bluuebunny/crossref_metadata_2025 huggingface dataset:
Total Syntheses of Carbohydrates. III. Dl-Glyceraldehyde and 2-Deoxy-Dl-erythro-pentose
Authors: Mimaki Kosuke , Masunari Michihiko , Nakaminami Gen , Nakagawa Masazumi
Published: July 2006

The synthesis of Dl-glyceraldehyde (III) by the Barton’s oxidation of Dl-isopropylideneglycerol (I) was described. 2-Deoxy-Dl-erythro-pentose (IX) (2-deoxy-Dl-ribose) has been synthesized by the Barton’s oxidation of 2-deoxy-3,4-O-isopropylidene-5-O-(tetrahydro-2-pyranyl)-Dl-erythro-pentitol (VIII) and by the hydroboration of Dl-erythro-4-pentyn-1,2,3-triol (XI) followed by hydrogen peroxide oxidation. The latter method gave crystalline 2-deoxy-Dl-erythro-pentose (IX) in a reasonable yield.
The Epoxidation of Homoallylic Alcohols and the Formation of Sesquiterpene Diols
Authors: Yamamura Shosuke , Iguchi Masanobu , Niwa Masatake , Hirata Yoshimasa
Published: July 2006

The epoxidation of homoallylic alcohols was effected with m-chloroperbenzoic acid in ether, and the resulting epoxides were reduced with lithium aluminum hydride to the corresponding diols. Particularly in the cases of calameone and isocalamendiol, the exocyclic double bond at the C3-position was attacked by the peroxy-acid from the side opposite to the axial hydroxyl group at the C5-position.
Kinetic Studies of Intermolecular Hydrogen Bonding in Carboxylic Acids by Means of Ultrasonic Absorption Measurement. I. Fatty Acids
Authors: Sano Takayuki , Tatsumoto Nobuhide , Niwa Toshio , Yasunaga Tatsuya
Published: July 2006

The ultrasonic absorptions in n-butyric, isobutyric, n-valeric, isovaleric, and n-caproic acids have been measured in the frequency range from 2.5 to 95 MHz in order to study the relationship between the ultrasonic absorption and the chemical structure of the alkyl group in carboxylic acids. The relaxation absorptions were observed for all the acids with relaxation frequencies in the range of 1.6–8.7 MHz. The kinetic parameters have been calculated on the basis of an assumption that the absorptions are associated with the breakage of one of the two hydrogen bonds in the dimer, as in the case of propionic acid. The values of the heat of reaction, ΔH, were calculated to be 4.7–6.4 kcal per mole of dimer. By an application of the results to Taft’s equation, logK=ρ*σ*+sEs, it is deduced that the change in the ΔH in a series of monocarboxylic acids is due to variations in the inductive effect of each alkyl group. However, the change in the heat of activation, ΔH≠, can not be explained in terms of the inductive effect.
A New Theory of Melting at High Pressures
Authors: Kanno Hitoshi
Published: July 2006

As an improvement of the significant structure theory, a new partition function of monatomic liquid was derived:

Zl(T, Vl)=\left{\overset3Nv\underseti=1Π\left[2sinh\left(\frachνi2kT\ight)\ight]−1\ight}\left{\left(\frac2πmkTh2\ight)3⁄2\fraceVfNt\ight}Ntexp\left{\fracΦl(Vl)kT\ight}

where 3Nv and 3Nt, (Nv+Nt=N; Avogadro number), are the numbers of freedom in vibrational and translational motions, respectively, vi the i-th normal vibration in the vibrational motion, m the mass of molecule, Vf the free volume of liquid, and Φl(Vl) the configurational potential energy of liquid. Melting of argon at high pressures is successfully interpreted by means of the partition function.
On the Change of Electrical Conductivity of Metal on Melting
Authors: Kanno Hitoshi
Published: July 2006

A partition function of liquid recently proposed by the present author has been applied to the change of the electrical conductivity of metal at melting point. The relation between σs⁄σl and θD⁄θl is more successfully interpreted by this partition function than that used by Mott.
Studies on the Interaction between Long Chain Alcohols and Alkyl Sulf ates. II. Molecular Association between Dodecyl Alcohol and Dodecyl Sulfate of Divalent Metals
Authors: Moroi Yoshikiyo , Motomura Kinshi , Matuura Ryohei
Published: July 2006

Molecular interaction between dodecyl alcohol and dodecyl sulfate of divalent metal cations such as Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Co2+, Ni2+, and Cu2+ was studied by measurement of heat of complex formation, differential thermal analysis and infrared spectroscopy. It was found that magnesium, manganese, cobalt, nickel, and copper dodecyl sulfates formed two or three kinds of complexes with dodecyl alcohol, differing in composition depending on temperature. On the other hand, no evidence of complex formation could be found by these experimental techniques for calcium, strontium and barium dodecyl sulfates, all of which are very small in solubility into water. For the former class of metal dodecyl sulfates the composition of complex was 3.5–4.0 in molar ratio of alcohol to sulfate at temperature below the melting point of alcohol, while it was 5.0–6.0 at temperature above it. The heat of complex formation above the melting point of alcohol was −40–−44 kcal/mol-sulfate. Two or three characteristic absorption bands could be found over the range 3200–3500 cm−1, suggesting that the complex formation is due to hydrogen bonding between two components.
The Kinetics and Mechanism of the Reactions of N-Sulfinylanilines with Formic Acid
Authors: Yamada Fukiko , Nishiyama Tomihiro , Emi Toshiharu
Published: July 2006

We have examined the kinetics of the reactions between N-sulfmylanilines and formic acid. The reactions follow this rate equation; rate=k[R–C6H4–NSO][HCOOH]. The kinetic runs were made over a wide temperature range (40–90°C) in order to obtain the values of the activation energy. The values for the reactions of N-sulfinylaniline, N-sulfinyl-p-toluidine, and N-sulfinyl-p-chloroaniline with formic acid are 14.6, 15.1, and 10.1 kcal/mol respectively. The reaction mechanism is discussed by means of their NMR spectral data.
Induced Optical Activity of Nucleic Acid-Toluidine Blue O Complex
Authors: Nakamura Tomoyasu , J. I’Haya Yasumasa
Published: July 2006

