bluuebunny/crossref_metadata_2025 huggingface dataset:
Reaction of α-Chloro Sulfoxides with Carbonyl and Thiocarbonyl Compounds
Authors: Tsuchihashi Gen-ichi , Ogura Katsuyuki
Published: July 2006

Ghloromethyl methyl sulfoxide undergoes a Darzens-type reaction with carbonyl compounds in the presence of potassium t-butoxide in t-butanol to afford methylsulfinyloxirane derivatives. The stereochemistry of this reaction has been studied. The reaction with a symmetrical ketone appeared to proceed stereospecifically to give only one isomer. On the other hand, the reaction with unsymmetrical ketones such as pinacolone or acetophenone produced a mixture of two diastereoisomers, in which a thermodynamically unstable isomer was predominant. The reaction with thiobenzophenone gave 1,1-diphenyl-2-methylsulfinylethylene which seems to have been formed from the intermediacy of 2,2-diphenyl-3-methylsulfinylthiirane. Mechanisms of these reactions are also discussed.
Aminosugars. XX. Synthesis of Some Derivatives of 2-Acetamido-2-deoxy-d-mannose
Authors: Yoshimura Juji , Sakai Hideo , Oda Nobuteru , Hashimoto Hironobu
Published: July 2006

Preparation of 2-acetamido-2-deoxy-d-mannose (2) by epimerization of the corresponding d-glucose was improved by addition of Ni2+ ion to the equilibration system, and several derivatives of (2) were synthesized. N-glycosides were obtained by using ammonium chloride as a catalyst, and p-nitrophenyl glycoside by a fusion method. The composition of four isomers in benzylglycosidation of (2) was determined to be 66% α-pyranoside (6), 11% β-pyranoside, 16% α-furanoside (5) and 7% β-furanoside. Benzylidenation of 6 gave the corresponding 4,6-O-benzylidene derivative which was converted into the 3-O-acetate (8) by acetylation, and to the corresponding 2-amino-2-deoxy derivative by treatment with ethanolic potassium hydroxide. Oxidation of 6 with oxygen in the presence of platinum-charcoal and following esterification gave the corresponding methyl uronate which was derived to the di-O-acetate (11). Periodate oxidation and the following hydrogenation of 5 gave benzyl 2-acetamido-2-deoxy-α-d-lyxofuranoside which was then derived to di-O-acetate (13). Nitromethane condensation of 2 in barium hydroxide solution gave one isomeric 1-C-nitro-1-deoxy-d-heptitol which was converted into methyl 3-acetamido-3-deoxy-d-gaycero-d-galacto-α-heptopyranoside (18). First-order analyses of NMR spectra of 8, 11, 13, and tetra-O-acetate of 18 are described.
Cationic Arylation. V. Reaction of Substituted Benzenes with p-Nitrophenyl Cation
Authors: Kamigata Nobumasa , Kobayashi Michio , Minato Hiroshi
Published: July 2006

The cationic arylation of substituted benzenes was investigated with p-nitrophenyl cation generated from p-nitrobenzenediazonium tetrafluoroborate in acetonitrile and from p-nitrophenylazo p′-tolyl sulfone in the presence of trifluoroacetic acid. The isomer distribution of substituted nitrobiphenyls produced and the partial rate factors indicated electrophilic character of the p-nitrophenyl cation. Selectivity of p-nitrophenyl cation is low compared with those of nitronium or sulfonyl cation, and similar to that of phenyl cation. These facts suggest that the p-nitrophenyl cation functions as a cation diradical with concerted uncoupling of a pair of π-electrons, one of which falls into the vacant sp2 σ-orbital.
The Migratory Aptitudes in the 1,3-Dipolar Cycloadducts of Substitiuted 1-Benzoyliminopyridinium Ylides with Dimethyl Acetylenedicarboxylate
Authors: Sasaki Tadashi , Kanematsu Ken , Kakehi Akikazu , Ito Gin-ichi
Published: July 2006

The 1,3-dipolar cycloaddition of substituted 1-benzoyliminopyridinium ylides (1, 6, and 9) with dimethyl acetylenedicarboxylate (DAG) produced the corresponding rearrangement compounds (3, 4, 7, 8, and 10). On the other hand, the similar reaction of 11 with DAC in acetonitrile gave 12, accompanied with a Sommelet-type rearrangement compound, 13. The structural elucidation of these products was accomplished by spectral inspections.
Stereochemical Studies of Monoterpene Compounds. XVIII. A Conformational Study of Monoterpene α,β-Unsaturated Ketones by Means of the Temperature-dependent Circular Dichroism
Authors: Suga Takayuki , Imamura Kiyoshi
Published: July 2006

The conformations of flexible, cyclic α,β-unsaturated ketones, (−)-p-menth-3-en-5-one (1), (+)-carvone (2), (−)-piperitone (3), (−)-carvenone (4), and (+)-pulegone (5), were examined by means of the temperature-dependent circular dichroism (CD) in the region of the n-π* transition. In polar solvents, the simultaneous occurrence of the conformational equilibrium and the asymmetric solvation was observed markedly for the compound 1 of these compounds, along with a change in the large rotational strength at lower temperatures.
The Diffusion of Gases at High Pressures. IV. The Diffusion of CTH3 in the CH4-CO2 System
Authors: Takahashi Shinji
Published: July 2006

The diffusion coefficients of radioactive methane (CTH3) in normal methane, in carbon dioxide, and in a mixture of normal methane with carbon dioxide (0.522 mol fraction of methane) were measured at the temperatures of 25, 50, and 75°C in the 15–250 atm pressure range. The measurements were made through a plug of porous bronze in the diffusion cell, using the radioactive tracer technique. The diffusion coefficient-density products, Dρ, for the CTH3–normal methane system and the CTH3- the binary mixture system increased slightly with an increase in the density in the lower-density region at 25 and 50°C, but they were nearly constant at 75°C. The Dρ for the CTH3–carbon dioxide system decreased with an increase in the density at each temperature. The Dρ-values at 1 atm, obtained by extrapolation, agreed fairly well with those reported in the literature. The density dependence of the Dρ values at high densities could not be predicted by Enskog-Thorne’s theory.
Catalytic Properties of BF3-treated Aluminas. IV. The Effect of BF3 Adsorption on the Acidic Properties of Aluminum Oxides
Authors: Matsuura Kanjiro , Suzuki Akira , Itoh Mitsuomi
Published: July 2006

