and the substituted species through the outer complex, respectively. In the N,N,N′,N′-tetramethyl-p-phenylenediamine-chloranil system, the inner complex was found to be formed via a clustering of the outer complexes.

The interactions between aromatic amines and chloranil were found to be classified into the following three types: (a) the charge-transfer (outer or inner) complex is formed between an electron donor and an acceptor and no further reaction proceeds; (b) the substitution reaction occurs through the outer and inner complexes; (c) the substitution reaction occurs through the outer complex and ionic species. The difference in the reactivities between mtfta-substituted derivatives of aniline and ortho- and para-substituted ones was explained by taking the π-electron density on the amino group into account.
Oxygen Exchange of Benzenesulfinic Acids in Water
Authors: Kobayashi Michio , Minato Hiroshi , Ogi Yoshikuni
Published: July 2006

When arenesulfinic acids were heated in water (H218O, 1.52 atom%) at 90–100°C for several hours, the 18O contents of the disproportionation products (thiolsulfonate and sulfonic acid) and the sulfinic acid recovered were approximately the same. The rate of oxygen exchange of p-toluenesulfinic acid was much faster than that of methyl phenyl sulfoxide, whereas the rate of oxygen exchange of benzoic acid was much slower than that of benzaldehyde. A mechanism consistent with the kinetic results is proposed for the oxygen-exchange reaction, involving the formation of the sulfinic anhydride (sulfinylsulfone) as an intermediate.
The Infrared Spectra and the Antiferroelectric Phase Transition of Copper Formate Tetrahydrate
Authors: Hiraishi Jiro
Published: July 2006

The infrared spectra of copper formate tetrahydrate are measured in the frequency region from 4000 to 24 cm−1 at various temperatures. This compound is known to undergo an antiferroelectric phase transition at −37.7°C. The bands due to the librational and translational modes of the crystalline water molecules in the antiferroelectric phase are quite different from those in the paraelectric phase, while no appreciable differences between the spectra in the two phases are observed for other bands. Those facts agree with the results obtained by the crystallographic study, which show that the ordering of the orientation of the water molecules occurs at the phase transition. The similarity of the librational and the translational modes of the water molecules to those of ice is also discussed.
The Catalytic Oxidation of Carbon Monoxide on Zirconium Dioxide
Authors: Hamamura Takuya , Onishi Yoshito , Iizuka Yasuo
Published: July 2006

The catalytic oxidation of carbon monoxide on zirconium dioxide was kinetically examined in order to compare with the results of titanium dioxide. The experiment was carried out under gas pressures of 10−2−100 mmHg at 400–550°C. The reaction rate was proportional to PCO and did not depend upon PO2, and there was no retarding effect by carbon dioxide. The rate constant of this oxidation reaction almost agreed with that of the reduction of zirconium dioxide by carbon monoxide. The reaction mechanism could be explained in the same manner as that on titanium dioxide. The catalytic activity of zirconium dioxide for this reaction was almost the same as that of rutile. The activation energy was about 12.5 kcal/mol, and this value was intermediate between those of anatase and rutile. The same relation was obtained in the activation energies of the thermal desorption of surface oxygen from these catalysts.
Molecular Structure of Propane
Authors: Iijima Takao
Published: July 2006

The structure of propane has been investigated by gas electron diffraction. The thermal average distances rg and rα-angles determined with the estimated limits of error were: C—C=1.532±0.003 Å, C–H=1.107±0.005 Å, ∠CCC=112±1°, and ∠HCH(CH3)=107±3°. By combining the diffraction results with the microwave data, the zero-point average structure has also been determined.
Ionization Energies and Rydberg States of Tetraaminoethylenes
Authors: Nakato Yoshihiro , Ozaki Masaru , Tsubomura Hiroshi
Published: July 2006

Absorption spectra and photo-ionization curves of tetrakis (dimethylamino) ethylene, (TMAE), and 1,1′,3,3′-tetramethyl-Δ2,2′-bi(imidazolidine), (TMBI), have been studied. It has been found that these compounds have very low ionization potentials (about 5.4 eV), which are even comparable with that of the lithium atom. The first ionization potentials of these compounds are nearly the same, although both their absorption spectra and their photo-ionization curves are considerably different from each other. These results can be explained semi-quantitatively by use of the results of simple, semi-empirical molecular orbital calculation with inclusion of direct interaction between four lone-pair orbitals on the N atoms, which was found to be important at the “perpendicular” structure. The first absorption bands of these molecules are assigned to the Rydberg bands, lying quite unusually near the visible region. The quantum defect δ is found to be 0.7 for the lowest Rydberg state of TMAE. The size of the Rydberg orbital for this state is estimated to be 2.9 Å from the maximum radial density, which is comparable with the core size. Higher Rydberg series are also observed for TMBI.
The Effects of Pre-irradiation Treatments on the Chemical Behavior of 64Cu Recoil Atoms in Neutronirradiated Copper Phthalocyanine
Authors: Kudo Hiroshi
Published: July 2006