The absorption, circular dichroism (CD) and optical rotatory dispersion spectra of DNA–toluidine blue O complexes were observed over the visible absorption spectral region. Effect of temperature on CD was examined at the temperatures 6–86°C. For the complex of a low DNA phosphate to dye ratio, the Krönig-Kramers transform was carried out and one positive and four successive negative CD bands were resolved. It is concluded that the shorter wavelength CD bands, one positive and one negative, are due to an exciton splitting of the dye dimers and that the rest may be induced by an asymmetric environment of the DNA deoxyribose residue.
Order of Quencher Participation in Photochemistry. I. Proton Transfer from the Excited p-Hydroxybenzophenone in Mixed Solvents of Cyclohexane and Alcohols
Authors: Hoshino Mikio , Koizumi Masao
Published: July 2006

The change in the absorption spectrum of p-hydroxybenzophenone (HOBP) and relative quantum yields Φrel for the photoreduction of HOBP have been studied in mixed solvents consisting of cyclohexane and four kinds of alcohol. The change in absorption spectrum occurs in two steps with methanol, ethanol, and 2-propanol, suggesting the following equilibria, HOBP+S\leftrightharpoonsA, and A+S\leftrightharpoonsB (S, alcohol molecule). Φrel changes in two steps with methanol and ethanol and in one step with 2-propanol and amyl alcohol roughly in line with the spectral change. The changes in Φrel have been interpreted to be due to the deprotonation of HOBP. Φrel=1⁄(1+K[S]n) holds for them with n=5.5 for 2-propanol and n=1 for other alcohols. A linear relation holds between 1⁄(n−1)logK and Hammett’s constant of alkyl group of alcohols, suggesting that the deprotonation tendency depends upon the specific interaction between alcohol molecules. The reactivity of A-species is considered to depend largely on the dielectric nature of the solvent.
On the First Singlet and Triplet Excited States of the Lithium Molecule
Authors: Kohda Susumu , Ohno Kimio , Taketa Hiroshi
Published: July 2006

The first singlet and triplet excited states of Li2 are studied by the MO and VB methods. As basis, only 1s and 2s AO’s are used. In the MO description, the antibonding MO is more diffuse than the bonding MO and the difference is bigger in 1Σu+ than 3Σu+ In the VB description, splitting of the 2s orbital in the purely ionic (1Σu+) and covalent (3Σu+) wave functions does not lead to any energy lowering. An interpretation of this result is suggested. The calculated singlet-triplet separation is compared with previous calculations.
Thermal Decomposition of Ammonium Salts of Transition Metal Oxyacids. II. The Determination of the Gas Constituents Evolved by Ammonium Paramolybdate Decomposition
Authors: Park Il-Hyun
Published: July 2006

Gases evolved by the decomposition of ammonium paramolybdate tetrahydrate have been analyzed by means of an omegatron mass spectrometer. Only water molecules of the hydration were eliminated during the first stage of decomposition, and the final stage was not the elimination reaction of ammonia but the oxidation reaction of ammonia by Mo(VI) oxide. Between 150 and 250°C, ammonia and water were evolved in a mole ratio of roughly 2:1, corresponding to the elimination of (NH4)2O. However, the range is not clear because of the overlap of the elimination of water at the lower limit and that of nitrogen at the upper limit. At higher temperatures, a small amount of NO was observed.
Kinetics of Multidentate Ligand Substitution Reactions. XIII. Substitution Reactions of 1-(Hydroxy-4-methyl-2-phenylazo)-2-naphthol-4-sulfonic Acid (Calmagite) with Nickel (II)-Glutamate, -Aspartate, -Iminodiacetate, -Nitrilotriacetate and -Diethylenetriamine Complexes and That with the Cobalt(II)-Nitrilotriacetate Complex
Authors: Kodama Mutsuo , Sato Takami , Karasawa Sadatsugu
Published: July 2006

The substitution reactions of calmagite with nickel(II)-glutamate, -aspartate, -iminodiacetate, -nitrilotriacetate, and -diethylenetriamine complexes, and that with the cobalt(II)-nitrilotriacetate complex, were studied by employing the stopped-flow technique. In the calmagite reactions with the nickel(II)-glutamate, -aspartate, and -iminodiacetate complexes, the reaction products were found to be mixed-ligand complexes involving calmagite and glutamate, aspartate, or iminodiacetate anions. In these reactions, the 1 : 2 ratio complex dissociates rapidly into the 1 : 1 ratio complex first; then, the 1 : 1 ratio complex reacts slowly with the calmagite anion to form a mixedligand complex. From a comparison of the observed rate constant with that estimated on the basis of the proposed reaction intermediate, it was concluded that the latter step proceeds through the outer-sphere complex between the calmagite anion and a 1 : 1 ratio complex, and that the water-loss from the 1 : 1 ratio complex is the slowest step. In the cases of the reactions of calmagite with nickel (II)-nitrilotraicetate and -diethylenetriamine complexes, and that with the cobalt (II)-nitrilotriacetate complex, all the reaction invariably gave a metal (II)calmagite complex with a 1 : 1 composition, MD-. These reactions were found to proceed through the completely-deprotonated and divalent calmagite anions.
Kinetics of Multidentate Ligand Substitution Reactions. XIV. Substitution Reactions of Ethylenediaminetetraacetic Acid (EDTA) and N-(2-Hydroxyethyl)ethylenediamine-N,N′,N′-triacetic Acid (EDTA-OH) with Nickel(II)-Ethylenediaminemonoacetate (EDMA) and -Diethylenetriamine (Dien) Complexes
Authors: Kodama Mutsuo , Hashimoto Michinori , Watanabe Toshiyuki
Published: July 2006

The kinetics of the substitution reactions of EDTA and EDTA-OH with nickel(II)-EDMA and -Dien complexes were studied using the polarographic technique. The substitution reactions of EDTA and EDTA-OH with the nickel(II)-EDMA complex were found to have a common reaction mechanism. They were first-order with respect to EDTA or EDTA-OH, and also first-order with respect to the nickel (II)-EDMA complex with a 1: 1 composition; their reaction mechanism could be formulated as:

(Remark: Graphics omitted.)