An account was given of the surface acidic properties of a series of BF3-treated aluminum oxides, ranging in their precalcination temperature up to 1000°C. It was concluded that all aluminum oxides dehydrated over 300°C were converted to solid acids with new strong acid centers of H0≤−8.2 by adsorption with BF3. This new acid centers would be certainly of the Brönsted type. Their catalytic activities in some carbonium ion type reactions are well correlated with the n-butylamine acidity in the presence of Hammett’s indicators, and the maximum number of acid centers was observed in catalyst samples precalcined at 450 and 800°C respectively. The present study also suggests that the acid centers developed on the surface of aluminum oxides are somewhat different in nature depending upon their precalcination temperatures. Since there was a good correlation between the amount of the remaining hydroxyl groups and that of the absorbed BF3, the surface hydroxyl groups, in addition to the aluminum atoms serving as the Lewis centers, which are not fully coordinated, were discussed as the most important factors in the formation of such acid centers.
Studies of the Synthesis of Furan Compounds. XXVI. The Reaction of 5-Nitro-2-furimidoylhydrazine with Acid Anhydrides
Authors: Hirao Ichiro , Kato Yasuhiko , Tateishi Hiromichi
Published: July 2006

Reactions between 5-nitro-2-furimidoylhydrazine (I) and acetic or propionic anhydride (or the corresponding acids) under various conditions afforded 5-methyl- (II) and 5-ethyl-2-(5-nitro-2-furyl)-1,3,4-oxadiazole (IV) and 5-methyl- (III), 5-ethyl- (IX), 1 -acetyl-5-methyl- (VII), 1-propionyl-5-ethyl- (VIII), 1-propionyl-5-methyl- (X), and 1-acetyl-5-ethyl-3-(5-nitro-2-furyl)-1,2,4-triazole (XI) respectively. The treatment of I with acetic and propionic anhydride in refluxing benzene or tetrahydrofuran gave 1-acetyl- (V) and 1-propionyl-2-(5-nitro-2-furimidoyl)-hydrazine (VI) respectively. Compounds, VII, VIII, X, and XI were also prepared by the cyclization of V with propionic anhydride and by that of VI with acetic anhydride in dioxane. The structures of the products were discussed on the basis of the spectral data.
Ultrasonic Absorption in Solutions of Propionic Acid
Authors: Tatsumoto Nobuhide , Sano Takayuki , Matsunaga Norihiko , Tochigi Eiso , Yasunaga Tatsuya
Published: July 2006

The effect of a solvent on the ultrasonic relaxation of propionic acid has been studied. The relaxation frequency is affected a little in hydrophilic solvents, while in non-hydrophilic solvents it shifts to a higher-frequency side. The activation enthalpy in a reaction from open to cyclic dimers decreases with dilution in the non-hydrophilic solvents; the magnitude of the change in the hydrophilic solvents is less than in the non-hydrophilic solvents. This means that the open dimer is destabilized by non-hydrophilic solvents. The sequence of the magnitude of the solvent effect on the relaxation frequency is consistent not with that estimated from the magnitude of the dielectric constant of the solvent, but with that estimated from the magnitude of the non-hydrophilic strength of the solvent. The stability of an open dimer in a hydrophilic or polar solvent is attributed to the interaction of the free OH group on the open dimer with the solvent.
An Isothermal Displacement Calorimeter for Measuring Enthalpies of Mixing
Authors: Tanaka Reiji , Murakami Sachio , Fujishiro Ryoichi
Published: July 2006

An isothermal displacement calorimeter of the Van Ness type has been constructed. The calorimeter was tested on three systems, benzene+cyclohexane, cyclohexane+n-hexane, and benzene+dichloromethane, at 25°C, and the performance of the calorimeter was discussed in connection with the literature values. The precision of the new calorimeter was within 0.5%; this was equal to, or better than, that of calorimeters of a similar type which have been constructed by several investigators.
The Reaction of Mono-, Di-, and Trisodium Orthophosphate in a Mixed Solution of Acetic Acid and Acetic Anhydride
Authors: Watanabe Makoto , Senda Tetsushi
Published: July 2006

Mono-, di-, or trisodium orthophosphate was heated at 100°C in an equivolume mixture of acetic acid and its anhydride. By X-ray diffractometry and paper chromatography, the products from these three sodium salts of orthophosphate were found to be sodium trimetaphosphate. At the end of the 30-hr reaction period, the purity of the trimetaphosphate was higher than 90%. The ease of formation of the trimetaphosphate ring under various conditions was shown, and the stability of the ring was discussed on the basis of the strain of the bonding angle.
Syntheses of 1,2-Dithiole Derivatives
Authors: Chinone Akiko , Inouye Kozo , Ohta Masaki
Published: July 2006

Sulfurization of 1,3-diarylpropanetrione (1) with hydrogen sulfide and hydrogen chloride afforded a mixture of 4-hydroxy-3,5-diaryl-1,2-dithiolium chlorides (3) and 3,5-diaryl-1,2-dithiolium chlorides (4). Treatment of a mixture of 3a and 4a with triethylamine in alcohol gave anhydro-4-hydroxy-3,5-diphenyl-1,2-dithiolium hydroxide (5a) and the 4-substituted product (6). Sulfurization of dibenzoyldibromomethane yielded 3,5-diphenyl-1,2-dithiolium bromide. Reactions of 5a with picric acid and acetic anhydride in the presence of perchloric acid were carried out.
Synthesis and Properties of Metal Complexes with a New Multidentate Schiff Base Containing Ethereal Oxygen Atoms
Authors: Murase Ichiro , Yamanouchi Kuniko , Yamada Shoichiro
Published: July 2006

