bluuebunny/crossref_metadata_2025 huggingface dataset:
The Effect of Adsorbed Amines on the ESR of Copper Oxide
Authors: Ueda Hisashi , Todo Naoyuki
Published: July 2006

The effect of several additives on the ESR of copper oxide was studied. Among the additives studied, amines and NH3 had peculiar effects on the ESR spectra. From the spectrum formed by NH3 it is concluded that the (Cu–NH3)2+ complex cation is formed on the surface of a CuO particle. The formation of this complex cation obeyed a pseudo-flrst-order rate and can be interpreted in terms of the surface reaction between the exposed Cu2+ and NH3. Among the amines studied, only primary amines gave ESR spectra which provide evidence for the existence of (Cu-amine)2+complex cations. The foregoing fact and the results obtained on the three isomers of chloroaniline indicate that a strong s-character of the lone-pair orbital is needed if an amine molecule is to occupy a surface defect of the O2−, by which the Cu2+ is exposed on the surface, thus forming a complex cation. By these facts, the d-orbital of Cu2+, which can overlap with the nitrogen lone pair of the amine molecule, is concluded to be dz2. The three principal values of the g-tensor for the (Cu–NH3)2+complex cation depend greatly on the temperature, indicating that this cation has some rotational and vibrational motions below 130°C, at which point Cu2+ and NH3 dissociate.
Mechanism of Redox Surface Reaction between Wüstite and CO2 or CO
Authors: Kurihara Seiichi , Fueki Kazuo , Mukaibo Takashi , Wada Yasuo
Published: July 2006

The redox reaction between thin wüstite foil and CO2 or CO was studied by means of a microbalance in a temperature range 900–1075°C. It was found that the reaction at the gas-wüstite interface is rate-controlling and that the reaction rate is expressed as

V_ox=k_OP_CO2a_O^-m/3 and V_red=k_O’P_COa_O^n/3

where aO is the oxygen activity of wüstite, and m and n are 2.1–2.2 and 0.8–1.2, respectively. On the basis of the theory by Kobayashi and Wagner, the most predominant mechanism is concluded to be

CO_2+2\ominus\ightleftarrowsCO+O^2-

Actigation energies for kO and kO′ were 35+3 and 32+3 kcal/mol, respectively.
Ionic Processes in the Radiolysis of Nitrous Oxide. The Effect of Electron Scavenger and Rare Gas Setisitization
Authors: Takao Satoshi , Shida Shoji
Published: July 2006

The effect of electron scavenger (SF6) on the radiolysis products of N2O was examined. The sensitization of N2O by various rare gases was also measured. In the presence of an electron scavenger we got 3.0 for the value of −ΔG(−N2O) in good agreement with the value of G(e−) for N2O. In the experiments of Xe or Kr containing small amounts of N2O, the G(−N2O) values were nearly equal to the respective G(e−) values for the rare gases, and the addition of SF6to the Xe-N2O system almost completely inhibited nitrogen formation. The results show that one electron decomposes just one molecule of N2O. This fact can not be accounted for by the hitherto assumed mechanism, and a new mechanism involving N2O− is proposed for ionic processes in the radiolysis of N2O. In the N2O-rare gas mixtures of various compositions, the sensitized yields of N2O decomposition per 100 eV energy absorbed by rare gases were divided into two groups, e.g., the yields from He, Ne mixtures were about twice as large as those from Ar, Kr and Xe mixtures. This result is discussed in terms of charge transfer and the Penning ionization.
Anodic Process of Thiosulfate at a Dropping Mercury Electrode
Authors: Murayama Teisuke , Sawaki Toshiko , Sakuraba Shukichi
Published: July 2006

In the anodic process of thiosulfate at a dropping mercury electrode, the formation of a species Hg(S2O3)34− is considerable even in dilute solution. An equation of current-potential curve is derived with proper consideration for the formation of the species. The successive stability constant of Hg(S2O3)34− was calculated to be 3×102 (at 25°C and an ionic strength of 0.2) by comparing the equation with experimental results.
An Internal-Reference Method for the Determination of Rubidium by Photon-Activation Analysis with Strontium Used as the Reference Element
Authors: Tsai Hui-Tuh , Kato Toyoaki , Oka Yoshinaga
Published: July 2006

We have studied a method for the determination of rubidium by activation analysis with brems-strahlung photons, with strontium used as the internal-reference element. This method is based on the γ-ray spectrometric measurement of the 84Rb activities produced by the 85Rb(γ,n) reaction and on the comparisons of those activities with that of 83Rb arising from strontium as a result of the (γ,p) reaction. The yields of various photonuclear reactions in rubidium and in strontium have also been examined as a function of bremsstrahlung maximum energies up to 60 MeV, and the best conditions for the determination of rubidium are proposed. When the maximum energy was set at 18 to 20 MeV, no interfering reactions occurred; a rubidium content down to about 2 μg can be determined accurately. A comparison of solid-state and scintillation γ-ray spectrometry in this method has also been included with respect to the sensitivity and the selectivity.
Oxidation of N,N′-Diarenesulfonylhydrazines
Authors: Kohara Yoshio , Kobayashi Michio , Minato Hiroshi
Published: July 2006

N,N′-Diarenesulfonylhydrazine was oxidized with several oxidizing regents, but diarenesulfonyl diimide was not isolated. Diarenesulfonyl diimide produced immediately decomposed with evolution of 1 mol of nitrogen, and afforded the corresponding sulfonyl bromide, α-disulfone and sulfonic acid. Plausible mechanisms of decomposition were discussed.
Studies of Peptide Antibiotics. XXL Synthesis of Tyrocidine C
Authors: Kuromizu Kenji , Izumiya Nobuo
Published: July 2006

A cyclic decapeptide, cyclo-(l-Trp-d-Trp-l-Asn-l-Gln-l-Tyr-l-Val-l-Orn-l-Leu-d-Phe-l-Pro-), having the amino acid sequence of natural tyrocidine C has been synthesized. Chemical and biological properties of this product have been described. An antibiological activity of the product toward Gram positive microorganisms was found to be nearly the same degree as that of tyrocidine B.
Studies on Aminosugars. XXV. The Synthesis of Position Isomers of α-d-Glucopyranosyl-2-deoxystreptamine
Authors: Nishimura Yoshio , Tsuchiya Tsutomu , Umezawa Sumio
Published: July 2006