The substitution reactions of EDTA and EDTA-OH with the nickel(II)-Dien complex were also studied under experimental conditions where the reaction could be treated as a pseudo-first-order reaction. The reactions were first-order with respect to the concentration of EDTA or EDTA-OH. However, their reaction rate were independent of the concentrations of the nickel(II)-Dien complex and of uncomplexed Dien. This fact was ascribed to the formation of a stable outer-sphere complex between the nickel(II)-Dien complex with a 1: 2 ratio and the EDTA or EDTA-OH anion, through which the substitution reaction proceeds.
The Extraction and Spectrophotometric Determination of Titanium(IV) with Tiron
Authors: Wakamatsu Yoshinobu , Otomo Makoto
Published: July 2006

A method has been described for the spectrophotometric determination of titanium(IV), which is based on the extraction of the titanium (IV)-Tiron chelate into n-butanol in the presence of 1,3-diphenylguanidinium salt. The extracted species containing titanium, Tiron, and diphenylguanidine in a molar ratio 1:2:4, has an absorption maximum at about 385 nm. The maximum extraction is obtained when the pH of the initial aqueous phase is controlled to about 3.0 to 4.0. Beer’s law is obeyed up to 25 μg titanium per 10 ml of n-butanol. The molar absorptivity of the extracted species is 1.4×10−4 at 385 nm. Molybdenum (VI) and chelating agents interfere with the determination of titanium.
Cobalt(II) and -(III) Complexes of 1,5-Dialkylpentane-2,4-diones
Authors: Yoshida Isao , Kobayashi Hiroshi , Ueno Keihei
Published: July 2006

Based on the spectral studies in visible, ultraviolet as well as in infrared regions, the dimeric octahedral structure was proposed for bis(heptane-3,5-dionato)cobalt(II) monohydrate, [Co(DNPM)2·H2O], bis(nonane-4,6-dionato)cobalt(II) monohydrate, [Co(DNBM)2·H2O], bis(2,8-dimethylnonane-4,6-dionato)cobalt(II) monomethanolate, [Co(DIVM)2·CH3OH], and bis(tridecane-6,8-dionato)cobalt(II) monomethanolate, [Co(DNCM)2·CH3OH]. The dimeric chelates of the type [CoL2·B], where B represented water or methanol, were stable in solid state, however, they freed the base B to form a tetrahedral monomeric complex in non-donating solvents. A red-pink solution of the cobalt(II) chelates were oxidized spontaneously in the period of a few days to give a green solution of cobalt(III) chelates of type [CoL3]. Cobalt(III) chelates of 2,6-dimethylheptane-3,5-dione (DIBM) and 2,2,6,6-tetramethylheptane-3,5-dione (DPVM) in addition to the above ligands were synthesized and their spectra were discussed in comparison with the corresponding cobalt(II) chelates.
Chemical Behavior of Carbon in High-purity Silicon in the Dissolution and Fusion of the Matrix
Authors: Nozaki Tadashi , Makide Yoshihiro , Yatsurugi Yoshifumi , Endo Yoshiyuki , Akiyama Nobuyuki
Published: July 2006

The behavior of carbon in high-purity silicon in the dissolution and fusion of the matrix was studied by the 11C-tracer technique. Silicon samples containing 11C, either atomistically dispersed or mainly coagulated as SiC, were prepared. In alkali dissolution, no loss of 11C was observed, and carbon originally dispersed in silicon was found to behave in a similar way to colloidal carbon under subsequent treatments. By HF–HNO3–KIO4 dissolution and succeeding KMnO4 treatment, the dispersed carbon was oxidized almost quantitatively but the SiC coagulates were not completely decomposed. In alkali fusion a part of 11C was lost. By fusion with Pb3O4-B2O3, carbon in both states was converted into CO2. The results suggest a possible application of activation analysis to the measurement of the coagulation degree of carbon in high-purity silicon.
Aroyl Arenesulfonyl Peroxides IV. The Mechanism of Carboxy-inversion of Benzoyl p-Toluenesulfonyl Peroxide
Authors: Hisada Ryuki , Minato Hiroshi , Kobayashi Michio
Published: July 2006

Benzoyl p-toluenesulfonyl peroxide (BTP) with 18O-labeled carbonyl oxygen and 18O-labeled sulfonyl oxygen were prepared. They were decomposed in benzene in the presence or in the absence of trifluoroacetic acid,and the phenyl p-toluenesulfonyl carbonate (PTC)-18O produced was isolated and analyzed. It was found that the carbonyl oxygen-18 of BTP was retained as the carbonyl oxygen of PTC, whereas the sulfonyl oxygen-18 of BTP was equilibrated with the peroxidic oxygen. The mechanism of the carboxy-inversion was discussed.
Heterocycles Structurally Influenced by a Side Chain. II. 7-Phenacyl-xanthopterins and 6-Phenacylisoxanthopterins
Authors: Iwanami Yasuo , Seki Taketsugu
Published: July 2006

Phenacyl derivatives of two naturally-occurring pteridines and their 4-amino analogues (III and V) have been synthesized for their structural study. Since these compounds are obtained by the condensation of ethyl benzoylpyruvates (II) with tri- or tetraaminopyrimidine (I), a carbon-nitrogen double bond, which is adjacent to the phenyl group of the side chain, may be expected in the ring (Remark: Graphics omitted.). However, their NMR spectra show that the double bonds of all the products are displaced onto the side chain (Remark: Graphics omitted.), the carbonyl of which is hydrogen-bonded with the secondary amino group thereby formed. This form of V makes striking contrast to alkyl isoxanthopterin-6-acetates (X), in which the corresponding double bond remains undisplaced. The intermediate products of V (IV) and V were hydrolyzed with acid or alkali into 6-methyl-isoxanthopterin (VI) and benzoic acids (VII).
Studies on Aminosugars. XXX. The Synthesis of 3′-Deoxykanamycin
Authors: Umezawa Sumio , Nishimura Yoshio , Hineno Hirokuni , Watanabe Kohei , Koike Soichiro , Tsuchiya Tsutomu , Umezawa Hamao
Published: July 2006