The chemical behavior of 64Cu recoil atoms was studied in copper phthalocyanine which had been quenched from an elevated temperature or exposed to 60Co γ-rays before the neutron irradiation. In the quenched β-crystal, the initial retention was found to increase with an increase in the temperature of pre-irradiation heating, while the plateau retention of the post-neutron annealing reaction decreased. These results were compared with those for cadmium phthalocyanine and were understood in terms of “dislocation” in the crystal, the recoil atoms being assumed to be trapped and stabilized in the “dislocation.” Although the variations were small, the irradiation with 60Co γ-rays caused a change in the chemical behavior of the recoil atom. The role of some radiation-induced species were discussed.
Polarographic Investigation of Biopolymers. II. Cu (II)-poly (α,l-Glutamic Acid) in the Helix-Coil Transition Region
Authors: Inoue Senkichi , Yamaoka Kiwamu , Miura Masaji
Published: July 2006

The pH-induced helix-coil transition of the complex of Cu(II)-poly(α,l-glutamic acid) was studied with polarographic method. The diffusion current was found to change very sharply in a narrow range of pH and this change depended on the amount of Cu(II) ions. The half-wave potential of the complex was also dependent on pH and mixing ratio. The effect of Cu(II) ions on the secondary structure of the polymer was discussed from the viewpoint that the helix-coil transition of PGA is responsible for the change of the mode of binding interaction between Cu(II) ions and PGA sites. Based on the data of diffusion currents versus mixing ratios, the helical fractions of the complex at pH 3.4 and 4.0 were evaluated to be 0.37 and 0.11, respectively. From a value of the diffusion coefficient of the complex at pH 5.0, the molecular size in a random-coil form was calculated to be approximately 70 Å in diameter. The coordination number of the complex in the coiled form depended on the mixing ratio; the number was 3.4 in excess of polymer and 0.2–0.3 for the mixing ratio between 3.2 and 13. These values were discussed in terms of the possible mechanism of coordination. Finally, the activation energy of diffusion was obtained for complexes in helical and random-coil forms.
An MO-theoretical Study of the Nucleophilic Bimolecular Ring-opening of Ethylene Oxide
Authors: Fujimoto Hiroshi , Katata Motohiro , Yamabe Shinichi , Fukui Kenichi
Published: July 2006

The results of an approximate molecular orbital (MO) calculation of the interaction energy of the ring-opening of ethylene oxide by a hydride ion are presented. The method of calculation is based upon the isolated-molecule approximation. The interaction energy was divided into the Coulomb, exchange, delocalization, and polarization interaction terms, and the changes in these four terms with the progress of the reaction were investigated. The wave function of the combined system of ethylene oxide and a hydride ion was obtained by the configuration interaction (CI) procedure. The changes in the electron populations of ethylene oxide and the hydride ion were calculated from the ground-state CI wave function. Among the unoccupied MO’s of ethylene oxide, two low-lying unoccupied MO’s were shown to be of special importance in the electron transfer from the attacking anion to ethylene oxide. The effect of the deformation of the molecular shape upon the interaction energy and the intermolecular bond formation is also discussed.
A Study on the Nature of the Electronic Absorption Bands of Formylpyrroles and Acetylpyrroles
Authors: Matsuo Taku , Shosenji Hideto
Published: July 2006

The electronic spectra of formyl- and acetylpyrroles were studied from both experimental and theoretical viewpoints. On the basis of the solvent effect and pH-dependence of the absorption spectra, the lowest energy transitions of 2- and 3-acetylpyrroles and the corresponding formylpyrroles, as well as the second lowest energy transitions of 3-acylpyrroles, were suggested to be accompanied by the electron-transfer from the pyrryl to carbonyl group. As to 1-acetylpyrrole (or 1-formylpyrrole), the longest wavelength absorption bands disappeared when the conjugation between the pyrryl and carbonyl groups were inhibited by steric hindrance. Solvent effects on the absorption band, however, were so small that the extent of electron-transfer was considered to change little during the transition. The results of VESCF MO calculations also supported the above suggestion based on experimental observations. The behaviors of the second lowest energy transitions of 1- and 2-acylpyrroles were too complicated to be accounted for straightforwardly.
Intermolecular Hydrogen Transfer Reactions in the Excited States of EDA-Complexes of Benzophenone with Aromatic Amines at Low Temperature
Authors: Arimitsu Satoshi , Tsubomura Hiroshi
Published: July 2006