Racemic O-isopropylidene derivative of N,N′-diethoxycarbonyl-2-deoxystreptamine was glucosidized with 2,3,4,6-tetra-O-benzyl-α-d-glucopyranosyl chloride to afford two kinds of position isomers of α-glucoside, which led to 4-O-(α-d-glucopyranosyl)- and 6-O-(α-d-glucopyranosyl)-2-deoxystreptamine. Structural assignments were made by the determination of Δ[M] of the glucosides in a tetramminecopper(II) sulfate solution.
The Mössbauer Effect in Triethyltin Phenyl Derivatives
Authors: Watanabe Noriyuki , Niki Eiji
Published: July 2006

Substituent effect of triethyltin phenyl derivatives was investigated by means of the 119Sn Mössbauer effect. The isomer shifts obtained for these compounds fall into the range −0.15–−0.18 mm/sec with respect to Pd119mSn source. p-Cl and m-Cl derivatives show broadened spectra, which may be ascribed to an unresolved quadrupole splitting. This small quadrupole interaction may be interpreted in terms of the partial ionicity of the bond formed between tin and carbon in phenyl group.
The Crystal Structure of a Colored Complex, C7H7OHg·C7H6O2N, Obtained in the Millon Reaction of p-Cresol
Authors: Kobayashi Yoshiko , Iitaka Yoichi , Kido Yasumasa
Published: July 2006

The crystal structure of the complex of 2-mercuri-4-methylphenol and 2-nitroso-4-methylphenol obtained in the modified Millon reaction was determined using three-dimensional X-ray diffraction data. The complex crystallizes in triclinic system, space group P\bar1, with a unit cell of dimensions a=10.26 Å, b=22.71 Å, c=5.61 Å, α=97.2°, β=93.1°, γ=91.1°, containing four complex molecules. Each of the two crystallographycally independent complex molecules both having essentially the same structure, forms a dimer with its nearest neighbor related by a center of symmetry through a pair of hydrogen bonds. The mercury atoms adopt a planar four-fold coordination with nitrogen, carbon and two oxygen atoms.
Luminescence in DNA-Acridine Dye Complexes. I. Phosphorescence and Delayed Fluorescence Due to the Triplet-Triplet Annihilation of Acridine Dyes in the Complexes
Authors: Kubota Yukio
Published: July 2006

When DNA-acridine dye complexes were excited by a visible light which was not absorbed by DNA, phosphorescence and a delayed fluorescence of the dye were observed. It was found, by comparing the excitation spectra with the absorption spectra, that the monomeric dyes mainly contribute to the fluorescence and phosphorescence emissions. The delayed fluorescence was interpreted as a result of the triplet-triplet annihilation which arises from two triplet dye molecules placed very close together. The decrease in the delayed fluorescence on the denaturation of DNA indicates that the interaction between the two triplets is sensitive to the conformation of the macromolecule.
The Photoreaction of 2,6-Diphenyl-4H-thiopyran-4-one and Its Related Compounds
Authors: Sugiyama Noboru , Sato Yoshiaki , Kashima Choji
Published: July 2006

The irradiation of 2,6-diphenyl-4H-thiopyran-4-one (1) or 2,6-diphenyl-4H-pyran-4-one (2) in an alcohol in the presence of oxygen gave benzoic acid and a benzoylacetic acid ester, while that of 2 in benzene or 2,6-dimethyl-4H-thiopyran-4-one (5) in various solvents gave the corresponding cage dimer, (9) or (10). No photoreaction could be observed in case of the irradiation of 1,2,6-trimethyl-4-pyridone (3) and 6-methyl-1,2-diphenyl-4-pyridone (4). A reaction mechanism via the triplet state of the substrate was also proposed.
Studies of the Thiocarbonyl Compounds. II. Syntheses and Thermal Rearrangement of Aryl Thionobenzoates
Authors: Araki Yoshiaki , Kaji Aritsune
Published: July 2006

Various aryl thionobenzoates were prepared. When maintained at elevated temperatures, they rearranged smoothly to aryl thiolbenzoates. The mechanism of this rearrangement was kinetically investigated. The rearrangement rates were correlated with the first-order kinetic equation, and the rearrangement was found to be facilitated by substitution with an electron-withdrawing group in the migrating aromatic rings. The Hammett ρ value was found to be 2.11 in diphenyl ether at 200.5°C. The entropies of activation were negative. A linear free-energy relationship existed between this rearrangement and the rearrangement of O,S-diaryl dithiocarbonates. From these observations, a four-membered cyclic structure can be suggested as the transition state for this rearrangement. The present results indicate that the existence of hetero atoms directly bound to the thiocarbonyl group is not essential for the thermal rearrangement with intramolecular 1,3 aryl migration from oxygen to sulfur.
Sugars Containing a Carbon-phosphorus Bond. II. Syntheses of Phosphinyl Sugars by the Michaelis-Arbuzov Reaction of Halogenated Sugars
Authors: Inokawa Saburo , Tsuchiya Yoshimi , Yoshida Hiroshi , Ogata Tsuyoshi
Published: July 2006

3,5-O-Benzylidene-6-deoxy-6-diethoxyphosphinyl-1,2-O-isopropylidene-α-d-glucofuranose was prepared in an 80% yield by heating a solution of 3,5-O-benzylidene-6-deoxy-6-iodo-1,2-O-isopropylidene-α-d-glucofuranose (1) in an excess of triethyl phosphite (5). Similarly, 6-deoxy-6-diethoxyphosphinyl-1,2;3,4-di-O-isopropylidene-α-d-galactopyranose was prepared in a 95% yield from 6-deoxy-1,2;3,4-di-O-isopropylidene-α-d-galactopyranose (2), and (5); 5-deoxy-5-ethoxyphenylphosphinyl-1,2-O-isopropylidene-3-O-methyl-α-d-xylofuranose was prepared in a 90% yield from 5-bromo-5-deoxy-l,2-O-isopropylidenne-3-O-methyl-α-d-xylofuranose and diethyl phenylphosphonite; 3,5-O-benzylidene-6-deoxy- 1,2-O-isopropylidene-6- (N,N′-tetraethyldiaminophosphinyl)-α-d-glucofuranose was prepared in a 44% yield from 1 and ethyl N,N′-tetraethylphosphorodiamidite (7); 6-deoxy-1,2; 3,4-di-O-isopropylidene-6-(N,N′-tetraethyldiaminophosphinyl)-α-d-galactose was prepared in a 70% yield from 2 and 7.
Synthesis of 5-Styryltropolones
Authors: Higashi Hidehiro , Kurosawa Kazu , Matsumura Hisashi
Published: July 2006