A new multidentate Schiff base, 1,4-bis(o-salicylideneaminophenyl)-1,4-dioxabutane having six atoms which may be available for bonding with a metal ion was prepared. With this ligand several metal complexes have been synthesized. From their magnetic properties, electronic absorption spectra and X-ray powder diagrams, it has been concluded that the cobalt(II), nickel(II), and zinc(II) complexes are isomorphous, having a five coordinated configuration, in which one of the ethereal oxygen atoms of the ligand is bound with the metal ion. The copper(II) complex with a similar composition has a different configuration.
Six-coordinate Chromium(III) Complexes with N,N′-Ethylene-bis(acetylacetoneiminate) as a Ligand
Authors: Yamanouchi(Formerly Iwasaki) Katsumoto , Yamada Shoichiro
Published: July 2006

Numerous six-coordinate chromium(III) complexes with N,N′-ethylene-bis(acetylacetoneiminate) (abbreviated as Acen) have been synthesized. The complexes obtained are of the type [Cr(Acen)X2]Y, where X=H2O, NH3, CH3NH2, n-C3H7NH2, and n-C4H9NH2 for Y=Cl and X=CN, NCS, and NO2 for Y=K. The complex [Cr(Acen)(H2O)2]Cl has been obtained by a reaction of anhydrous chromium(III) chloride with N,N′-ethylene-bis(acetylacetoneimine) in tetrahydrofuran. The other complexes have been derived from the diaquo-complex. Infrared spectra show that the nitrite ions in [Cr(NO2)2(Acen)]− and the thiocyanate ions in [Cr(NCS)2(Acen)]− are bound with the chromium(III) ion through oxygen and nitrogen atoms, respectively. Electronic absorption bands of all these complexes, which arise from internal transitions within the ligand Acen, differ greatly from those of the free ligand, suggesting that the electronic states of the ligand in the complexes differ from those of the free ligand.
Cobalt(I) Tetraphenylporphin
Authors: Kobayashi Hiroshi , Hara Tetsuo , Kaizu Youkoh
Published: July 2006

Cobalt(I) tetraphenylporphin was prepared by reduction of tetraphenylporphinatocobalt(II) with sodium benzophenone ketyl in tetrahydrofuran (THF) and was purely isolated. The compound was identified as Na-[Co(I)TPP]·5THF (tetraphenylporphin is abbreviated to TPP). On the basis of electronic absorption spectrum, magnetic circular dichroism, magnetic susceptibility and NMR spectrum, the complex formed was concluded to be a complex of cobalt(I). Although some part of cobalt electron is migrated into the conjugated system of porphin, an electron furnished by the reducing reagent is mainly trapped by the central cobalt. The compound should be named sodium tetraphenylporphinatocobaltate(I).
Electronic Absorption Spectra of Tris(2,2′-bipyridine)- and Tris(1,10-phenanthroline) Complexes of Vanadium(II) and Chromium(II)
Authors: Fujita Ichiro , Yazaki Takanori , Torii Yasuo , Kobayashi Hiroshi
Published: July 2006

Electronic absorption spectra of tris(2,2′-bipyridine) complexes of vanadium(II) and chromium(II) were measured. When methyl groups are introduced into the coordinating bipyridine, (d, d*) transitions in the central metal, (π, π*) transitions in the coordinating ligand, and “metal to ligand” charge-transfer transitions show their respective characteristic shifts. Thus the visible and near-infrared bands of tris(2,2′-bipyridine) complexes of vanadium(II) and chromium(II) are assigned to “metal to ligand” charge-transfer transitions as well as the visible bands of tris(2,2′-bipyridine)iron(II). A comparison between the corresponding bands of tris(2,2′-bipyridine) complexes and tris (1,10-phenathroline) complexes also verifies the assignment.
Polarographic Study of the Rates of the Dissociation Reactions of the Nickel(II)-, Zinc(II)-, and Cadmium(II)-2,2′-Ethylenedioxybis[ethyliminodi(acetate)] (GEDTA) Complexes
Authors: Kodama Mutsuo , Oyama Noboru
Published: July 2006

In GEDTA solutions with pH’s lower than 7.00, the nickel(II), zinc(II), and cadmium(II) ions were found to yield the one-step, two-step, and three-step polarographic waves respectively. The polarographic wave of the nickel(II) ion, the first step of the zinc(II) ion, and the first and second steps of the cadmium(II) ion showed a kinetic-controlled nature. In this study, the polarographic wave of the nickel(II) ion, the first step of the zinc(II) ion, and the second step of cadmium (II) ion were studied systematically. From an experimental examination of the nature of the kinetic currents of these complexes, the mechanisms for the above polarographic steps were determined as:

(Remark: Graphics omitted.)

where CdHY−* is the electroactive cadmium(II)-GEDTA complex. By comparing the dissociation rate constant of the nickel(II)-GEDTA complex with that of the nickel(II)-aspartate complex, the detailed dissociation mechanism was determined. The rates and mechanisms of the dissociations of zinc(II) and cadmium(II)-GEDTA complexes were also discussed in detail.
Phytosterols and Triterpenes in the Roots of the “Kidney Bean” (Phaseolus vulgaris L.)
Authors: Katsui Nobukatsu , Matsue Hajime , Hirata Tomohiko , Masamune Tadashi
Published: July 2006

In connection with the studies of hatching substances for soybean cyst nematodes, the neutral fraction of the roots of the “kidney bean” (Phaseolus vulgaris L.) has been examined. It was found that phytosterols and triterpenes exist in the roots of plants.
The Bromine Nuclear Quadrupole Resonance of the Molecular Complex of Aluminum Tribromide with Benzene
Authors: Okuda Tsutomu , Furukawa Yoshihiro , Negita Hisao
Published: July 2006

The bromine nuclear quadrupole resonance (NQR) and its Zeeman effect have been observed in the molecular complex of aluminum tribromide with benzene at room temperature. The resonance frequencies are 79.99, 90.10, and 91.18 MHz for 81Br at 301°K. The asymmetry parameters of the field gradient are 28.9±1.1, 8.6±1.0, and 6.0±0.9% for the bromine atoms in the order of increasing resonance frequency. Aluminum tribromide forms the dimer in the complex crystal as well as in the pure state. The bond angle between a pair of terminal bromine atoms and the interbond angle at the bridging bromine atom are found to be 117.3±0.5° and 95.5±0.2° respectively; these values correspond to those of 122±2° and 87±2° obtained from the X-ray analysis. Furthermore, the charge-transfer from the benzene ring to the bromine atom is discussed on the basis of the NQR parameters.
On the Emission Spectra of the Unimolecular Reaction of Methylamine by Electron Impact
Authors: Fukui Kiyoshi , Fujita Iwao , Kuwata Keiji
Published: July 2006

