bluuebunny/crossref_metadata_2025 huggingface dataset:
The Isomerization of n-Butenes over Acidic Ion-exchange Resin
Authors: Uematsu Takayoshi
Published: July 2006

The isomerization of n-butenes and the polymerization of propylene were studied in a gas-phase reaction on a sulfonic acid-type resin catalyst. These reactions were considered to proceed via the carbonium ion formation on the functional groups, and a strong correlation was found between the activities in these two reactions. The acidity and the acid strength of the resin catalyst were measured by means of amine titration in a nonpolar solvent using Hammett indicators. The value of the acidity obtained at pKa=6.8 seemed to correspond to the number of the ion-exchangeable hydrogen on the functional groups. The effects of poisoning by ion exchange with Na+, Mg2+ or by adsorption of NH3 were also studied. The decrease in the activity for the isomerization was not proportional to the amount of cations exchanged. The catalytic activities of the protonic hydrogen seemed not to be equal as was suggested by the result of resin catalysts in polar solvents. The possible heterogeneity of the active sites on the resin catalyst was discussed. The six relative rate constants were calculated on the basis of the mutual interconversion among the three isomers of n-butene. The apparent energy of activation for the double-bond migration of 1-butene was found to be 17 kcal/mol on the H-form resin, but it was changed by ion exchange with Na+. The selectivities were characteristic of solid acid catalysts of the protonic type.
Fractionation of Tritiated Water in Potassium Chromium Sulfate Dodecahydrate
Authors: Tanaka Haruhiko , Kado Tsutomu , Negita Hisao
Published: July 2006

A considerable dilution of tritiated water in the water of crystallization was observed in the crystal-growth process of KCr(SO4)2·12H2O from a slightly supersaturated aqueous solution. This was explained in terms of an ionic process in aqueous solution and a surface-diffusion mechanism of crystal growth. It was also found that the tritium content in the hexahydrate was appreciably smaller than that in the liberated water during the course of reaction;

KCr(SO4)2·12H2\xrightarrow[in vacuo]40°CKCr(SO4)2·6H2O+6H2O.

It seems that the step wise dehydration supports the dehydration mechanism proposed by Garner.
Deuteron Magnetic Resonance Studies of Structures and Phase Transitions in the Tantalum-Deuterium System
Authors: Nakamura Keikichi
Published: July 2006

The deuteron magnetic resonance in the tantalum-deuterium system has been measured as a function of the composition (0.45 to 0.198 D/Ta) and of the temperature (90 to −179°C), and the results has been discussed in relation to the neutron diffraction and the heat capacity data. The most probable arrangement of the deuteriums in the polymorphic varieties has been proposed. For the low temperature form β1 form), it has an ordered structure which belongs to the space group A222, with the four tantalums at the 4K positions and the two deuteriums at the 2a positions. Since the deuterium positions are described by a single Z′ principal axis direction, which coincides with the c axis, the quadrupole coupling constant is not averaged by the rapid diffusion of the deuteriums. For the intermediate temperature form (β2 form), a structure constructed with four types of domains has been proposed. In this structure, the space group is the same as that of the β1 form, and the deuterium positions in the domains are 2a, 2b, 2c, and 2d respectively. For the high temperature form (α form), the observed quadrupole coupling constant, which is averaged to zero, can be accounted for if the deuteriums are randomly distributed over all the available tetrahedral sites. However, the calculated configurational entropy based on this assumption is larger than the measured value.
Electron Spin Resonance Study of Amino Acid Radicals Produced by Fenton’s Reagent
Authors: Taniguchi Hitoshi , Hasumi Hideyo , Hatano Hiroyuki
Published: July 2006