5-Styryl-, 5-(p-bromostyryl)-, 5-(p-chlorostyryl)-, 5-(p-methoxystyryl)-, 5-(p-methylstyryl)-, 5-(m-chlorostyryl)- and 5-(m-methylstyryl)tropolone were synthesized by the Wittig reaction of 5-formyltropolone. Their UV and NMR spectra were determined.
Studies on Hydroxy Amino Acids, III. The Synthesis of Cyclic Peptide Containing L-Serine
Authors: Iwai Michio , Nakajima Kiichiro , Uno Akio , Hase Satoe , Takeuchi Ikuko , Okawa Kenji
Published: July 2006

Modified gramicidin S pep tides, cyclo(Ser-Orn-Ser-d-Phe-Pro)2 and cyclo(Ser-Orn-Ser-d-Phe-Pro), were synthesized in order to clarify the correlation between the component amino acids and the antibiotic activity. To obtain the cyclic peptides, we examined several sets of conditions for cyclization reactions. The antibiotic activity of these peptides could not be found against some microorganisms in vitro. It was concluded that the lipophilic amino acids residues are the essential groups contributing to gramicidin S activity.
The Synthesis of a Partial Sequence of Proinsulin Using the A-Chain of Natural Insulin
Authors: Shimonishi Yasutsugu
Published: July 2006

Elongation reactions of the S-sulfonate of the A-chain of bovine insulin were carried out with acylamino acid-active esters or with acylpeptide azide; the following derivatives of the A-chain were thus synthesized: S-sulfonates of NG-nitro-l-arginyl-, l-lysyl-NG-nitro-l-arginyl-, and l-prolyl-l-prolyl-l-glutaminyl-Nε-benzyloxycarbonyl-l-lysyl-NG-nitro-l-arginyl-A-chain. Thus, this was demonstrated to be a useful procedure for the partial synthesis of proinsulin.
ζ-Potentials of Synthetic Fibers in Aqueous Solutions of Sodium Alkyl Sulfates and Viscosities of Their Solutions
Authors: Iwadare Yoshio
Published: July 2006

In order to study the surface-adsorption behavior of anionic surfactants on fibers, the ζ-potentials of some synthetic fibers in aqueous solutions of sodium alkyl sulfates and their mixtures mainly above the critical micelle concentration (CMC), were measured. Further, the viscosities of aqueous solutions of pure surfactants were determined. Consequently, it can be presumed, on the basis of the viscosity data, that the structure of the micelles of these agents varies at the break of the ηspm⁄cm  vs. cm curve. The ζ-potentials (negative) of fibers in aqueous solutions of the agents rapidly changed with an increase in the agent concentrations, but it remained nearly constant above the CMC. At much higher concentrations, the ζ values gradually changed; thereafter, passing a break or a minimum, they became approximately constant again. The concentration at the break or the minimum observed nearly corresponded to that at the break of the ηspm⁄cm  vs.  cm curve. It may, therefore, be suggested that the change in ζ-potentials at high concentrations is connected with that in the structure of the micelles. The ζ-potentials (negative) of fibers in aqueous mixed solutions changed sharply with an increase in the concentration of the mixtures and thereafter, passing a maximum in the vicinity of the CMC, complicatedly changed as the total concentrations and mixing ratios changed.
Mechanism of Hydrogen Formation in the Vapor Phase Radiolysis of Methanol
Authors: Yamamoto Tatsuo
Published: July 2006

The yields of isotopic hydrogen in the vapor phase radiolysis of deuterated methanol (CH3OD) were found to be G(H2)=6.1, G(HD)=5.3 and G(D2)=0.2. The molecular yields of isotopic hydrogen were also determined by adding propylene as a radical scavenger, GM(H2)=1.5, GM(HD)=0.6 and GM(D2)∼0. In order to estimate the contribution of ionic species for the formation of hydrogen, the ion-molecule reaction of CH3OD has also been investigated by using a mass spectrometer of the differential pumping type. The product ions, such as (CH3OCH3CH3OD)D+ or (CH3OD)3D+, which were considered to be formed by the higher order ion-molecule reactions were observed. The mechanism of hydrogen formation was discussed on the basis of the ionic, the molecular and the radical mechanisms.
Catalytic Activity and Reactivity of Aromatic Nitrile and Alkali Metal Ion Radical Salt. II. Hydrogen Exchange on Benzonitrile Ion Salt as a Function of Alkali Metals
Authors: Tsuda Motoyuki
Published: July 2006

The para-orthohydrogen conversion (rate constant keH and the deuterium exchange reaction (rate constant keD) over the benzonitrile-alkali metal ion radical salt were investigated as functions of the donor component–alkali metal. The sort of alkali metals in the ion radical salts greatly affected the catalytic activity and the reactivity. The activation energies obtained from the temperature dependence of keH and keD, EH and ED, and the value of α(depending on the ratio of keH to keD monotonously decreased as Na→K→Rb, but those values showed an irregular trend for the Cs-complex. The results suggest that the catalytic activity cannot be understood only in terms of the nature of the components; must also be considered the structural nature of the solid phase of the ion radical salt.
The Thermal Decomposition of CuBr2·2NH3 and CuBr2
Authors: Tanaka Nobuyuki , Kagawa Masahiro
Published: July 2006

The thermal decomposition of CuBr2·2NH3 has been examined at the constant temperature, about 220°C. Copper(II) was reduced to copper(I), when bromine gas was found as one of the decomposition products, indicating that bromide anion may be the reducing agent for copper(II). The decomposition reaction of CuBr2 has been investigated by measuring the weight loss under the condition of the constant temperature. In a closed system, the reaction,

CuBr_2(s)\leftrightarrowsγ-CuBr(s)+\frac12Br_2(g)

attained to equilibrium, and ΔG° for this reaction was determined in the range from 160°C to 220°C to be given by the equation,

ΔG°(cal.)=1.10×10^4-19.3 T (160°C–220°C).