The emission spectra of the following excited species produced from methylamine by electron impact (the energy of 150 eV) at a low pressure were observed: NH(A3Π–X3Σ), CN(B2Σ–X2Σ), CH(A2Δ–X2Π), and H(Balmer series). It was confirmed that the excited species are produced by a unimolecular reaction of methylamine. The replacement by deuterium decreases the production of the excited hydrogen atom from methylamine by about 40%, this supports the idea that the excited hydrogen atom is produced through a superexcited state of methylamine. It was also determined that the production of the excited hydrogen atom of the methyl group was less than that of the amino group by about 20%. This is in contrast to the findings on the mass spectrum of CD3NH2, where the peak of CD2NH2+ was much higher than that of CD3NH+. The NH radical in the A3Π state was produced from methylamine and dimethylamine, while the NH radicals in the A3Π and the c1Π states were produced from ammonia.
Kinetic Study of the Formation and Decomposition of Amylose-iodine-iodide Complex
Authors: Yamagishi Akihiko , Imamura Taira , Fujimoto Masatoshi
Published: July 2006

The complex formation reaction among amylose, iodine and iodide ion in aqueous solution was investigated with a stopped-flow apparatus. The forward reaction rate was found to be expressed as v=k[Amylose]([I3−]–θ) for [I3−]>θ, where θ is a critical value determining the mechanism. For [I3−]>θ, the rate was considered to be determined by the process between a free amylose unit and free I3−. For [I3−]<θ, the rate-determining step is considered to be intramolecular conversion from an intermediate to a final product. The rate of the reaction between amylose units and I3− is close to that of a diffusion-controlled process (7×108  m−1 sec−1). These conclusions are supported by the study of the decomposition reaction of complex, using Na2S2O3 or Ce(SO4)2.
Energy Transfer in the γ-Irradiated Benzene Solutions of Carbonyl Sulfide, Nitrous Oxide, and Carbon Dioxide
Authors: Sato Shin , Hosoya Kiyoshi , Shishido Seishi , Hirokami Shun-ichi
Published: July 2006

The γ-radiolysis of benzene solutions containing carbonyl sulfide, nitrous oxide, and carbon dioxide has been investigated at room temperature and at 0°C. Carbonyl sulfide was shown to be an effective electron scavenger and to give carbon monoxide as the product. By comparing the solute concentration dependences of G(N2) and G(CO), it was concluded that the collision of secondary electrons with benzene does not efficiently produce the first excited singlet state, the G-value of which is less than 0.2 if it is produced at all. The concentration dependences of the G(CO) and G(phenol) from the benzene solution of carbon dioxide also suggested that the superexcited state or the highly-excited state of benzene is too short-lived to transfer its energy to the solute.
The Dehalogenation of Haloalkanes on SiO2-supported Metals
Authors: Anju Yasuhide , Mochida Isao , Yamamoto Hiroko , Kato Akio , Seiyama Tetsuro
Published: July 2006

The dehalogenations of haloethanes and halopropanes over metals (Cu, Ag, Au, Fe, Co, Ni, Pd, and Pt) supported by silica gel were studied by means of the microcatalytic pulse technique in order to elucidate the mechanism of dehalogenation. The dechlorination reactivities of cis- and trans-1,2-dichloroethylenes and the dechlorination products from dl- and meso-2,3-dichlorobutanes were observed from the viewpoint of stereoselectivity. The order of catalytic activities among the metals for the dehalogenation of haloethanes was: Pt>Cu≈Ni>Ag≈Co≈Pd>Fe≈Au. Dehalogenation proceeded exclusively in the 1,2-dihaloethanes. However, dehydorhalogenation took place in the 1,2-dihalopropanes to an appreciable extent when the product distributions of dehydrohalogenation were similar to those on solid acids. Both 1,1,2-trichloroethane and 1,2-dichloropropane were more reactive than 1,2-dichloroethane. 1,2-dichloroethylenes from 1,1,2,2-tetrachloroethane and 2-butenes from dl- and meso-2,3-dichlorobutanes were nearly in an equilibrium ratio of cis/trans forms. From a comparison of these results with those of the dehydrohalogenation on solid acids, it is concluded that the dehalogenation of haloalkanes on metals proceeds through a radical-step-by-step mechanism.
On the Equivalence of Two Expressions for Potentiometric Titration of Polyelectrolytes
Authors: Maeda Hiroshi
Published: July 2006

Two expressions for potentiometric titrations of polyelectrolytes are proved to be equivalent, being derived from a common basis. A thermodynamic interpretation of the term representing the non-ideality of polyelectrolyte solutions is also explicitly given.
Studies on Microcapsules. XIII. Effect of Span 85 and pH of Aqueous Phase on the Formation of Polyamide Microcapsules
Authors: Ogawa Tomoharu , Takamura Kouichi , Koishi Masumi , Kondo Tamotsu
Published: July 2006

The effects of the pH of aqueous phase containing piperazine and the concentration of Span 85, a nonionic surfactant with chemical description of sorbitan trioleate (Atlas Power Co., U.S.A) on the formation of polyphthalamide microcapsules were systematically investigated by the interfacial polycondensation method in the organic phase containing p-phthaloyl dichloride. The presence of Span 85 facilitated the formation of microcapsules by increasing the transfer of undissociated diamine molecules into the organic phase in the pH range 9.0–12.0, outside of which Span 85 did not significantly contribute to the formation of microcapsules. An increase in the pH in this range gives rise to an increase in the number of undissociated diamine molecules, promoting the transfer of diamine.
Behavior of Positive Hole in a γ-Irradiated 3-Methylpentane Glass at 77°K
Authors: Irie Masahiro , Yoshida Hiroshi , Hayashi Koichiro , Okamura Seizo
Published: July 2006