Free-radical intermediates in the reaction of the hydroxyl radical with amino acids and structurally related compounds such as alcohols, amine, and carboxylic acids have been studied by ESR spectroscopy using a continuous-flow method. The hydroxyl radical is generated by a ferrous ion-hydrogen peroxide system (Fenton’s reagent). ESR spectra with fairly good signal-to-noise ratios are obtained for the first time in a Fenton’s reagent system from glycine, valine, leucine, glutamic acid, lysine, methionine, tyrosine, ethylamine, acetic acid, pro-pionic acid, n-butyric acid, and succinic acid. Structures, g-values, and hyperfine coupling constants of these radicals are tabulated. The analysis of ESR spectra shows that the same radical species are produced mainly in a Fenton’s reagent system as in a titanous chloride-hydrogen peroxide system. This is consistent with the existence of the hydroxyl radical in both systems. The observed ratio of C2–H to C1–H proton hyperfine coupling constants gives information concerning steric conformations, freedom in the internal rotations, and s-character of the intermediate radicals.
The Temperature Dependence of the Fractionation of Tritiated Water in an Equilibrium between Crystalline Alum and Its Aqueous Solution
Authors: Tanaka Haruhiko
Published: July 2006

The temperature dependence of the fractionation of tritiated water (HTO) was examined during the crystal growth of alum from its tritiated aqueous solution. When the ratios of the mole fractions of HTO in the water of crystallization to that of the mother liquid, S, at various temperatures are compared, the following order is established:

S 19.90≈S29.50>S36.52>S41.95>S47.43>S53.70≈S69.50,

where the suffixes represent the crystallization temperatures, and where S19.90=0.975 and S69.50=0.949. The concept of the hydration of ions developed recently was applied to the problem of the crystal growth from the solution. Two kinetic parameters, such as the relaxation time of the aluminum ion for entering the surface, τc, and that of the hydrated aluminum ion, Al(OH2)63+, for the exchange of the water with bulk water, τe, were taken into account to explain the fractionation. A surface-diffusion mechanism was suggested as essential in the crystal growth of alum from the solution. The activation free energy for the crystal growth from an unstirred solution was found to be 18.17 kcal/mol, a value which was in good agreement with the value given by Bennema.
The Crystal Structure of the Polymerization Catalyst of Acetaldehyde and Its Derivatives. III. The Crystal and Molecular Structure of the Bis(dimethylaluminum N-Phenylbenzimidate-Acetaldehyde) Complex, [(CH3)2Al·O·C(C6H5):N(C6H5), CH3CHO]2
Authors: Kai Yasushi , Yasuoka Noritake , Kasai Nobutami , Kakudo Masao
Published: July 2006

The molecular structure of a stereospecific (isotactic) polymerization catalyst of the acetaldehyde-monomer complex, [Me2Al·O·CPh: NPh,MeCHO]2, has been determined on the basis of three-dimensional X-ray data collected photographically. The crystal belongs to the orthorhombic system (space group Pcca) with four dimer formula units in a cell with the dimensions of: a=15.83(3), b=12.61(1), and c=17.66(1) Å. The structure was established by the heavy-atom method and refined by block-diagonal, least-squares procedure. The molecule is dimeric and has a C2-2 symmetry. A monomer molecule, acetaldehyde, is inserted in the Al–N bond of the original polymerization catalyst. The oxygen atom bridges both aluminum atoms, Al–O=1.858(6) and 1.985(6) Å. The α-carbon atom of acetaldehyde bonds to the nitrogen atom of the amide moiety, C–N=1.469(12) Å. The aluminum atom is penta-co-ordinated and has a trigonal bipyramidal conformation.
The Crystal Structure of the Polymerization Catalyst of Acetaldehyde and Its Derivatives. IV. The Crystal and Molecular Structure of Dimethylaluminum N-Phenylbenzimidate-O-(Trimethylaluminum)-Acetaldehyde Complex, [(CH3)2Al·O·C(C6H5):N(C6H5), CH3CHO, Al(CH3)3]
Authors: Kai Yasushi , Yasuoka Noritake , Kasai Nobutami , Kakudo Masao
Published: July 2006