Electronic absorption and emission spectra of the mixtures of benzophenone and aromatic amines have been studied in rigid solutions. From absorption spectral measurements, it has been concluded that benzophenone as an acceptor forms the molecular complexes with various aromatic amines as donors. Emission spectra different from those of the component molecules were observed at longer wavelengths in the same systems. The maxima of the anomalous emission spectra of these systems were found to shift slightly to lower frequencies with the decrease in the ionization potentials of donor molecules. On account of their decay times, the emissions may be ascribed to the phosphorescence of benzophenone-aromatic amine complexes. Photolysis of benzophenone-aromatic amine complexes in rigid matrices always resulted in the appearance of the visible absorption spectrum of benzoketyl radical, together with ESR spectra, the analysis of which indicated that there is an interacting pair of radicals which is in the combined triplet (S=1) state. From the evaluation of the zero field splitting constants, the average distances between the interacting radicals were estimated. These results suggest that intermolecular hydrogen atom transfer from aromatic amines to benzophenone occurs, yielding the ketyl and aromatic amine radicals which lie close to each other. The reaction was found to proceed by way of the lowest excited triplet state of benzophenone.
Thermodynamic Properties of an Aqueous Solution of Tetraethylene Glycol Diethyl Ether
Authors: Nakayama Haruo
Published: July 2006

The excess Gibbs energy of mixing, GE; the excess enthalpy of mixing, HE, and the excess volume of the mixing, VE, of the tetraethylene glycol diethyl ether+water system have been measured as functions of the composition at 25°C. The GE, which has been determined through the isopiestic measurement of the water activity, is positive over the entire range of composition and has its maximum at 40 mol% ether. As has been found for analogous systems, the s-curve of HE is again found; that is, HE is large and negative (exothermic) in the water-rich region and positive (endothermic) in the ether-rich region. The VE is negative over the whole range of composition and has a minimum at 23 mol% ether. These results are discussed in the light of the structural modifications of water in the immediate neighborhood of the ether molecule.
A Dilatometric Study of Compatible Polymer Mixtures
Authors: Akiyama Saburo
Published: July 2006

Polymer mixtures of poly(vinyl nitrate) (PVONO2), and poly(vinyl acetate) (PVOAc), which had previously been concluded to be compatible with each other, were investigated by the dilatometric method. As a result, a characteristic behavior of the mixtures was observed. Each mixture showed a single glass-transition temperature (Tg) over the whole range of composition; this temperature was higher than those of pure polymers in the middle region of composition. The transition temperatures of the mixtures obeyed a modified Gordon-Taylor expression. The thermal expansion coefficients of the mixtures are discussed in relation to the effect of blending.
Trace Analysis of Metals by ESR. I. Microdetermination of Copper by Means of Solvent Extraction of Copper(II) Diethyldithiocarbamate
Authors: Yamamoto Daijiro , Fukumoto Tuneo , Ikawa Noriaki
Published: July 2006

A new method was developed for the direct determination of copper using ESR. Cupric diethyldithiocarbamate complex dissolved in benzene shows a unique ESR spectrum. The bivalent complex in benzene gave a very strong ESR signal with intensity sensitive to 0.005 ppm of Cu(II)-ion. Thus the ESR signal can be utilized for the trace analysis of Cu(II)-ion. The ESR signal intensity was linear in the ranges 1.0–0.1 γ/ml and 0.1–0.01 γ/ml of Cu(II)-ion. Mg2+, Fe2+, Ba2+, Mn2+, Zn2+, Co2+, Pb2+, Ni2+, I−, Br−, and NO3− did not interfere with the determination, while Hg2+ and CN− did. Comparing this method with photometric determination, we see that a very low content of Cu(II)-ion can be determined with a very small amount of sample.
Nickel(II) Complexes of 1,5-Dialkyl-2,4-pentanediones
Authors: Yoshida Isao , Kobayashi Hiroshi , Ueno Keihei
Published: July 2006