In order to elucidate the behavior of a positive hole in irradiated alkane glasses, the effect of solutes having ionization potential lower than that of a glass matrix molecule upon the decay of a trapped electron was examined in a 3-methylpentane glass at 77°K by means of electron spin resonance. The decay was found to be explained in terms of the superposition of two exponentially decaying processes, as in the absence of a solute. Although the fast process was not affected by a solute, the slow process was further slowed by the addition of a solute. The effect of a solute is described by the empirical relation, k⁄k0=1⁄(1+fN), where k and k0 are the rate constants of the slow decay in the presence and in the absence of a solute, respectively. N is the mole fraction of a solute. The observed values of the slowing-down efficiency, f, increase in parallel with the decreasing values of ionization potential of solutes: 2-methyltetrahydrofuran, diethylether, methylvinylether, 2-methylpentene-1 and n-butylvinylether. The results are interpreted in terms of trapping of a positive hole by a solute molecule and positive hole tunneling from a hole trap to a trapped electron.
The Structural Transformation of Ferric Oxyhydroxides and Their Activity to Sulfur Dioxide
Authors: Ishikawa Tatsuo , Inouye Katsuya
Published: July 2006

α-, β-, and γ-FeOOH calcined at various temperatures up to 500°C have been examined by determining adsorption isotherms in order to relate the reactivity to SO2 with the structural transformation. For each ferric oxyhydroxide, the amount of chemisorbed SO2 per unit surface area (Ac), a measure of reactivity to SO2, decreases with the progress of transformation into α-Fe2O3. At temperatures of calcination below 200°C the Ac value of β-FeOOH is larger than that of α-FeOOH or γ-FeOOH. It is shown by thermogravimetric analysis that the weight loss of β-FeOOH caused by heating is larger than the theoretical value corresponding to the dehydration of hydroxyl groups; 2FeOOH→Fe2O3+H2O. Changes in the X-ray diffraction patterns and Cl content of β-FeOOH with calcination indicate that β-FeOOH is transformed into α-Fe2O3 with elimination of inherently contained Cl at a higher temperature than other oxyhydroxides. The high reactivity to SO2 and large weight loss of β-FeOOH caused by heating have been discussed with respect to the particular crystal structure of β-FeOOH containing Cl and molecular H2O, in addition to hydroxyl groups.
Studies of Built-up Films by Means of the Polarized Infrared ATR Spectrum. III. Elaidic Acid Films
Authors: Takenaka Tohru , Nogami Kazuko
Published: July 2006

Attenuated total reflection studies with polarized infrared radiation have been made of multilayers of elaidic acid built up on a germanium plate by the Blodgett technique. It is concluded that the built-up films prepared from the tap-water substrate are made of calcium elaidate monohydrate. From the intensity changes in the regularly-spaced peaks (progression bands) in the region from 1350 to 1180 cm−1, the planarity of the chain segment between the carboxylate group and the double bond is found to be dependent upon the surface pressure applied in the process of monolayer transfer onto the germanium plate. Studies of the anisotropy of the absorption index in the films show that the molecules assume a uniaxial orientation with respect to the axis normal to the germanium-sample interface (the z-axis), with an angle from 30° to 33° (in average) between the z-axis and the molecular axes. Furthermore, from the changes in the reflectivity with the number of layers, the film thickness per layer is estimated to be ca. 21.9 Å, a value which is in good agreement with the half-value of the long spacing, 44.16 Å, of the films as determined by X-ray diffraction studies. This apparently indicates that the films appear as the Y type.
Vibrational Spectra of Propionamide and Its C- and N-Deuterated Compounds
Authors: Kuroda Yoshihiro , Saito Yutaka , Maghida Katsunosuke , Uno Toyozo
Published: July 2006

The infrared and Raman spectra of CH3CH2CONH2, CH3CD2CONH2 and their N-deuterated compounds in the solid state have been measured. The normal coordinate analysis has been made by assuming the molecular symmetry of Cs. A Urey-Bradley force field was used for the in-plane vibrations and a valence force field for the out-of-plane vibrations of the amide group. The ethyl group was treated by a Urey-Bradley type force field as well as a valence type force field. The assignments of the fundamental frequencies have been made by referring to the infrared and Raman intensities, isotopic frequency shift and the calculated frequencies by using the force constants which were taken from n-paraffins and acetamide. The agreement between the observed and the calculated frequencies in the initial calculation was good for the CH3 and the amide group vibrations but was not good enough for some vibrations involving the α-carbon atom. Only the force constants related to these vibrations were refined by the least squares method in order to obtain the best fit. The calculated frequencies in this way fit to the observed satisfactorily.
On the Mechanism of H-Atom Formation by Reaction of Electrons in Frozen Acidic Solutions at 77°K
Authors: Ohno Shin-ichi , Sasaki Teikichi , Koike Mitsuru
Published: July 2006

A model for the reaction of radiation-produced electrons in frozen acidic solutions is presented to explain anomalies. It does not assume the inertness of the hydrogen ion as an electron scavenger in the solid phase but involves a process in which an H-atom, the product of the (e−+H+) reaction, is transferred to an adjacent water molecule through an H-bonded network until it finds a suitable site where it can be trapped or a species with which to react. Results from ESR-measurements on photolysed frozen solutions of ferrocyanide ions in the presence of nitrate ions and 2-propanol as well as the data on H/D isotope effects were used as evidence supporting the model.
The Kinetics and Mechanism of the Photo-oxidation of N,N′-Diphenyl-p-phenylenediamine. Electron-transfer from the Upper Excited Singlet State to Oxygen
Authors: Shizuka Haruo , Sawaguri Yasuyoshi , Morita Toshifumi
Published: July 2006