While the pressure of bromine gas was kept zero, CuBr2 decomposed following a first-order rate law in the beginning of the decomposition, and the activation energy was found to be 25.4 kcal/mol.
The Acetylation of 2,3-Dimethyl-bz-halobenzofurans and Some Reactions of the Products
Authors: Kawase Yoshiyuki , Hori Sachiko
Published: July 2006

The acetylation of bz-chloro- and bz-bromo-2,3-dimethylbenzofurans with acetyl chloride and aluminum chloride in carbon disulfide at room temperature was studied; it was found that the acetylation occurred at the 6- or 4-position, which is activated by the furan ring, regardless of whether the halogen atom is at the o-, the m-, or the p-position. In the cases of 7-halo compounds, diacetylation occurred to give the 4,6-diacetyl compounds, and the migration of the bromine atom of 6-acetyl-5-bromo-2,3-dimethylbenzofuran and of the methyl ester of the corresponding carboxylic acid occurred, as a result of the action of aluminum bromide in carbon disulfide at room temperature, to give the 4-bromo compounds. The haloketones thus obtained were then converted to the corresponding carboxylic acids by the bromoform reaction.
Electrochemical Properties of α-Ferric Oxide in Sulfuric Acid Solutions
Authors: Yoneyama Hiroshi , Tamura Hideo
Published: July 2006

I-V curves of the α-Fe2O3 electrode containing different amounts of Ti were obtained potentio statically in H2SO4 solutions. The anodic current, indicating the dissolution reaction, was almost constant and was not affected by the aH+ of the electrolyte in the potential range 0.4–1.0V vs. SCE, but it was dependent on the conductivity of the electrode. It was suggested that the dissolution reaction of this electrode is governed by the electron-transfer mechanism, much as is that of the heavily-doped N-type Ge. The flat-band potential of the α-Fe2O3 electrode was estimated on the basis of the capacity measurement. This potential changed with the aH+ of the electrolyte.
Tri(hetero)substituted Carbonium Ions. IV. Reactions of N,N′-Dimethyl-S,S′-dimethyldithiocarbamidium Ion with Various Nucleophiles
Authors: Nakai Takeshi , Okawara Makoto
Published: July 2006

A wide spectrum of electrophilic reactivity has been shown by N,N-dimethyl-S,S′-dimethyldithiocarbamidium perchlorate (II). Results obtained reveal that II behaves toward nucleophiles as an ambident electrophile with two reactive sites, a centered electron-definicent carbon and S-methyl carbon atom. The electrophilic behavior of II has been compared with that of a cyclic analog, 2-dimethylamino-1,3-dithiolanylium ion, and of a sulfur analog, tris (methylthio)-carbonium ion. Attempts to utilize II for synthetic reactions were made. Reactions of II with active methylene compounds gave ketone N,S-acetals which are of great interest from the standpoint of structural chemistry. o-Phenylenediamine and o-aminophenol reacted with II to give 2-dimethylamino-benzimidazole and -benzoxazole, respectively, in good yields. The reactions may provide a new method of introducing 2-dialkylamino groups into these heterocycles. Reactions of II with two equivalents of primary amines afforded tetrasubstituted guanidines. Reactions of II with p-toluenesulfonylhydrazine and an enamine were also studied.
The Synthesis of 1-Methyl-2-pyridones from 2-Chloromethylpyridines
Authors: Matsumura Eizo , Nashima Takeo , Ishibashi Fumihide
Published: July 2006

The reaction of 2-chloromethylpyridine (Ia) and its homologs, 5-ethyl- (Ib), 6-methyl- (Ic), and 4-methyl-2-chloromethylpyridine (Id), with pyridine gave the corresponding 1-(2′-pyridylmethyl)-pyridinium chlorides (II), from which, on heating with dimethyl sulfate, 1-methyl-2-(pyridiniomethyl)-pyridinium salts (III) were obtained. The pyridinium salts were treated with aqueous alkali at a low temperature to yield 1-methyl- (IVa), 5-ethyl-1-methyl- (IVb), 1,6-dimethyl- (IVc), and 1,4-dimethyl-2-pyridone (IVd). The reaction sequence, in combination with the 1-oxidation of 2-picolines and followed by the reaction of the 1-oxides with tosyl chloride to yield 2-chloromethylpyridines, is recommended as a convenient route for the synthesis of 1-methyl-2-pyridones starting with 2-picolines.
The Syntheses of 2-Phenethyl-2,3-dihydro-4(1H)-pyridones
Authors: Sugiyama Noboru , Yamamoto Makoto , Kashima Choji
Published: July 2006

In the presence of three moles of potassium amide in liquid ammonia, the reactions of β-diketones with cinnamylidenaniline gave derivatives of 1-phenyl-2-styryl-2,3-dihydro-4-pyridone. By the catalytic hydrogenation of 6-methyl-1-phenyl-2-styryl-2,3-dihydro-4-pyridone, 6-methyl-2-phenethyl-1-phenyl-2,3-dihydro-4-pyridone was obtained. When β-diketones were treated with cinnamaldehyde azine, instead of cinnamylidenaniline, 1-cinnamylidenamino-2-styryl-2,3-dihydro-4-pyridones were produced; these were then catalytically hydrogenated to the corresponding 2-phenethyl-2,3-dihydro-4(1H)-pyridones, accompanied with 2-phenethyl-1-(3-phenylpropylamino)-2,3-dihydro-4-pyridones.
Linear Conjugated Systems Bearing Aromatic Terminal Groups. III. The Synthesis and the Electronic Spectra of 1,1′-Dinaphthyl- and 2,2′-Dinaphthylpoly-ynes
Authors: Nakasuji Kazuhiro , Akiyama Shuzo , Akashi Kazuko , Nakagawa Masazumi
Published: July 2006