The molecular structure of a stereospecific (isotactic) polymerization catalyst of the acetaldehyde-monomer-Lewis acid complex, [Me2Al·O·CPh:NPh,MeCHO,AlMe3], has been determined from three-dimensional X-ray-diffraction data collected photographically. The crystal belongs to the monoclinic system (space group P21⁄n), with four formula units in a cell with dimensions of: a=13.60(3), b=13.74(2), c=12.40(2) Å, β=95.9(2)°. The structure was solved by the heavy-atom method and was refined by the block-diagonal, least-squares procedure. The trimethylaluminum forms a bond with the electron-rich oxygen atom of acetaldehyde through the electron-deficient aluminum atom. The polymerization mechanism can reasonably be concluded to be the “co-ordinated cationic polymerization”.
Conditions Favorable for the Formation of γ-FeOOH by Aerial Oxidation in an Acidic Suspension of Iron Metal Powder
Authors: Kiyama Masao , Akita Toshikazu , Shimizu Shigeki , Okuda Yoshiro , Takada Toshio
Published: July 2006

Dilute solutions of ferrous sulfate, sulfuric acid, hydrochloric acid, nitric acid and acetic acid in which iron powders are dispersed have been oxidized at below 80°C by blowing air into them. The resulting precipitates have been examined by means of X-ray diffraction, chemical analysis and optical and electron microscopy. When the iron powder is well dispersed, γ-FeOOH is formed with or without α-FeOOH, α-Fe2O3, or Fe3O4. The mode of formation depends on such factors as particle size, amount of iron powder, kind of anion present and temperature. Particle size greatly influences the formation of γ-FeOOH in the sulfate system, but not in the other systems.
Determination of the Formation Constants of Actinoid and Lanthanoid Lactate Complexes by Means of Electrophoresis
Authors: Sakanoue Masanobu , Nakatani Mitsuo
Published: July 2006

Determination of the complex formation constant of actinides (Am, Cm) and lanthanides (Pm, Eu, Lu) with lactic acid was carried out by means of the electrophoretic method. “Cellogel”, a gelatinized cellulose acetate was used as the supporting medium for electrophoresis at 10°C. Electrolyte solutions of various pH at an ionic strength of 1.5 were prepared from 0.5m lactic acid solution for electrophoresis at various pH values. The migration zones of α- and β-emitter were determined by α track on cellulose nitrate and autoradiographic image on X-ray film, respectively. The mobility of each nuclide at different pH was analyzed to obtain the formation constants of lactate complex of each element with reference to dissociation equilibrium. The β1 values thus obtained were consistent with those obtained by other methods. The method was found to be especially useful for determining the complex formation constants of trans-uranium elements with only tracer amounts of these elements.
Potentiometric Titration of Iron(III) with Hydrazine Sulphate at Room Temperature
Authors: Rao G Gopala , Rao P V Krishna , Rao G Bala Bhaskara
Published: July 2006

Conditions have now been developed for a direct potentiometric titration of iron(III) with hydrazine sulphate at room temperature. Osmium tetroxide markedly catalyses the reaction in medium of 2.0–3.0 pH. Under the conditions prescribed four moles of iron(III) are reduced per every mole of hydrazine oxidised. Application of the new method to the assay of iron(III) in an alloy is also considered.
Substituent Effects on Suspected Phenonium Ion Reactions
Authors: Kingsbury Charles A , Best D C
Published: July 2006

The stereochemistry of the various conversions in the 1,2-diphenyl-1-propyl system was measured as a function of aromatic substituent. For β-anisyl groups the reaction occurred with retention of configuration. For compounds with indifferent electron donating aryl groups, the conversions were stereoselective forming mostly threo product. For β-p-nitrophenyl groups the stereochemical course of the reaction was “racemization.” The latter reactions were associated with the presence of open ions. In certain reactions, acetate products were formed in low yield with retention of configuration, irrespective of substituent. The kinetics of ethanolysis were consistent with (partial) bridged ion formation for the threo isomers and with extensive open ion formation for the erythro species.
The Determination of Sulfide- and Sulfate-Sulfur in Igneous Rocks with Tin(II)-Strong Phosphoric Acid and Strong Phosphoric Acid
Authors: Nagashima Shigeru , Yoshida Minoru , Ozawa Takejiro
Published: July 2006