The photo-oxidation of N,N′-diphenyl-p-phenylenediarnine (DPPD) has been studied spectrophotometrically. The quantum yield for the diimine formation, Φ, in aerated cyclohexane at 2537 Å and 20°C did not change with variations of the irradiation time, the concentration of DPPD, or the light intensity. However, the Φ values increased, as did the decrease in the fluorescence quantum yields, as the excitation energies increased. The dissolved oxygen had the optimum concentration (1.2×10−4m), giving the maximum value of Φ in aerated cyclohexane at 2537 Å, and none of the product, the diimine, was obtained in the degassed system. When about 0.13m of ethanol or methanol was added to aerated cyclohexane, the maximum value of Φ was measured, and the addition of a highlypolar solvent, acetonitrile or H2O, decreased regularly in Φ. On the basis of these results, it can be said that the photo-oxidation of DPPD originates from the Franck-Condon state of the upper excited singlet state, 1(RH2)n. It seems that, in the primary processes of the reaction, the electron transfers take place from the Franck-Condon state of 1(RH2)n directly to the oxygen molecule (3Σg−) and to the solvent, resulting in a trapped electron which immediately jumps into the oxygen molecule. Then, the (RH2)+O2− ion pair may be formed, and subsequently the intermediate, (RH2)+O2−, may be converted to the product or the starting materials. The dissolved oxygen and the polar solvents are responsible for the electron-transfer processes, but they deactivate the ion pair, resulting in the decrease in Φ.
Stereochemical Studies of Monoterpene Compounds. XIII. The Conformational Analysis of the Acetyl Group of 4-Methyl-10-nor-8-oxomenthols by Circular Dichroism
Authors: Suga Takayuki , Watanabe Satoru
Published: July 2006

The conformational analysis of the acetyl group of a stereoisomeric pair of 4-methyl-10-nor-8-oxomenthols was made by means of the temperature-dependent circular dichroism. (1R:3S:4R)-(+)-4-Methyl-10-nor-8-oxoneomenthol (1) exhibited a double-humped Cotton effect at a low temperature. This phenomenon seems to indicate the existence of a conformational equilibrium among 1b, 1c, and 1d, but not 1a. On the other hand (1R:3R:4R)-(−)-4-methyl-10-nor-8-oxomenthol (3) exhibited an inversion in the sign of the Cotton effect when the solvent and the temperature were changed. This phenomenon was interpreted in terms of the conformational equilibrium among 3a, 3b, and 3c. These phenomena were interpreted in terms of the competition of the steric factor and the intramolecular hydrogen bonding.
The Crystal Structure of μ-Oxo-bis{pentamminechromium(III)} Chloride Monohydrate, [(NH3)5Cr-O-Cr(NH3)5]Cl4·H2O
Authors: Urushiyama Akio
Published: July 2006

The crystal structure of μ-oxo-bis{pentamminechromium(III)} chloride (basic rhodochromic chloride) monohydrate, [(NH3)5Cr–O–Cr(NH3)5]Cl4·H2O, has been determined from the three-dimensional X-ray data. The crystals are orthorhombic. The cell dimensions are: a=11.94±0.01, b=11.71±0.01, and c=13.40±0.02 Å. The space group is Pbca, with four formula units in a unit cell. The structure was refined by the least-squares method, with anisotropic temperature factors, to R=0.14. A bridging oxygen atom of the basic rhodochromic complex ion is situated on the inversion center. Therefore, the complex has a center of symmetry and, accordingly, a linear Cr–O–Cr system. The N–Cr–O angles are nearly 90° or 180°, and the Cr–N bond distances are in the range from 2.09 to 2.14 Å (average 2.11 Å). The complex ion has approximately a D4h symmetry. The Cr–O distance is 1.80 Å, which is quite short compared with that found in the other Cr(III) complexes. The linear Cr–O–Cr system and its short bond distance suggest the presence of an extensive π-bonding in this system. The single-crystal polarized absorption spectra in the visible and ultraviolet regions were also measured. It was found that the characteristic sharp absorption bands of the basic rhodochromic complex ion are all polarized along the fourfold rotation axis of the complex.
Dipole Moment Functions of CO and HCl
Authors: Suzuki Isao
Published: July 2006

A general formalism is presented for the least-squares determination of dipole moment functions of diatomic molecules in which the radial part wave functions obtained as numerical solutions of vibration and vibration-rotation Hamiltonian matrix are used. Although this approach is purely numerical, the advantage of using orthonormal basis and perturbed wave functions is retained. Attempts have been made on the determination of the cubic dipole moment functions for the CO and HCl molecules. All the available data of dipole as well as transition moments and the Herman-Wallis factors for these molecules are considered in the refinement process. The following cubic dipole moment functions are obtained (in Debye): M(Δr)=0.1243–3.0722(Δr)+0.1909(Δr)2+2.1856(Δr)3 for CO and M(Δr)=1.093+0.949(Δr)+0.034(Δr)2–0.78(Δr)3 for HCl.
Self-Diffusion Coefficients and Interdiffusion Coefficient in Acetone–Benzene System
Authors: Kamei Yoshinobu , Oishi Yasumichi
Published: July 2006

Self-diffusion coefficients of acetone and benzene have been determined in the whole composition range of the binary system at 25°C by a capillary-cell method using the 14C-marked tracer. The results were in a good agreement with those determined by the NMR spin-echo method by McCall and Douglass. The products of the respective self-diffusion coefficients and the viscosity of this system showed a relatively constant compositional dependence. Bearman’s relation was shown to hold between the self-diffusion coefficients and the partial molar volumes for the system. The validity of Darken’s equation was confirmed for the self-diffusion coefficients and the interdiffusion coefficient of the system.
Temperature Dependence of Corona-charging Properties on TiO2-Polymer Dispersion Layers
Authors: Iida Takeaki , Nonaka Toyokazu , Nozaki Hiroshi
Published: July 2006

The corona-charging properties of TiO2-polymer dispersion layers were determined in the dark at temperatures 0°–35°C by the turn-table method. Dispersion layers of TiO2 (rutile) and polyvinyl acetate, coated on an aluminum foil to about 15 μ thickness, were used. The results showed the rising rate of the surface potential has a maximum at around 20°C. The saturation potential decreases slightly with a rise in temperature. The decay potentials were represented by the plot logV  vs. \sqrtt. The relation between logV and \sqrtt is linear in certain range of the surface potential, and the gradient increases in proportion to the rise in temperature. This is discussed with the use of an equivalent-circuit model.
Fluorinated Ligands. I. Chelating Behavior of 1-Amino-3,3,3-trifluoro-2-propanol with Copper(II) Ion and Preparation of Copper(II)-, Cobalt(III)-, and Nickel(II) Complexes
Authors: Yoshida Isao , Kobayashi Hiroshi
Published: July 2006