1,1′-Dinaphthylpoly-ynes (In, n=1–6) and 2,2′-dinaphthylpoly-ynes (IIn, n=1–6) were synthesized, and their electronic spectra were measured. The In-series gave an excellent agreement with the λmax∝n1.5 relationship, and the IIn-series followed a straight line, λmax∝n1.3. These relationships are different from those of 1,1′-dianthryl- and 9,9′-dianthrylpory-ynes, in which the plots of λmax  versus  n2 give excellent straight lines (Bull. Chem. Soc. Jap., 39, 2320 (1966); 40, 340 (1967)). The new linear relationships found in the dinaphthyl-series offer further evidence of the prominent effect of the terminal groups upon the electronic spectral properties of the conjugated poly-yne system.
The Constituents of Hops. V. The Volatile Composition of Humulus japonicus Sieb. et Zucc.
Authors: Naya Yoko , Kotake Munio
Published: July 2006

The steam-volatile constituents of Humulus japonicus Sieb. et Zucc. have been studied, and 50 compounds of the oil have been identified mainly by means of the temperature-programmed capillary GLC mass-spectra method. Beside the previously-reported principal components of hops (α-humulene, caryophyllene, α-copaene, α- and β-selinenes, γ-cadinene, caryophyllene-oxide, and humulene-epoxide-II), benzyl alcohol and phenethyl alcohol were found in high concentrations, whereas the myrcene was negligible. The proportion of the main compound, humulene, to the next highest one, caryophyllene, was approximately in the ratio of two to one, as in the essential oil of H. lupulus. As far as the chemical composition of the essential oils is concerned, H. japonicus seems to be related rather more closely to H. lupulus than to H. cordifolius.
Redox Reactions on α-Ferric Oxide Electrode
Authors: Yoneyama Hiroshi , Hamamatsu Shi\v{n}iichi , Tamura Hideo
Published: July 2006

The redox reactions of Fe(CN)64−/Fe(CN)63−, Fe2+/Fe3+, and Ce3+/Ce4+ systems on α-Fe2O3 electrodes containing different amounts of titanium were studied. The anodic current showed a tendency to be saturated in the Fe(CN)64−/Fe(CN)63− and Fe2+/Fe3+ systems. The forward direction of the current flow in these systems was the reverse of the case with the lithiated NiO electrode. On the other hand, the cathodic current flow was negligible and the redox potential was not observed for the Ce3+/Ce4+ system. It was concluded that the reaction proceeds through electron transfer and that I–V curves are determined by the influence of the potential barrier formed on the electrode surface over which an electron transfers from the electrode into the electrolyte or in the reverse direction.
The γ-Radiolysis of Liquid n-Hexane. The Effects of Radical, Electron, and Positive-ion Scavengers
Authors: Shinsaka Kyoji , Shida Shoji
Published: July 2006

The effects of various additives, SF6, NH3, C2H5OH, N2O, NO, SO2, and C2H4, on the product yields in the γ-radiolysis of liquid n-hexane at room temperature have been investigated. The following conclusions have been drawn: (i) The added SO2 acts mainly as a radical scavenger. (ii) The added NO shows not only the effect of radical scavenging, but also other effects. Therefore, it is inadequate to use NO as a simple radical scavenger, (iii) The C7-C12 products are formed from a combination reaction of alkyl radicals, but not from an ion-molecule reaction, (iv) The formation of C6H13+ ions by the direct action of radiation is suggested, (v) The G-value of ionization is evaluated to be 4.0. A brief discussion concerning the formation of N2 in the presence of N2O is also given.
Far Infrared Transmission Spectra and Lattice Vibrations of RbNiF3 and CsNiF3
Authors: Kohn Kay , Nakagawa Ichiro
Published: July 2006

The infrared absorption spectra of RbNiF3 and CsNiF3, both with a perovskite-like structure, have been measured in the region 500–50 cm−1 at room temperature and at liquid nitrogen temperature. The observed bands can be classified into three groups, corresponding to the three absorption bands in perovskite. These bands can reasonably be assigned on the basis of the crystal symmetry of the investigated compounds. A normal coordinate analysis of a crystal as a whole has been performed, where the interatomic force constants between the atom pairs within a distance of 3.5 Å are taken into account. It was shown that the normal coordinate treatment of the opticallyactive vibrations on the basis of a molecular dynamics model is useful for the interpretation of the lattice vibrations in these fluorides. The effects of the structural differences of the lattice vibrations are discussed.
The Behaviour of the Copolymer of l-Proline and O-Benzyl-l-Tyrosine in a n-Propanol and Water System
Authors: Iio Takayoshi , Takahashi Sho , Kobayashi Shoyu
Published: July 2006

A copolymer consisting 95.8% of l-proline and 4.2% of O-benzyl-l-tyrosine was transformed in conformation from Form I to Form II as the propanol content changed from 100% to 74%. In Form I, the copolymer took a rod-like structure like that of poly-l-proline Form I, and the O-benzyl-l-tyrosyl residue moved independently of the molecular motion of the copolymer. On the other hand, the copolymer became flexible in Form II and the components associated with each other, forming an amorphous aggregation, when the propanol content decreased further, below the transition point. The hydrophobic interaction between the O-benzyl-l-tyrosyl side chain and the prolyl residue was the main factor which made the components of the copolymer associate with each other and form an amorphous aggregation. This was verified by a fluorescence study of the O-benzyl-l-tyrosyl residue.
Kinetics of Multidentate Ligand Substitution Reactions. VIII. Substitution Reactions of Diethylenetriaminepentaacetic Acid with Nickel(II) Iminodiacetate and Aspartate Chelates and of Cyclohexane-1,2-diamine-N,N,N′,N′-tetraacetic Acid with the Nickel(II) Aspartate Chelate
Authors: Kodama Mutsuo , Ueda Teiko
Published: July 2006

The substitution reactions of diethylenetriaminepentaacetic acid (DTPA) with nickel(II) chelates of iminodiacetic acid (IDA) and aspartic acid (Asp) and of cyclohexane-1,2-diamine-N,N,N′,N′-tetraacetic acid (CyDTA) with the nickel(II) chelate of aspartic acid were studied by employing the polarographic method. All the reactions studied were found to proceed through the following two simultaneous reaction paths:

(Remark: Graphics omitted.)