3′-Deoxykanamycin has been totally synthesized from 6-O-(2-O-benzyl-3-deoxy-3-ethoxycarbonylamino-4,6-O-isopropylidene-α-d-glucopyranosyl)-N,N′-diethoxycarbonyl-2-deoxystreptamiine and 6-azido-2,4-di-O-benzyl-3,6-dideoxy-α-dribo–hexopyranosyl chloride. It has been found that the 3′-deoxykanamycin has strong antibacterial activity not only against common bacteria but also against kanamycin-resistant bacteria.
Syntheses and Reactions of Ferrocene-Containing Polymers, VI. Polarography and Electron Transfer Equilibria of Some Ferrocene-Containing Polymers
Authors: Nakashima Toshihide , Kunitake Toyoki
Published: July 2006

Polarography and electron transfer equilibria of some ferrocene-containing polymers were studied in comparison with small-molecule analogs. The oxidation half-wave potentials of polyvinylferrocene and polydivinylferrocene (almost completely cyclized) in CH2Cl2 were close to those of ferrocene and [3]ferrocenophane, respectively. This is in line with structural similarity. Only one oxidation step was observed in the polarogram of triferrocenylbenzene and polyethynylferrocene, suggesting that the electronic interactions between ferrocene units are small in these compounds. Electron transfer equilibrium was observed between ferrocene units in polymer and iodine. Equilibrium constants of the [3]ferrocenophane unit were greater than those of the unbridged ferrocene unit. The ferrocene unit in polymer showed greater equilibrium constants than those of their small-molecule analogs.
Studies on Tritylated Sucrose. II. Di-O-Tritylsucroses
Authors: Otake Toshiki
Published: July 2006

Three isomeric di-O-tritylsucrose were isolated from a mixture of tritylated sucrose by the reaction of sucrose and trityl chloride in mole ratio 1:2 Structures of isomeric diethers were established by application of NMR to the hexa acetyl derivatives. They are recognized as 6,6′-, 1′,6-, and 1′,6′-di-O-tritylsucrose. The former two substances were crystallized as colorless prisms.
Aroyl Arenesulfonyl Peroxides. VI. Benzoyloxylation and p-Toluenesulfonyloxylation of Aromatic Compounds with Benzoyl p-Toluenesulfonyl Peroxide
Authors: Hisada Ryuki , Kobayashi Michio , Minato Hiroshi
Published: July 2006

Benzoyl p-toluenesulfonyl peroxide (BTP) was decomposed in benzene, toluene, chlorobenzene, nitrobenzene, or anisole in a nitrogen or oxygen atmosphere. Yields of aryl benzoates and p-toluenesulfonates were always greater in an oxygen atmosphere than those in a nitrogen atmosphere, except those with nitrobenzene. The isomer distributions of these aryl benzoates and p-toluenesulfonates were determined. The rate of decomposition in anisole was considerably greater than those in other arenes. When BTP[carbonyl-18O] was decomposed in anisole, the o- or p-anisyl benzoate formed was found to contain about equal amounts of oxygen-18 at both the carbonyl and phenoxy oxygens. On the basis of these findings the mechanisms of benzoyloxylation and p-toluenesulfonyloxylation were discussed.
Rate-controlling Processes in the Phosphidation of Copper by Phosphorus Vapor
Authors: Sasaki Yoshinori , Ueda Shiro
Published: July 2006

The phosphidation kinetics of a copper exposed to a phosphorus atmosphere from 1 to 10 Torr absolute pressure in the temperature range of 150–250°C have been determined with a closed system. The reaction rate in the earlier periods of time was linear and, subsequently, parabolic; therefore, it can be considered that the rate-determining process changes from adsorption to diffusion. The linear rate constants were expressed as a function of the phosphorus pressure on the basis of the Langmuir adsorption isotherm. The P4 molecule is chemically adsorbed as two —P=P—, whereas at higher temperatures and pressures the solubility process appears to be predominant. From the phosphorus distribution in cross sections of scaling films, it has been revealed that, in the adsorptoincontrolled regions, the phosphorus content is maintained at a constant concentration, corresponding to Cu3P, and that, in the diffusion-controlled regions, solid solutions more rich in phosphorus than Cu3P are formed at the outer layers. The faceted crystals of Cu3P have sometimes developed with an orientation of the (300) plane, depending on the reaction conditions.
Ternary Diffusion in the 20Ne–22Ne–CO2 System
Authors: Oishi Yasumichi , Sugisaki Masayasu , Kamei Yoshinobu , Shono Yasuyuki
Published: July 2006

Self-diffusion coefficients of CO2 of the binary system of Ne and CO2 were measured for the whole composition range at 25°C under 760 mmHg. The system was also analysed as a ternary system of 20Ne, 22Ne, and CO2. The isotope separation of 20Ne and 22Ne during the course of diffusion was measured and analyzed by means of the ternary diffusion equations obtained by an extension of Darken’s binary diffusion equation. The experimentally observed 22Ne/20Ne ratios agreed well with the values calculated by the equations. The results show that the concept of the intrinsic diffusion flux density, introduced by Darken for binary diffusion, is valid and applicable to ternary diffusion in the gaseous system.
Photochemistry of Acridines. XVIII. Photoreduction by Nonpolar H-donors and the Disproportionation of C-Radicals
Authors: Hoshino Mikio , Niizuma Shigeya , Koizumi Masao
Published: July 2006

It was found that the photoreduction of acridine in cyclohexane and toluene occurs via molecular and radical mechanisms. The T-energy transfer experiments using biacetyl as an energy acceptor have revealed that the molecular mechanism occurs in the T(n–π*) state, and the radical in the singlet excited state. The effect of the addition of piperylene on the quantum yield of photoreduction was investigated in cyclohexane, methanol, ethanol and isopropanol. The results have been interpreted on the following assumptions. 1) Complete T-energy transfer from acridine to piperylene. 2) No quenching action of piperylene on the singlet excited acridine. 3) Complete transformation of C-radicals of acridine to stable products by piperylene. The results have led to the conclusion that the C-radical undergoes disproportionation in cyclohexane, methanol and ethanol, while it is completely transformed to an acridan-type compound in isopropanol.
Statistical Thermodynamics and Adsorption
Authors: Tykodi Ralph J
Published: July 2006