In the reaction of 1-amino-3,3,3-trinuoro-2-propanol (LOH) with cupric ion in aqueous solutions two kinds of complex species were found to be formed: One was a complex ion of [Cu(LO)(H2O)2]+1, which was of major abundance in the solutions where mole ratio of the ligand to the metal ion was less than 3, and the other was an inner complex of [Cu(LO)2] predominating in the solutions which contained a large excess of the ligand or a small amount of alkali. The structures of the species in the solution phases were assigned by the spectral data. Chelate compounds of inner complex type, [Cu(LO)2(H2O)], [Co(LO)3], and [Ni(LO)2], were synthesized from the present ligand and corresponding metal ion. These are insensitive to moisture in the air. Structures of the chelates are discussed on the basis of spectroscopic observations.
Schiff Bases Derived from Heptane-2,4,6-trione and Ethylenediamine, and Its Copper(II) and Oxovanadium(IV) Chelates
Authors: Yano Tairoku , Ushijima Tetsuaki , Sasaki Masaomi , Kobayashi Hiroshi , Ueno Keihei
Published: July 2006

The copper(II) and oxovanadium(IV) complexes of a new Schiff base derived from heptane-2,4,6-trione and ethylenediamine were prepared. Of a macrocyclic two-to-two and an open jaw-shaped two-to-one (trione to diamine) condensation product, only the latter gave mononuclear copper (II) and oxovanadium(IV) complexes. The coordinating sites to the metal ion in each complex are discussed referring to the spectroscopic results.
Polarographic Behavior of Nickel(II) in Propionitrile and Benzonitrile in the Presence of Thiocyanate Ions
Authors: Itabashi Eiki
Published: July 2006

The effect of the cation of the supporting electrolyte on the electrode reaction of nickel(II) in propionitrile and benzonitrile solutions containing thiocyanate ion was investigated by DC polarography and i-t curve analysis. In the absence of thiocyanate ion, a propionitrile solution of nickel(II) gives a single irreversible wave in LiClO4 and NaClO4 supporting electrolytes and a double wave in Et4NClO4 and n-Bu4NClO4, and a benzonitrile solution of nickel(II) gives a double wave in alkali metal and quaternary ammonium perchlorates. Nickel(II) in these nitrile solvents in the presence of thiocyanate ion exhibits a catalytic pre-wave in alkali metal perchlorates and a catalytic maximum wave in quaternary ammonium perchlorates. The double wave of nickel(II) in the absence of thiocyanate ion is due to the inhibition of the charge transfer process by the relatively weak adsorption of quaternary ammonium cations and not to the presence of two electroactive species. A mechanism which involves the cyclic regeneration of adsorbed thiocyanate ion for the catalytic pre-wave and the catalytic reduction of thiocyanate ion with the electroreduced metallic nickel for the maximum wave has been presented.
Mixed Solvent Deuterium Isotope Effects on the Hydrolysis of UO22+ and Be2+ Ions
Authors: Maeda Masunobu , Amaya Toshihiko , Ohtaki Hitoshi , Kakihana Hidetake
Published: July 2006

Stability constants of the hydrolysis species of UO22+ ion were determined in pure light water and 80% heavy water containing 3m NaClO4 as an ionic medium at 25°C, and the results were compared with those in pure heavy water. The decrease of the stability constants in hydrolysis reactions of UO22+ ion, as well as of Be2+ ion, was discussed in terms of the equilibrium theory of the solvent deuterium isotope effects, which is based on the assumptions that activity coefficients of chemical species in isotopic exchange equilibria remain unchanged with the change in the deuterium atom fraction in the solvent, that the solvated hydrogen ion possesses three equivalent lyons, and that the isotopic equilibria are subject to the rule of the simple geometric mean. Satisfactory agreements were found between the observed and calculated values for the relative stability constants of the hydrolysis species of UO22+ and Be2+ in water of various hydrogen isotopic compositions.
Some Metal Complexes Containing Ethyl Acetoacetate or Ethyl Malonate as a Neutral Ligand
Authors: Morita Hideyoshi , Nakamura Yukio , Kawaguchi Shinichi
Published: July 2006

The following metal complexes containing ethyl acetoacetate (etacH) or ethyl malonate (etmalH) as a neutral ligand have been prepared: CoCl2L, CoBr2L, ZnCl2L (L=etacH or etmalH), and MnBr2(etmalH). These compounds are all hygroscopic and unstable, releasing the ester ligand below 100°C in vacuo or in donor solvents. The infrared spectra show that the ratio of keto and enol tautomers in etacH complexes is similar to that for the free ligand. The ν(C=O) band attributable to the enol tautomer of etmalH is observed in the complexes, though not in the free ligand. The electronic spectra measured in Nujol suggest that the cobalt(II) complexes are tetrahedral. The structure of MnBr2(etmalH) is not yet certain.
The Reaction of Hydrosilanes with Chlorosilanes in the Presence of Grignard Reagents. A New Method of Silicon-Silicon Bond Formation
Authors: Hosomi Akira , Sakurai Hideki
Published: July 2006

A new method has been developed for the formation of a silicon-silicon bond. Hydrosilanes having at least one phenyl or one trimethylsilyl group on a silicon atom were subjected to reaction with chlorosilanes to give unsymmetrically substituted disilanes in the presence of secondary or tertiary Grignard reagent which was inert to both chlorosilanes and hydrosilanes. The method was extended to the preparation of benzyl, allyl, and alkylsilanes.
Magnetic Circular Dichroism of Nickel(II) and Copper(II) Complexes with 1,4,8,11-Tetraazacyclotetradecane Derivatives
Authors: Kobayashi Hiroshi , Korybut-Daszkiewicz Bohdan
Published: July 2006