where NiX0 and NiX22− denote nickel(II)-IDA or Asp chelates of 1-to-l and 1-to-2 compositions respectively, and where Zm− indicates a completely-deprotonated DTPA or CyDTA anion. From a comparison of the rate constants of substitution reactions involving the nickel(II)-aspartate chelate with the corresponding rate constants of substitution reactions involving the nickel(II)-iminodiacetate chelate, the six-membered ring of the nickel(II)-aspartate chelate, as compared with its five-membered ring, was concluded to be more labile in the substitution reaction.
Studies of Hydrogenolysis. LVII Catalytic Hydrogenation of Benzalacetophenone Oxide
Authors: Sohma Akiko , Mitsui Sekio
Published: July 2006

The effects of catalysts and an additive, sodium hydroxide, on the catalytic hydrogenation of benzalacetophenone oxide (I) have been studied for the purpose of elucidating the selectivity of the catalysts on the hydrogenation. The catalytic hydrogenation over palladium or Raney nickel led to the formation of the hydroxyketones as the primary products resulting from the hydrogenolysis of the epoxide ring. 1,3-Diphenylpropane-1,2-diol (III) was obtained by the catalytic hydrogenation over palladium, while 1,3-diphenylpropane-1,3-diol (VI) and III were yielded over Raney nickel. Under the basic conditions III was predominantly produced even over Raney nickel. Over platinum oxide, 2,3-epoxy-1,3-diphenylpropan-1-ol (VIII) was the primary product of the hydrogenation of the carbonyl group of I. In the hydrogenolysis of VIII, 1,2-diol (III) was produced regardless of the species of the catalysts.
A Comparative Study of the Constituents of Volatile Oils of Zanthoxylum
Authors: Sakai Tsutomu , Yoshihara Kazuo , Hirose Yoshio
Published: July 2006

The constituents of the volatile oils of three Zanthoxylum species were studied on the basis of the preceding exhaustive analysis of fruit oil from the Japanese pepper. It seems that the fragrance quality among the genera Zanthoxylum depends on the content of citronellal in the essential oil. That is, the unripe fruit oil of Japanese pepper with the strongest characteristic aroma contained the largest amount of citronellal. Ripe fruit oil of Z. simulans containing a trace amount of citronellal had a poor flavor.
The Double Cycloaddition of Disulfene and Its Related Reactions
Authors: Hirai Koji , Tokura Niichiro
Published: July 2006

The reactions of methanedisulfonyl chloride (II) with ketene diethylacetal (III), 1 -morpholinocyclohexene (IV), and 1-piperidinopropene (V) in the presence of triethylamine were studied. The products obtained were the double cycloadduct, spiro bithietane tetroxide (VI), and the substitution products (X and XV). These findings suggest that triethylamine dehydrochlorinates methanedisulfonyl chloride to produce disulfene. However, as yet we cannot say whether the formation of disulfene is the one-step dechydrochlorination mechanism (ClSO2CH2SO2Cl → SO2=C=OS2) or the two-step one (ClSO2CH2SO2Cl → ClSO2CH=SO2 → SO2=C-SO2).
Addition of Tellurium Tetrachloride to Olefins and Pyrolysis of the Adduct
Authors: Ogawa Masao , Ishioka Ryoji
Published: July 2006

The tellurium tetrachloride-cyclohexene adduct, 2-chlorocyclohexyltellurium trichloride (I) and bis(2-chlorocyclohexyl) tellurium dichloride (II), both gave, on pyrolysis, chlorocyclohexane as the chlorinated compound. An intermolecular hydrogen transfer is required for the formation of chlorocyclohexane from I. Chloro-n-propyltellurium trichloride (III) and bis(chloro-n-propyl)-tellurium dichloride (IV) were formed by the addition of tellurium tetrachloride to propylene. The pyrolysis of III afforded allyl chloride, 1,2-dichloropropane, and hydrogen chloride, while tellurium was simultaneously reduced. Besides these products, isopropyl chloride was also obtained from IV. Some properties of the adduct and the effect of the temperature on the thermal decomposition were studied.
Aromatic Sulfonylation. II. Attacking Species under Various Conditions.
Authors: Kohara Yoshio , Kobayashi Michio , Minato Hiroshi
Published: July 2006

p-Toluenesulfonylation of toluene and anisole in the presence of AlCl3, SbCl5 or TiCl4 was investigated in methylene chloride, nitromethane and nitrobenzene. Substitution took place at 8.6–13.4% and 86.6–91.4% para positions for toluene in methylene chloride, but 42.0–45.7% ortho and 54.2–58.0% para isomers were obtained in nitromethane and nitrobenzene. Sulfonylation of toluene with p-CH3C6H4SO2+ ClO4− afforded 44.8–46.3% ortho and 53.7–55.2% para isomers. Partial rate factors for toluene were pf=52.5 in methylene chloride, of=12.6±0.9, pf=31.4±2.0 in nitromethane, and of=16.0±1.7, pf=38.3±4.2 with p-CH3C4H4SO2+ClO4−. A plausible mechanism is proposed, in which the attacking species is TsCl-MCln complex in methylene chloride, but it is an ion pair, ArSO2+MCl−n+1, in nitromethane and nitrobenzene.
Measurement of the Adsorption of Tritium Labelled Sodium Stearate at Air/Water Interface using Thin Windowed Geiger-Müller Counter Tube
Authors: Sekine Keiichi , Seimiya Tsutomu , Sasaki Tsunetaka
Published: July 2006

The adsorption of tritium labelled sodium stearate at various pH values and temperatures was directly measured by using a thin end-windowed Geiger-Müller counter. The disturbances due to the application of high electrical potential and the introduction of counting gas were avoided, which are inevitably encountered in an ordinary windowless 2π counter. Precautions were taken to avoid both surface evaporation effect and contamination of solution due to the absorption of carbon dioxide from the air. The results show that free stearic acid is considered to be the main surface active species in an aqueous sodium stearate.
Electronic Structures and Electronic Absorption Spectra of Cyclohexadienyl and Related Radicals Produced by γ-Irradiation
Authors: Shida Tadamasa , Hanazaki Ichiro
Published: July 2006