Bis(heptane-3,5-dionato)nickel(II) monohydrate [Ni(DNPM)2·H2O], bis(nonane-4,6-dionato)nickel(II) monohydrate [Ni(DNBM)2·H2O], bis(2,6-dimethylheptane-3,5-dionato)nickel(II) monohydrate [Ni(DIBM)2·H2O], bis(2,8-dimethylnonane-4,6-dionato)nickel(II) monohydrate [Ni(DIVM)2·H2O] and bis(tridecane-6,8-dionato)nickel(II) monohydrate [Ni(DNCM)2·H2O] were prepared, and a dimeric octahedral structure was proposed for each of them by means of spectroscopic studies. These dimeric chelates, (NiL2·H2O)2 were stable in solid state, however they disproportionated in non-coordinating solvents to afford dimeric monohydrates, Ni2L4·H2O, and monomeric dihydrates, NiL2·2H2O. DTA studies show that these monohydrates dehydrate in two steps and that the temperature of dehydration decreases in the order of the ligands, DNPM, DNBM, DIBM, DIVM, and DNCM. The dehydrated chelates are green in the neighborhood of room temperature while they changed into red at an elevated temperature. This thermochromism indicates that the chelates are in the trimeric octahedral form at low temperature and in monomeric tetra-coordinated square planar form at high temperature. On the other hand a nickel(II) chelate of 2,2,6,6-tetramethylheptane-3,5-dione (DPVM) was obtained as a pentacoordinated monodioxane adduct from aqueous dioxane. The coordinated dioxane was readily released to afford a monomeric tetra-coordinate square planar, red colored complex, Ni(DPVM)2.
Reaction Rates and Mechanisms of the Formation of Gallium(III), Indium(III), and Thallium(III) Complexes with Semi-Xylenol Orange in Aqueous Solutions
Authors: Kawai Yoichi , Takahashi Tetsuro , Hayashi Katsuyuki , Imamura Taira , Nakayama Hiroaki , Fujimoto Masatoshi
Published: July 2006

The kinetics for the complex formation of Ga(III), In(III), and Tl(III) with Semi-Xylenol Orange (SXO) in acid solutions were studied by stopped-flow technique. Kinetic results are interpreted in terms of a two-step mechanism involving pre-equilibrium. The increase in the reaction rate with decreasing hydrogen ion concentration is interpreted as the sum of several parallel pathways including monohydroxo metal ions and a few charge types of the ligand. The mechanisms and the rates of the three different d10-system metal ions are discussed. The phenomena of the slower increase in absorbance of Ga(III)-SXO complex after the rapid increase and the slow color fading of Tl(III)-SXO complex are also discussed.
The Electrochemical Behavior of the Low-valent Transititon-metal Complexes. I. Nickel-2,2′-Dipyridyl Complexes.
Authors: Misono Akira , Uchida Yasuzo , Yamagishi Takamichi , Kageyama Hironori
Published: July 2006

The electrochemical behavior of zero-valent nickel-2,2′-dipyridyl complexes (Ni(dipy)2, Ni(CH2CHCN)2-(dipy), and Ni(NCCHCHCN)2(dipy)) was examined in a hexamethylphosphoric triamide solution by polarographic and ESR measurements. In the polarography, these complexes were first reduced at a very anodic potential (E1⁄2: about −0.6–−0.8 V vs. Ag wire). At this reduction step, the anion radical of the complex was observed for all the complexes by means of ESR analysis. The spectra of the anion radicals and their g-values suggested the localization of an unpaired electron on the ligand side. The addition of 2,2′-dipyridyl to the solution increased the height of the second wave, the half-wave potential of which was also more anodic than that of free 2,2′-dipyridyl, and the anion radical of 2,2′-dipyridyl was observed at this reduction step. It was concluded that the dianion species formed at the second reduction step dissociated to give the 2,2′-dipyridyl anion radical, and that the anion radical of the complex was reproduced in the presence of excess 2,2′-dipyridyl.
Stereochemical Studies of Metal Chelates. IX. The Preparation and Stereochemistry of Cobalt(III) Complexes Coordinated with the meso-Form of 3,6-Diaza-2,7-dimethyl-1,8-diaminooctane
Authors: Saburi Masahiko , Yoshikawa Sadao
Published: July 2006