The magnetic circular dichroism (MCD) spectra of nickel(II) and copper(II) complexes with 1,4,8,11-tetraazacyclotetradecane derivatives were measured. An anomalous MCD dispersion was observed in a (d, d*) band at 22000 cm−1 for the copper(II) complexes and at 22000–23000 cm−1 for the nickel(II) complexes. In the ultraviolet region, the nickel(II) complexes show a normal MCD dispersion in the 35500 cm−1 band which appears only for the ligands with >C=N- double bonds, while the copper(II) complexes show an anomalous dispersion in the 39000 cm−1 band which appears even if the ligand lacks >C=N- double bonds. The 35500 cm−1 band of the nickel(II) complexes is assigned to a “metal to ligand” charge-transfer transition leg→π* and the 39000 cm−1 band of the copper(II) complexes to a “ligand to metal” charge-transfer transition leu→2b1g. In the nickel(II) complex of a ligand with two isolated and two conjugated double bonds shows a normal MCD dispersion in the 25000 cm−1 band. The absorption band is assigned to a “metal to ligand conjugated double bonds” charge-transfer transition rather than a (d, d*) transition.
The Autoxidation of Phenols Catalyzed by Phthalocyanine-Fe(II) and Salcomine-pyridine
Authors: Tada Masaru , Katsu Takashi
Published: July 2006

The autoxidation of 2,4,6-tri-t-butylphenol (1), 2,6-di-t-butylphenol (2), and 2,4-di-t-butylphenol (3) is catalyzed by phthalocyanine-Fe(II) (PC-Fe(II)) and salcomine-pyridine (SAL-Py). PC-Fe(II) gives, preferentially, the coupling product of such phenoxy radicals as 4, 7, and 8. SAL-Py, on the other hand, gives o-and p-benzoquinones, such as 5 and 6, resulting from the coupling of the phenoxy radical and the hydroperoxy radical. Metal phthalocyanines including Mn(II), Co(II), Ni(II), or Cu(II) as the central metal ion are inactive as catalysts for the oxidation. PC-Fe(II) does not catalyze the autoxidation of phenol itself and mono-alkylated phenols.
Restricted Rotation in Aromatic Ketones. I. Substituent Effects on the Barrier to Rotation about the Benzene-to-Carbonyl Bond
Authors: Nakamura Nobuo , Oki Michinori
Published: July 2006

Several aryl isopropyl ketones and aryl benzyl ketones were synthesized and their NMR spectra were recorded at various temperatures. Their temperature dependence was accounted for in terms of the restricted rotation about the benzene-to-carbonyl bond, whose free energies of activation at the coalescence temperatures varied from 9 to 15 kcal/mol according to the steric effect of ortho substituents, the buttressing effect of meta substituents, and the steric effect of the side-chain groups.
The Codimerization of Butadiene and Ethylene Catalyzed by Cobaltous Chloride-Ditertiary Phosphine Complexes-Grignard Reagent-ROH. Effects of Ditertiary Phosphine Ligands and Alcohols
Authors: Kagawa Teruhiko , Hashimoto Harukichi
Published: July 2006

Butadiene-ethylene codimerization is accomplished by means of the catalyst derived from the reactions of CoCl2(Ph2P(CH2)nPPh2)m with a Grignard reagent and then with appropriate amounts of alcohols to obtain 1,4-cis-hexadiene selectively. The yield of 1,4-hexadiene depends on the number of ditertiary phosphine ligands (m), the methylene-chain length of the ligand (n), and the kind of alcohol. A hydride complex, HCo(Ph2P(CH2)2-PPh2)2 also has codimerization activity in the presence of both n-PrMgCl and alcohols. It is considered that the resulting alkoxymagnesium chloride activates the catalyst.
Linear Conjugated Systems Bearing Aromatic Terminal Groups. VI. Syntheses and Electronic Spectra of 6,6′-Dichrysenylpoly-ynes
Authors: Akiyama Shuzo , Nakagawa Masazumi
Published: July 2006

6,6′-Dichrysenylpoly-ynes (In, n=1–6) have been synthesized and their electronic spectra were measured. It was found that the bathochromic shifts of the longest-wavelength absorption peaks (λmax) along with an increase in the number of acetylenic bond (n) were proportional to n1.6 (λmax=5.8n1.6+394nm).
Base-catalyzed Condensation of o-Nitroacetophenone. V. Hydrogenation of Compound A, a Condensation Product. Formation of a 4-Quinolone from an Indoline System
Authors: Miwa Toshio
Published: July 2006

The catalytic hydrogenation of compound A, a base-catalyzed condensation product of o-nitroacetophenone, followed by treatment of the product with acid gave a 4-quinolone. The quinolone proved to be 2-[1-(o-aminophenyl)-1-hydroxyethyl]-4-quinolone by the oxidative degradation of the corresponding quinoline derivative.
Aminocyclitols. XXVIII. Bromination of Inosamines and Inosadiamines
Authors: Suami Tetsuo , Ogawa Seiichiro , Yanagida Shinichi , Nojima Kazuhiro
Published: July 2006

Bromination of four inosamines (myo-2 (1), chiro-1 (2), muco-1 (3), and scyllo (4)) and three inosadiamines (neo-1,4 (11), muco-1,5 (14a,b), and muco-1,4 (19)) with acetyl bromide and acetic anhydride in a sealed tube at 130–160°C has been studied. 2,5-Dibromo-2,5-dideoxy-chiro-inosamine-3 tetraacetate (8), was obtained from 1,2, and 3, and, as a monobromide, only 2-bromo-2-deoxy-chiro-inosamine-3 pentaacetate (7) could be isolated from the bromination product of 3. From 11, monobromide (12) and dibromide (13) were obtained. From 14a or 14b, 2-bromo-2-deoxy-chiro-inosadiamine-3,5 pentaacetate (15) was obtained, and, under a more drastic condition, 15 was further brominated to afford 1,5-dibromo-1,5-dideoxy-chiro-inosadiamine-2,4 tetraacetate (16). The bromo compounds so obtained were converted into the corresponding deoxy or dideoxy derivatives by hydrogenolysis. All the structures of the new compounds have been confirmed on the basis of proton magnetic resonance (PMR) spectroscopy using their acetyl derivatives. Considering from the structures of the bromides, a mechanism of a bromination reaction has been proposed.