The proper correlation of thermodynamic quantities derived from experimental gas-solid adsorption systems with those derived from statistical mechanical models is discussed; the usual method of making the correlation is found to be unsatisfactory, and a new method is proposed.
The Catalytic Exchange of Hydrogen-Deuterium on Copper-Nickel Alloy Plates after Various Surface Treatments
Authors: Takasu Yoshio , Yamashina Toshiro
Published: July 2006

The catalytic activities of nine copper-nickel alloys (5 cm2 in area) in hydrogen-deuterium exchange were examined at 1.5 Torr partial pressures of hydrogen and deuterium, using an ultra-high vacuum apparatus incorporated with an omegatron mass spectrometer for continuous gas analysis. Without any surface treatment, the activity was greatest on pure nickel, decreased gradually as the content of copper in the alloys increased and virturally vanished in the alloys containing copper more than 70%. The activity of each alloy sample was observed to be extremely enhanced by a slight surface treatment of oxidation-reduction (Po2=2.3 Torr at 500°C for 1 min, PH2=16 Torr at 300°C for 2 hr). The activity of the 85% copper alloy after the oxidation-reduction treatment was greatest, one hundred times that of pure nickel. Annealing for a short time in an ultra-high vacuum subsequent to the oxidation-reduction treatment caused the catalytic activity to decrease abruptly at a critical temperature (425°C). On the bases of the electron microscopic observations and the measurement of the surface roughness changed by the pre-treatments, the nature of active sites on copper-nickel alloys was discussed.
Infrared Absorption Intensities of Out-of-plane CH Bending Vibrations of Substituted Benzenes. IV. Solvent Effect on the Intensities of the Bands of Aniline
Authors: Higuchi Seiichiro , Kuno Eisaku , Tanaka Shigeyuki , Kamada Hitoshi
Published: July 2006

The infrared absorption intensities of out-of-plane CH bending and ring out-of-plane deformation vibrations of aniline have been measured in an acetone solvent mixed with various quantities of acetic acid. When such solvents are used, new peaks attributable to aniline interacting with the acid appear as shoulders of each of the original bands. A marked decrease in the sums of the intensities of the above two modes (Ao) has been observed for the bands of aniline interacting with the acid. It is demonstrated that the degree of such a decrease in intensity depends on the molar ratios of aniline and the acid. When there exists enough the acid in comparison with aniline, the values of Ao become minimum. On the other hand, when the numbers of the exsiting acetic acid molecules are much smaller than those of aniline, the values of Ao are considerably greater than those in the former case. In this case, a farily long time is needed until the interaction reaches an equilibrium state. Finally, when a very large amount of the acid is added, the bands attributable to aniline interacting with the acid are no longer observed. An attempt has been made to interpret these phenomena in terms of the state of the aggregation of aniline, acid and acetone molecules in the solutions.
Properties of Water in Macromolecular Gels. IV. Proton Magnetic Resonance Studies of Water iu Macromolecular Gels
Authors: Aizawa Masuo , Mizuguchi Jun , Suzuki Shuichi , Hayashi Shoichi , Suzuki Teruo , Mitomo Noriko , Toyama Hiroshi
Published: July 2006

Electrochemical and dilatometric studies have indicated that at least three states of water exist in macromolecular gels. The properties of each state of water in gels such as agarose gels were investigated by highresolution and broadline PMR over the temperature range from +50 to −60°C. The linewidth of water protons in gels was found to depend markedly on the water content of gels, and the linewidth vs. water content curve gave two inflection points. One of the inflection points can be attributed to the so-called bound water, but the other cannot be explained unless three states of water are assumed in gels. Three kinds of transition temperatures were confirmed by anomalous changes in the PMR linewidth below 0°C. The so-called bound water exhibited no transition temperature between 0 and −20°C, and free water gave the transition temperature at 0°C. Moreover, the transition temperature of a quantity of water was distributed in the range from 0 to −20°C. On the basis of the transition temperature, the properties of water in macromolecular gels are discussed.
Molecular Vibrations, Conformational Analyses, and Force Fields of Normal and Monodeuterated (Methylthio)methanethiol
Authors: Ohsaku Masaru , Shiro Yuji , Murata Hiromu
Published: July 2006

(Methylthio)methanethiol, CH3SCH2SH, and (methylthio)methanethiol-d1, CH3SCH2SD, were prepared, and their infrared spectra were obtained in the gaseous, liquid, and solid states. The obtained spectra have been assigned. The frequency shifts by D-substitution, gaseous-liquid transition, and liquid-solid transition have also been discussed. The normal coordinates of these thiols have been treated by a modified Urey-Bradley force field. The force constants used in the computation have been transferred from those previously reported, but we adjusted them to produce the experimental wave numbers. The calculated wave numbers correspond well with those observed. The stable molecular conformations of the normal and deuterated species have been determined by the aid of the normal coordinate treatment. In the gaseous and liquid states, at least three to four forms from among TT, TG, GT, GG, and GG′ have been confirmed to exist. In the solid state, though, CH3SCH2SH or GH3SCH2SD exists in only one form: GG.
Order of Quencher Participation in Photochemistry. II. Quenching Action of Ethanol on the Photoreduction of p-Aminobenzophenones
Authors: Hoshino Mikio , Koizumi Masao
Published: July 2006

The effect of the addition of ethanol (quencher of the reaction) on the photoreduction of p-aminobenzophenone (NH2BP) and dimethyl-p-aminobenzophenone in cyclohexane and in ether has been studied. The order of quencher participation for ethanol has been found to be two for the former and one for the latter. The results were interpreted to be due to the formation of intramolecular C–T state during excitation, promoted by the attachment of one ethanol (or ether) molecule to the NH2-group and one ethanol molecule to O=C of NH2BP.
Heat Capacities of Antimony Trichloride and Tribromide
Authors: Takeyama Kuniko , Atoda Tetsuzo
Published: July 2006