The electronic absorption spectrum for the cyclohexadienyl radical produced upon γ-irradiation of pure benzene and benzene-alcohol solutions both at 77°K was investigated. In addition to the absorption band at 3.9 eV, a weak band with a prominent vibrational structure was observed at 2.2 eV. An SCF-CI molecular orbital calculation was carried out for the radical taking into account explicitly the hyper conjugation effect of methylene group. The theory predicts the two observed bands with satisfactory accuracy. The calculated spin densities are also in good agreement with the existing ESR data of the radical. Vibrational analysis was carried out for the band system at about 2 eV as well as for the corresponding bands of isotopically mixed radicals, C6H6D, C6D6H, and C6D7. Parallel calculations for hydronaphthyl radicals are also in harmony with the available experimental data of optical and ESR measurements.
The Photochemical Rearrangements of N-Acetyl Diphenylamine and N-Acetyl Carbazole
Authors: Shizuka Haruo , Kato Motonobu , Ochiai Toshio , Matsui Kohji , Morita Toshifumi
Published: July 2006

The photochemical reactions of N-acetyl diphenylamine and N-acetyl carbazole in solution have been studied. N-Acetyl diphenylamine and N-acetyl carbazole undergo the photo-Fries-rearrangement by means of 2537Å irradiation. The reaction products consist of the ortho- and para-isomers, plus corresponding amines transformed through the deacetylation of the original compounds. The quantum yields in the early stages of the rearrangement were measured under various conditions by spectrophotometry. The reaction mechanism has been discussed on the basis of the relation between the rate constants of the rearrangement and the odd π electron densities obtained from simple Hückel MO calculations.
Kinetics of the Ligand Substitution Reaction of the Copper(II)-4-(2-Pyridylazo)resorcinol Complex with (Ethylene glycol)-bis(2-aminoethyl ether)-N,N,N′,N′-tetraacetic Acid
Authors: Funahashi Shigenobu , Yamada Shinkichi , Tanaka Motoharu
Published: July 2006

The kinetics of the ligand substitution reaction of the copper(II)-4-(2-pyridylazo)resorcinol complex (Cu(II)-PAR) with (ethylene glycol)bis(2-aminoethyl ether)-N,N,N′,N′-tetraacetic acid (EGTA) has been studied spectrophotometrically at pH 9–10 at μ=0.10 (NaClO4) and at 25.0°C. The reaction proceeds through the 1:1 Cu(II)-PAR complex resulting from the predissociation equilibrium of the 1:2 Cu(II)-PAR complex:

-d[CuR_2^2-]/dt=10^6.15[CuR_2^2-][H^+][Y’]/[HR^-]=10^2.9[CuR][Y’]

where R2- refers to the divalent anion of PAR (H2R) and Y′ the free EGTA not combined with any metal. The release of PAR from the mixed ligand intermediate RCuY is the rate-determining step. The substitution reaction for the copper(II)-PAR complex proceeds in the same mechanism with that for the zinc(II)-PAR complex. The difference in reactivity of these complexes is discussed. Cu-PAR bond is weakened in a distorted octahedron of the intermediate RCuY before the release of PAR.
Photochemical Studies of the Esters of Aroylphosphonic Acids
Authors: Terauchi Ken-ichi , Sakurai Hiroshi
Published: July 2006

The photochemical behavior of several dialkyl benzoylphosphonates and para-substituted benzoylphosphonates in various solvents has been studied using product isolation, ultravioletspectral change, the electron spin resonance (ESR) technique, and quantum yield measurements. Upon irradiation to a degassed solution of these benzoylphosphonates through a Pyrex filter, the photo-pinacolization reaction was observed, except in the case of diethyl benzoylphosphonate; it was effectively quenched by 1,3-pentadiene or oxygen. On the other hand, the ESR spectra of photo-irradiated aroylphosphonates at 77°K have a large anisotropic doublet of 53–128 gauss separation; this separation is thought to be due to the interaction between an unpaired electron and the phosphorus nucleus. The structure of these radicals is also discussed. From these observations, it can be considered that the photochemical reaction proceeds via the ketyl radical formed by the hydrogen abstraction of the lowest excited triplet state of these aroylphosphonates. Irradiation to the diethyl benzoylphosphonate solutions in various solvents gave, not the pinacolized product, but 2,4,6-triphenyl-2,4,6-tris[diethylphosphoryl]-1,3,5-trioxane almost quantitatively. The quantum yields (Φ) of the disappearance of several para-substituted derivatives are highly sensitive to the electron-inductive abilities of the substituents; that is, Φ drops from 2.10 in the p-methoxybenzoylphosphonate derivative to 1.79 in the p-chloro derivative at room temperature. Such a substituent effect can be considered to result in the difference in the conformation between the carbonyl and phosphoryl groups. On the basis of these studies, the mechanism of the photochemical reaction of aroylphosphonates is described and discussed.
Studies of Peptide Antibiotics. XV. The Synthesis of cyclo-(l-Valyl-l-ornithyl-l-leueyl-d-phenylalanyl-l-prolyl-glycyl-glycyl)
Authors: Abe Okitoshi , Kuromizu Kenji , Kondo Michio , Izumiya Nobuo
Published: July 2006

A cyclic heptapeptide, cyclo-(l-Val-l-Orn-l-Leu-d-Phe-l-Pro-Gly-Gly-), was synthesized in order to investigate a contribution for an antibacterial activity of a ring size of a cyclic peptide. A linear heptapeptide p-nitrophenyl ester, in which an δ-amino function of ornithine residue was protected with benzyloxycarbonyl group, was transformed to the cyclic benzyloxycarbonyl-substituted heptapeptide which was hydrogenated to afford the desired cyclic heptapeptide as hydrochloride. The cyclic peptide thus obtained showed no activity against any of microorganisms tested.
The Emission Spectra of Hydrogen Atoms Produced from Methanol by Electron Impact
Authors: Fujita Iwao , Hatada Motoyoshi , Ogawa Teiichiro , Hirota Kozo
Published: July 2006