A method for the determination of minute amounts of sulfide- and sulfate-sulfur in igneous rocks was investigated. A rock sample is easily dissolved by heating with tin(II)-strong phosphoric acid or strong phosphoric acid. When the rock sample is dissolved with tin(II)-strong phosphoric acid, total-sulfur is evolved as hydrogen sulfide. With strong phosphoric acid, sulfide-sulfur is evolved as hydrogen sulfide, but sulfate-sulfur is not. The hydrogen sufide evolved is fixed as zinc sulfide, and then determined by the photometric method, using mercuric thiocyanate and ferric iron. The conditions for separating sulfide- and sulfate-sulfur in rocks were examined by using samples which had been prepared by mixing rock or silica (each of them, <0.001% S) with sulfides or sulfates. The application of the method to some igneous rock samples gave results with a coefficient of variation of about 5% for sulfur contents of 0.01–0.02%. The sulfur in samples with more than 0.001% can be determined by using about 0.1 g of samples. The sulfide- and sulfate-sulfur in two standard rock samples were also determined: W-1 (Total-S, 0.012%; Sulfide-S, 0.005%; Sulfate-S, 0.007%) and G-1 (Total-S, 0.004%, Sulfide-S, <0.001%; Sulfate-S, 0.004%).
Isomerism of the Metal Complexes Containing Multidentate Ligands. II. The Cobalt(III), Cobalt(II), and Nickel(II) Complexes of N,N,N′,N′-Tetrakis(2-aminoethyl)ethylenediamine and-1,2-propanediamine and Their Absolute Configurations
Authors: Yoshikawa Yuzo , Fujii Ekyo , Yamasaki Kazuo
Published: July 2006

The cobalt(III), cobalt(II), and nickel(II) complexes of N,N,N′,N′-tetrakis(2-aminoethyl)ethylenedianime and -1,2-propanediamine were prepared, and the cobalt(III) complex of the former ligand was resolved by fractional crystallization and column chromatography on SE-Sephadex. The absolute configurations of the cobalt(III) complexes were assigned on the basis of the stereospecificity of the latter ligand; they were later confirmed by the X-ray analysis. The electronic absorption, circular dichroism, and optical rotatory dispersion spectra of the complexes prepared were also measured.
Electron Spin Resonance during Photolysis of p-Benzoquinone and Its Derivatives in Ethanol
Authors: Yoshida Hiroshi , Hayashi Koichiro , Warashina Tetsuo
Published: July 2006

Electron spin resonance measurements were carried out at room temperature during photolysis of solutions containing p-benzoquinone, 2-methyl-p-benzoquinone, 2,5-dimethyl-p-benzoquinone and 1,4-naphthoquinone in ethanol. From all quinones, the semiquinone radicals and semiquinone anions are found to form simultaneously. When the solution is made acidic, the semiquinone anion transforms into the semiquinone radical, so that the spectrum of the latter is easily determined. For benzoquinone, the semiquinone radical is formed efficiently by light of λ≈300 nm, and has a life of about 0.05 sec. The semiquinone anion is formed by light of λ≈460 nm and is rather long-lived (about 0.5 sec). These results suggest that the semiquinone anion may be formed mostly by photodissociation of charge-transfer complex between benzoquinone and alcohols. Observed proton hyperfine coupling constants were subjected to the molecular orbital treatment. The coupling constants in all the semiquinone anions examined are well interpreted by McLachlan’s approximate SCF-MO method and Colpa-Bolton’s relation with Q=27G and K=12.8 G However, good agreement is not attained between the observed coupling constants and the calculated ones for the semiquinone radicals.
Positive Charge Distribution of Secondary Alkylamines and Its Correlation with the Bond-Scission Probability Appearing in Their Mass Spectra
Authors: Yamamoto Masao , Fujita Iwao , Itoh Michiyasu , Hirota Kozo
Published: July 2006

With respect to the correlation between scission probabilities and positive charge distributions on the skeletal bonds of amines appearing in their mass spectra, further research is reported on four secondary amines (diethylamine, dipropylamine, dibutylamine and methylbutylamine). In each secondary alkylamine the fragment ions formed by the scission of α–CC bond are the most abundant experimentally, i.e., the scission probability of α–CC bond is the largest in monoamines as well. Agreement between experiments and LCBO-MO calculations on four secondary alkylamines is found to be satisfactory as in the case of propylamine, using the same semi-empirical parameters as those of monoamines in the calculation. It is shown that from detailed calculations of diethylamine by CNDO method the scission of α–CC bond is also easy due to concentration of the positive charge at the bond, theoretically in accordance with the semi-empirical calculation. Change of mass spectra vs. ionizing voltage is explained on a generalized scheme, which combines two existing theories of fragmentation (QET and MOT).
The Resonance Raman Effect of Azobenzene and p-Aminoazobenzene
Authors: Koide Shiro , Udagawa Yasuo , Mikami Naohiko , Kaya Koji , Ito Mitsuo
Published: July 2006