Heat capacities of liquid antimony trichloride and tribromide saturated with their respective vapors were determined with an adiabatic calorimeter as follows: 35.2 cal K−1mol−1 in the range, 90–210°C, for trichloride, and 34.6 cal K−1mol−1 in the range, 130–270°C, for tribromide.
Electronic Spectra and Structures of Organic π-Systems. III. Electronic Spectra of Nitrocyclopentadienide Anion and Formylcyclopentadienide Anion
Authors: Yoshida Zen-ichi , Kobayashi Tsunetoshi , Konishi Akihiko
Published: July 2006

The electronic spectra of sodium nitrocyclopentadienide and sodium formylcyclopentadienide have been measured in several solvents. The electronic states of these compounds have been calculated by variable integrals methods I and II (modified Pariser-Parr-Polpe method). The longest wave-length strong absorption band of nitrocyclopentadienide (304 mμ) or formylcyclopentadienide (280 mμ) in isooctane has been assigned to the superimposed band of two intramolecular chage-transfer transitions from the five-membered ring to the nitro or formyl group. Agreement between the calculated and observed transition energies in isooctane is satisfactory.
The Kinetics of Electron-transfer Reactions between Oxalato-Cobalt(III) Complexes and Iron(II) in Acid Aqueous Solutions
Authors: Ohashi Kousaburo
Published: July 2006

An investigation of the Fe2+ reductions of Co(ox)(NH3)4+, Co(ox)(en)2+, Co(ox)(trien)+, Co(ox)(dip)2+, Co-(ox)2(en)−, and cis-Co(ox)2(NH3)2− has been carried out spectrophotometrically. The rate constants of Co(ox)N4+-type complexes increase in this order: Co(ox)(phen)2+>Co(ox)(dip)2+>Co(ox)(NH3)4+>Co(ox)(en)2+>Co(ox)-(trien)+, and these of Co(ox)2N2−-type complexes, cis-Co(ox)2(NH3)2−>Co(ox)2(en)−. The variation in reactivity is mainly ascribed to a change in the enthalpy of activation. The rate constants of Co(ox)(NH3)4+, Co(ox)(en)2+, cis-Co(ox)2(NH3)2−, and Co(ox)33− increase with the values of the hal-wave potential of the polarographic reduction (CoIII→CoII) and with the decrease in the wave number of the maxima of the absorption spectra of the complexes.
Stereoselectivity in Mixed Tris-type Complexes of Cobalt(III) with Glycine and l-Glutamic Acid
Authors: Kawasaki Kiyoshi , Shibata Muraji
Published: July 2006

The following ten complexes have been isolated from a reaction mixture of the [CoCO3(gly)2]− ion and l-glutamate in the presence of active charcoal: mer-[Co(gly)2l-glutH] (two isomers), mer-Cogly(l-glutH)2], mer-Λ-[Co(l-glutH)3],fac-Λ and Δ-[Co(gly)2(l-glutH], fac-Λ and Δ-[Cogly(l-glutH)2], and fac-Λ and Δ-[Co(l-glutH)3]. These complexes have been characterized by various spectral data. The Δ/Λ ratios in the fac isomers have been estimated to be ca. 60/40, 68/32, and 75/25 for the bis(glycinato), bis(l–glutamato) and tris(l–glutamato) complexes respectively, while no appreciable stereoselectivity has been found in the corresponding mer isomers.
Derivatographic Studies on Transition Metal Complexes. VIII. Thermal Deaquation-Anation Reaction of cis-[CoX(H2O)N4]Y2 Type Complexes in Solid Phase
Authors: Tsuchiya Ryokichi , Suzuki Masatatsu , Kyuno Eishin
Published: July 2006

The deaquation-anation reaction of cis-[CoX(H2O)N4]Y2 type complexes, where X is chloride or bromide ion, N4 is tetraammine or bis(ethylenediamine), and Y is chloride, bromide or nitrate ion, was investigated by means of both derivatographic and isothermal methods. Some of these reactions were found to include the stereochemical changes, the structure of reaction products formed by deaquation-anation reaction being considerably affected by the counter ionic species: the chloride complexes, where Y=Cl, were deaquated with retention of cis-structure, whereas the bromide complexes, where Y=Br, underwent cis-to-trans stereochemical change. According to the isothermal measurement in the isomerization of cis-[CoCl(H2O)en2]Br2·H2O, cis-[CoCl(H2O)en2]-Br(NO3) and cis-[CoBr(H2O)en2]Br2·H2O, these rates were found to obey the first-order rate law and the activation energies, Ea, were obtained to be 38±5, 68±6 and 37±5 kcal mol−1 and the enthalpy changes, ΔH, 13.5±2.0, 7.5±2.0 and 13.3±2.0 kcal mol−1 for the respective complexes.
Electronic Spectra and Structures of Organic π-Systems. IV. Electronic Spectra of Nitropyrroles
Authors: Yoshida Zen-ichi , Kobayashi Tsunetoshi , Yamada Hidenori
Published: July 2006

The electronic spectra of 2-nitropyrrole and 3-nitropyrrole have been measured in various solvents and compared with the values calculated by the variable integrals method II. Agreement between the observed and the calculated transition energies is satisfactory. From eigenvectors of both nitropyrroles, the localization of molecular orbitals to the moiety of molecule has been discussed. The π-electon densities and π-bond orders of both molecules have also been calculated.
Reactions of Cuprous Acetate with Organic Halides
Authors: Kawaki Takao , Hashimoto Harukichi
Published: July 2006

Cuprous acetate was prepared from phenylcopper and acetic acid, and its reactivity for organic halides was investigated. The mixed anhydrides containing an acetyl group are formed easily from cuprous acetate and acyl halides. The reaction of cuprous acetate with CH3I, C2H5I, CH2=CHCH2Br, and PhCH2Cl in acetonitrile gives the corresponding ester. The addition of ethylenediamine converts the above reaction to a reductive coupling reaction, resulting in bibenzyl (50% yield) from benzyl chloride and 1,5-hexadiene (95–98% yield) from allyl chloride or bromide. The reaction of cuprous acetate-ethylenediamine with aryl bromide or iodide in DMF gives a reductively dehalogenated product, i.e., the corresponding hydrocarbon, in a small yield.
The N1→N2 Migration of the s-Triazinyl Group of 4-Substituted N1,N1-Bis-(s-triazinyl)-o-phenylenediamines
Authors: Nakamura Kenji , Nohara Noboru , Matsui Kohji
Published: July 2006