The emission spectra of several fragmental species, especially of hydrogen atoms, produced by the electron impact (energy:240 eV) of gaseous methanol and deuteromethanols have been investigated. The intensity ratios of the Balmer-β lines of the H and D atoms are ca. 2.9:1 for CH3OD and ca. 1:1.8 for CD3OH, indicating that the excited hydrogen atoms result from the O–H bond scission, as well as from the C–H bond scission, of the parent methanol molecules. The ratio of the scission probability of a C–H bond to that of the O–H bond is calculated to be 0.8, taking into account the correction of the isotope effect. It was concluded that the excited hydrogen atoms are produced by the primary process of fragmentation via a superexcited species.
Electron-Transfer Reactions of Multidentate Ligand Cobalt(III) Complexes. II. The Effect of Nonbridging Ligands
Authors: Kurimura Yoshimi , Ohashi Kousaburo
Published: July 2006

The specific rates for the Fe2+ reductions of cis-Co(en)2ACl2+ (A=methyl-, ethyl-, propyl-, butyl-, ethanol-, and propanolamine), Co(dien)(en)Cl2+ and Co(tetren)Cl2+ have been determined. The observed rates are relatively insensitive to the cis-ligand of the A. The rate constant for the cis-Co(en)2ACl2+ decreases with an increase in the size of the A ligand. In such cases as that of the aminoalcohol ligand, the rate is greater than that of the corresponding alkylamine ligand complex. The effect of chelation by nonbridging ligands has been discussed by comparing the relative effectiveness for Fe2+ reductions of CoN5Cl2+ (N5=(NH3)5, (en)2NH3, (dien)(en), and tetren) with that for Cr2+ reductions of some Co(III) complexes.
The Preparation and Reactions of Benzoylnitrile Oxide from Dimethylphenacylsulfonium Bromide
Authors: Otsuji Yoshio , Tsujii Yasuhiro , Yoshida Akihiko , Imoto Eiji
Published: July 2006

The nitrosation of dimethylphenacylsulfonium bromide (I) with sodium nitrite and hydrochloric acid in water gave 3,4-dibenzoyl-1,2,5-oxadiazole 2-oxide (II) in a 76% yield. The nitrosation of I in a similar manner in 1 : 1 dioxane-water afforded ω-chloro-ω-isonitrosoacetophenone (III) in an 80% yield. The treatment of III with triethylamine produced II through benzoylnitrile oxide (IX). 1,3-Dipolar cycloadditions of IX generated from III were conducted, using methyl methacrylate, styrene, acrylonitrile, and ethyl chloroformate as dipolarophiles, to yield the expected cycloadducts. The mechanisms of these reactions are discussed.
A General Matrix Method for Treating Elastic Constants of Molecular Crystals; Application to Orthorhombic Polyethylene
Authors: Shiro Yuji , Miyazawa Tatsuo
Published: July 2006

A general method is developed for treating elastic constants of molecular crystals, with the B matrices as commonly used in normal-coordinate treatments. Equations are written in matrix forms, convenient for calculating elastic constants from intramolecular and intermolecular force field and are readily programed for electronic computations. Partial derivatives of elastic constants with respect to force constants are also derived, for least-square adjustments of force fields with reference to experimental elastic constants as well as vibrational frequencies. Matrix treatments of elastic constants are much simplified by the use of crystal symmetry, just as are treatments of normal vibrations. The matrix methods are explained for the example of orthorhombic polyethylene.
The Mechanism of Vinyl Polymerization by Dialkylbis(dipyridyl)iron(II)
Authors: Yamamoto Takakazu , Yamamoto Akio , Ikeda Sakuji
Published: July 2006

Kinetics of polymerization of vinyl compounds (acrylonitrile, methacrylonitrile, acrolein, methyl vinyl ketone, methyl acrylate, alkyl methacrylates, and 2-vinylpyridine) with dialkylbis(dipyridyl)iron(II), FeR2(dipy)2  1 (R=CH3, C2H5, n-C3H7), was studied. By comparison with previous kinetic results in which the decomposition of 1 was followed spectroscopically, a polymerization mechanism including a slow initiation process followed by rapid propagation and unimolecular termination processes was proposed. The effects of the concentration of monomer, the addition of dipyridyl and the coordinating ability of solvent on the molecular weight of the polymer were explained by competitive coordination to the iron complex having a growing polymer chain. Results of copoly-merization experiments were explained in terms of competitive coordination and insertion reactions between the monomers involved. A linear relationship was found between log(1⁄r1) values and the logarithms of stability constants of nickel-olefin π-complexes with methacrylonitrile as the reference (M1). From the formation of C2-H5D in the polymerization of β-cis-d1-methyl methacrylate with Fe(C2H5)2(dipy)2 a unimolecular termination process involving abstraction of β-hydrogens of the growing chain by the alkyl group or the iron complex was proposed.
Nitrate as an Oxidant in the Reaction of Silver(I) Salts with Grignard Reagents
Authors: Tamura Masuhiko , Kochi Jay K
Published: July 2006

The reaction between various Grignard reagents and silver(I) salts in the presence of nitrogen-containing oxidants such as lithium nitrate, nitrogen dioxide, and methyl nitrate has been examined in tetrahydrofuran solutions. Coupling dimer is formed in high yields almost independently of the structure of the Grignard reagent. From the stoichiometry, it is concluded that these oxidants oxidize two equivalents of metallic silver formed in situ to silver(I) species under proper reaction conditions. Other transition metal halides are also oxidized by these oxidants in a similar manner. Soluble forms of reduced silver complexes formed in the reaction of silver(I) nitrate and Grignard reagent are also described.
The Substituent Effect. III. The Basicities of Polynuclear Aryl Methyl Ketones
Authors: Yukawa Yasuhide , Tsuno Yuho , Sawada Masami
Published: July 2006

The basicities of nine polynuclear aryl methyl ketones have been determined spectrophotometrically in various aqueous sulfuric acid solutions. The electronic effects of unhindered polynuclear aryls on pKBH+ can be successfully correlated with our LArSR equation,

logk⁄k0=ρ(σ0+rΔ\barσ\overset+R),

using ρ and r values established from meta- and para-substituted acetophenones. The applicability of this equation to polynuclear aryls is also shown for some other electrophilic reactivities. The Δ\barσ\overset+R parameters for polynuclear aryls are derived empirically from the solvolysis of α-arylethyl chlorides; these show a good linearity with the theoretical reactivity indices of the localization energies.