The meso-form of 3,6-diaza-2,7-dimethyl-1,8-diaminooctane (meso-3,8-dimetrien), one of the triethylenetetramine derivatives, was prepared. Dinitro- and dichlorocobalt(III) complexes with this ligand were also prepared and characterized. The Λ-cis-β(SS) and/or the Δ-cis-β(RR) configuration were assigned to these complexes. The trans-dichlorocobalt(III) complex of meso-3,8-dimetrien derived from the cis-β-dichloro complex was determined to have the meso-trans configuration (the absolute configurations of the coordinated secondary nitrogen atoms were antimeric to each other, namely, R and S), on the basis of proton magnetic resonance measurements.
Chlorination of Olefins with Thallium(III) Chloride Tetrahydrate
Authors: Uemura Sakae , Sasaki Osamu , Okano Masaya
Published: July 2006

In CCl4, TlCl3·4H2O reacted with mono- and diolefins to give vic-dichlorinated compounds (I) in 20–41% yields together with monochlorinated ones (II). The yields of I were intensely increased by adding CuCl2·2H2O or FeCl3 and bubbling oxygen into the reaction system, although such additives alone gave none of I in CCl4. In acetic acid, the reaction gave diacetoxylated compound. As to the vic-dichlorination, it was proposed that the reacting species was a polarized form of dimeric TlCl3 and not free chlorine evolved from TlCl3·4H2O.
The Base-catalyzed Condensation of o-Nitropropiophenone
Authors: Sakan Takeo , Hayashi Shoji , Miwa Toshio
Published: July 2006

Treatment of o-nitropropiophenone with sodium acetylide in liquid ammonia at −70°C gave a yellow phenol, C18H18O3N2, as a major product. The permanganate oxidation of the phenol gave 2-(1-carbamoylethyl)-2-methyl-3-indolinone, which was synthesized independently. From this result and the spectral data, the structure of the phenol was postulated to be 1-(o-hydroxyphenyl) derivative of the above indolinone. The neutral fraction of the reaction mixture gave three new compounds: 3-(o-Nitrophenyl)-1-pentyn-3-ol, 2-methyl-2-(2-methyl-3-indolinon-2-yl)-3(2H)-benzofuranone, and 3,3a-dihydro-2-hydroxy-3,3a-dimethyl-2-(o-nitrophenyl)-4(2H)-isoxazolo[2,3-a]indolone. Their structures were assigned from their spectral data. A mechanism for the formation of these products as well as for the base-catalyzed condensation of o-nitroacetophenone is discussed.
Reactions of Aryloxycopper(I) with Organic Halides
Authors: Kawaki Takao , Hashimoto Harukichi
Published: July 2006

Some aryloxycoppers were synthesized by the interaction of phenylcopper with phenols and then characterized. The reaction of aryloxycopper and organic halide in diglyme generally gave the corresponding ether. From these and other results, it is suggested that aryloxycopper (I) is an intermediate in the Ullmann condensation, etc.
Oxidation by Transition Metal Complexes. III. Oxidation of Cinnamaldehyde Catalyzed by Rhodium Compounds
Authors: Takao Kiyotomi , Wayaku Masami , Fujiwara Yuzo , Imanaka Toshinobu , Teranishi Shiichiro
Published: July 2006

The catalytic activity of RhCl(PPh3)3 and RhCl(CO)(PPh3)2 for oxidations of styrene and cinnamaldehyde has been studied. Under oxygen atmosphere, these complexes can cause catalytically oxidation of cinnamaldehyde to give benzaldehyde, glyoxal, benzene and styrene. The reaction is complicated because decarbonylation reaction takes place with oxidation, and the carbonyl complex formed plays a catalytic role for the oxidation.
Mercaptoacetate Derivatives. I. Reaction of Thiocyanatoacetic Esters with Aldehydes
Authors: Hayashi Toshio
Published: July 2006

An equimolar reaction of thiocyanatoacetic esters with aromatic aldehydes in the presence of sodium hydride, followed by treatment with hydrogen chloride, led to a mixture of 4-alkoxycarbonyl-5-aryl-2-imino-1,3-oxathiolane hydrochloride (3) and α-(S-carbamoylthio)-βchlorodihydrocinnamic ester (4). When excess aldehyde was used in the reaction, a small amount of 2,10-bis(α-chlorobenzyl)-4,8-dioxo-6-phenyl-5,7-diaza-3,9-dithiaundecanedioate (5) was obtained, together with the products 3 and 4. The NMR studies revealed that product 3 isolated exists all in one isomer which has the 4-ester and 5-aryl groups cis about a single bond in the ring. It was suggested that product 4 was formed by rearrangement of the trans isomer of 3.