Several 4-substituted N1-[bis-(diethylamino)-s-triazinyl]-N1-(dimethoxy-s-triazinyl)-o-phenylenediamines were synthesized, and the migrations of the s-triazinyl group were investigated in these compounds. In methanol, every 4-substituted N1,N1-bis(s-triazinyl)-o-phenylenediamine gave only 4-substituted N1-[bis-(diethylamino)-s-triazinyl]-N2-(dimethoxy-s-triazinyl)-o-phenylenediamine by the migration of the dimethoxy-s-triazinyl group; the rearrangement was assumed to proceed through an intramolecular nucleophilic attack by the ortho amino group upon the ring carbon of the dimethoxy-s-triazinyl group. However, in the presence of a small amount of acid, the N1→N2 migration of the bis(diethylamino)-s-triazinyl group occurred preferentially, and two kinds of rearranged products were obtained. The kinetics of the rearrangement have also been studied spectrophotometrically in methanol, and the effects of the substituents on the rearrangement have been discussed.
The Stereochemistry of Nucleophilic Addition. V. The Reformatsky Reaction of 2-Phenylpropanal with Methyl α-Bromopropionate
Authors: Matsumoto Takashi , Hosoda Y\={u}kei , M\={o}ri Kiyomi , Fukui Kenji
Published: July 2006

The Reformatsky reaction of 2-phenylpropanal (I) with methyl α-bromopropionate gave the diastereomeric methyl 3-hydroxy-2-methyl-4-phenylvalerates, IIa, IIb, IIe, and IId, in a 5 : 24 : 16 : 55 ratio. The configurations of these β-hydroxy esters were assigned by the following experiments. The reduction of IIa–IId with LiAlH4 gave the corresponding diols, IIIa–IIId, which were then converted to the monotosylates, IVa–IVd. The further reduction of IVa or IVc and IVb or IVd with LiAlH4 gave the epimeric 2-methyl-4-phenyl-3-pentanols, V and VI respectively. Since V and VI were also obtained as minor and major products (20 : 80 ratio) of the Grignard reaction of I with isopropylmagnesium iodide, the configurations of the C-3 and C-4 positions in IIa–IId were assigned. The Wittig reaction of I with carbomethoxyethylidenetriphenylphosphorane gave methyl 2-methyl-4-phenyl-2-cis-pentenoate (VII) and its trans-isomer (VIII), which were then reduced to the corresponding alcohols, IX and X respectively. The cis-hydration of IX gave IIIc and IIId, while a similar treatment of X gave IIIa and IIIb. From this experiments, the relative configurations from the C-2 position to the C-3 position in IIa–IId were also assigned. These configurational assignments of IIa–IId were further confirmed by the ozonization of IIa–IId.
Electronic Spectra and Structures of Organic π Systems. V. SCFMO Calculations of Some Fulvenes and Fulvalenes with the Variable Integrals Methods
Authors: Yoshida Zen-ichi , Kobayashi Tsunetoshi
Published: July 2006

The electronic states of fulvene, 6-vinylfulvene, 6-aminofulvene, 6,6-dialkoxyfulvene, 6-amino-6-alkoxyfulvene, heptafulvene, 8-vinylheptafulvene, sesquifulvalene, and fulvalene have been investigated with the variable integrals methods. The effect of bond alternation is taken into account in the SCF procedure. Agreement between the calculated and observed transition energies is satisfactory.
Studies of the Synthesis of Furan Compounds. XXVIII. Syntheses and Steric Configurations of 3-(5-Nitro-2-furyl)-2-(2-furyl)acrylonitrile and Its Bromine Derivatives
Authors: Kato Yasuhiko , Kuboyama Takashi , Hirao Ichiro
Published: July 2006

In continuing a previous report concerning the syntheses and steric configurations of 3-(5-nitro-2-furyl)-2-(2-furyl)acrylic acid derivatives, trans and cis 3-(5-nitro-2-furyl)-2-(2-furyl)acrylonitrile and their related compounds have been synthesized. The isomerization was involved in the conversion of cis-3-(5-nitro-2-furyl)-2-(2-furyl)acrylamide (I) to trans-3-(5-nitro-2-furyl)-2-(2-furyl)acrylonitrile (II) upon the treatment of phosphoryl chloride. II was converted to its cis isomer (III) by treating it with hydroxylamine, hydrazine hydrate, or hydrochloric acid. II and III were treated with bromine at 5–10°C in carbon tetrachloride to afford dibromo compounds, (3S : 5S and 3R : 5R)-(IV) and (3S : 5R and 3R : 5S)-3-(5-nitro-2-furyl)-3-bromo-2-(5-bromo-2,5-dihydro-2-furylidene)propionitrile (V) respectively. When the bromination was carried out at a higher temperature (70–73°C), a monobromo compound, cis-3-(5-nitro-2-furyl)-2-(5-bromo-2-furyl)acrylonitrile (VI), was obtained from both II and III. VI was also produced by heating IV or V in refluxing acetone. The structures and configurations of these compounds were discussed on the basis of their experimental and spectral data.
Compounds Related to Acridine. VIII. Reaction of 9-Vinylacridine with p-Substituted Nitrosobenzenes
Authors: Tsuge Otohiko , Torii Akiyoshi
Published: July 2006

In the presence of hydrochloric acid, 9-vinylacridine reacts with nitrosobenzenes having electron-donating groups such as p-nitroso-N,N-dialkylaminoaniline and p-methylnitrosobenzene to yield a four-membered oxazetidine, as the first example of a non-fluorinated oxazetidine ring system. A new 2:2 adduct, to which the perhydro-1,2,7-oxadiazepine structure is assigned tentatively, is formed in the reaction of 9-vinylacridine with nitrosobenzene or p-chloronitrosobenzene under similar conditions.
Calculation of Infrared Band Intensities of Various Chlorinated Ethanes
Authors: Tanabe Kazutoshi , Saëki Shinnosuke
Published: July 2006

Infrared absorption intensities of fundamental bands of three molecular species, CH3CCl3, CD3CCl3 in the vapor phase, and C2Cl6 in dilute solution in carbon disulfide have been measured. From the intensity data of four kinds of chlorinated ethanes C2H6, C2D6, CH3CCl3, CD3CCl3, the least number of common intensity parameters has been determined using the least squares method. Intensities of C2Cl6 calculated using the determined values of intensity parameters have been compared with the observed intensities in solution. It has proved that for almost all electro-optical parameters, it is possible to determine values commonly applicable to various chlorinated ethanes, while for μCH and δμCH⁄δrCH, it is not possible to find commonly applicable values, as in the case of chlorinated methanes.
Photochemical Reactions of 3-Alkyl-4-phenylsydnones
Authors: Huseya Yoshiharu , Chinone Akiko , Ohta Masaki
Published: July 2006

Photochemical reaction of 3-cyclohexyl-4-phenylsydnone (4) in nitrogen atmosphere afforded 2-cyclohexyl-4,5-diphenyl-1,2,3-triazole (5), 1,2-biscyclohexylazo-1,2-diphenylethylene (6) and 4-cyclohexyl-2-phenyl-Δ2-1,3,4-oxadiazoline-5-one (7). The results showed that the reaction of 4 in the presence of carbon dioxide, carbon disulfide and dimethyl acetylenedicarboxylate proceeded via nitrile imine intermediate. Irradiation of 3-t-butyl-4-phenylsydnone (11) afforded 1-benzoyl-2-t-butyl-4-phenyl-1,2-diazetidine-3-one (12). Variation of the absorbance of 4 at the longest wavelength with irradiation was affected by 1,3-pentadiene, but not that of 11. This shows that the excited triplet state is responsible for the photochemical reaction of 4.
Adsorption of N-Vinyl-2-pyrrolidone at the Mercury/Solution Interface
Authors: Yoshida Tadashi , Ohsaka Tetsuya , Yamamoto Hajime
Published: July 2006

The adsorption of N-vinyl-2-pyrrolidone (NV2P) or the monomer of polyvinylpyrrolidone (PVP) at the mercury/solution interface was examined by means of differential capacity vs. potential relations (C-E curves). The usual C-E curve obtained in 1 n sulfuric acid was similar to that of the saturated aliphatic compounds. However, in 1 n sodium sulfate or sodium hydroxide potential dependence of Cmin (minimum differential capacity) was observed as a result of π-electron interaction of adsorbed molecules. The adsorption behavior in 1 n sulfuric acid followed the Langmuir isotherm. The peculiar behavior in 1 n sodium sulfate or sodium hydroxide was explained by means of the Frumkin isotherm with the potential dependence of interaction constant (g), which varied linearly with potential in a range more negative than ca. −0.6 V (SCE) in contrast to nearly constant values in a more positive range. At a relatively high bulk concentration, there was a slight deviation from the Frumkin isotherm and the standard free energy of adsorption (ΔG0) vs. θ3⁄2 plot revealed a sharp break in the same way as pointed out by Gonway and his co-worker. The Cmin value of NV2P coincided approximately with that of its polymer of PVP in aqueous sulfuric acid, sodium sulfate or sodium hydroxide, respectively. The results are utilized for the discussion on the configuration of adsorbed PVP at the interface.
The Effects of Higher-boiling Compounds on the Liquid-phase Isomerization of m-Xylene over a Silica-Alumina Catalyst under Pressure
Authors: Takaya Haruo , Todo Naoyuki , Hosoya Tadasuke , Oshio Hideki , Yoneoka Mikio , Minegishi Toshio
Published: July 2006

The liquid-phase isomerization of m-xylene was studied over a silica-alumina catalyst under pressure on the additions of 2% of 8 higher-boiling compounds and 20–50% of benzene to reactant m-xylene. The catalyst activity in the isomerization was not greatly affected by hexamethylbenzene, naphthalene, α-methylnaphthalene, diphenyl, or s-dibenzyl. On the other hand, the activity was greatly lowered by 1,6-dimethylnaphthalene, diphenylmethane, and anthracene. Moreover, a very rapid exchange reaction occurred between an aromatic ring of diphenylmethane and a reactant xylene molecule, while the content of the isomerization product decreased linearly with an increase in the amount of benzene. From these results, the chemisorption states of xylene were discussed as follows. Most xylene molecules may be deduced to be chemisorbed on acid sites by those benzene rings. On the other hand, the fact that diphenylmethane inhibits the isomerization implies the existence of such a chemisorption state of xylene as a methylbenzylcarbonium ion, which may be an intermediate in the disproportionation reaction of xylene. The acid sites available for the chemisorption of diphenylmethane and for the disproportionation were speculated to be common and to have both acidic characters, protonic and Lewis.
Directly Bonded Carbon-Hydrogen Coupling Constants of n-Pentane
Authors: Ando Isao , Nishioka Atsuo , Kambe Masao
Published: July 2006

The values of the directly-bonded carbon-hydrogen coupling constants (JC–H) of the methyl and methylene groups in n-pentane were calculated by using the CNDO/2 method, taking into account its rotational isomers, and it was found that the calculated values of JC–H agree closely with the observed values.
Far-infrared Spectra of Zinc Halide Complexes with Acetonitrile
Authors: Kamo Tomoichi , Kimura Masao
Published: July 2006

The infrared spectra of zinc halide complexes with acetonitrile, ZnX2·2CH3CN (X=Cl, Br, I), in the solid state were recorded in the region from 4000 to 96 cm−1. The Zn–N stretching bands for the chloride and bromide were observed, at 210 and 212 cm−1 respectively, as composite bands of the A1 and B1 species. For the iodide, the Zn–N stretching band of the B1 species was observed at 219 cm−1, while the A1 mode was coupled with the Zn–I stretching mode and was absorbed at 252 and 179 cm−1. The N–Zn–N bending bands were observed at 163, 162, and 153 cm−1 and the Zn–N≡C bending bands, at 125, 128, and 132 cm−1, for the chloride, bromide, and iodide respectively. The normal coordinate analysis was carried out by the use of the Urey-Bradley force field, and the Zn–N stretching force constant was obtained as 0.56 mdyn/Å. The force constant is much smaller than the corresponding ones in complexes containing nitrogen donors in the sp3 and the sp2 valency states.