The resonance Raman spectra of azobenzene and p-aminoazobenzene were measured precisely at various excitation wavelengths. It was found that the π–π* excited state played a dominant role in the Raman intensities but not the n–π* excited state and that there was no correlation between the Raman intensity and the absorption coefficient at excitation wavelength.
Mass Spectrometry of 1-Phenylazo-2-naphthols
Authors: Kobayashi Kousuke , Kurihara Kenji , Hirose Kazutoyo
Published: July 2006

In order to examine the azo-hydrazone tautomerism of substituted 1-phenylazo-2-naphthols and to estimate the effect of substituents on the equilibrium, mono-substituted 1-phenylazo-2-naphthols were synthesized and the spectra were compared with those of the respective acetylated derivatives and β-naphthoquinone-methylphenylhydrazone as references of the azo and hydrazone forms respectively. The spectra of acetylated derivatives show the same pattern as those of the original samples except for the molecular ion and ion at m⁄e: 43. Moreover, β-naphthoquinone-methylphenylhydrazone displays a different fragmentation process, the cleavage of the N–N bond. In conclusion, the substituted 1-phenylazo-2-naphthols exist in the gaseous state as only the azo form; this is different from the results in the liquid and solid states. The fragmentation processes, in which the reactions of M+→ (m⁄e: 171)+→ (m/e: 143)+→(m⁄e: 115)+ mainly occur, are clarified on the basis of these results. The effect of substituents on the reaction rate of the formation of ions at m⁄e: 171 from molecular ions is examined. The correlation with the Hammett σ constants is ρ=0.078 for meta substituents, and the plots for para substituents lie under the line, which means that the reaction rate for para substituents is slow. This is explained on the basis of the resonance effect.
The Stereoselective Reactivities of Dl-Amino Acid N-Carboxyanhydrides for (−)-Menthol
Authors: Hayakawa Tadao , Yamamoto Hiroyuki , Murakami Yukiko , Yobiko Yoshihiro , Mitani Shunji
Published: July 2006

The stereoselective reactivities of some neutral Dl-amino acid N-carboxyanhydrides for (−) -menthol were studied by varying the concentration of hydrogen chloride as a catalyst and the reaction temperature. From the results of gas-liquid-chromatographic analyses, the esterification rates of d-amino acids were shown to be higher than those of l-amino acids in all cases. The highest ratio of the esterification rate, VD⁄VL, is 2.37. The recovered unreacted amino acids were always enriched in the l-form. The stereoselective reactivities were influenced by the catalyst concentration and not influenced by the reaction temperature.
Studies of Dithiobiurets. III. The Preparation and Properties of 3,5-Disubstituted 3H-1,2,4-Dithiazoles
Authors: Iwataki Isao
Published: July 2006

3,5-Disubstituted 3H-1,2,4-dithiazoles were prepared by the oxidation of dithiobiurets, S-benzylisodithiobiurets, and alkyl trithioallophanates, and then 3-acyl or carbamoylimino derivatives were obtained by the direct acylation or carbamoylation of the dithiazole salts. From the spectral data of these compounds, it is concluded that the carbonyl group affects the pseudoaromatic character of the dithiazole ring system.
Oxidative Dimerization of Pyrrole Derivatives. III. Studies on the 3-Carbonyl Substituted Pyrryl Radicals.
Authors: Tomita Kuniyuki , Yoshida Norio
Published: July 2006

The thermochromic properties of the dimers in solution, obtained by oxidation of 3-carbonyl substituted pyrroles, was determined as being due to the reversible dissociation into pyrryl radicals. The structure and character of the pyrryl radicals are discussed on the basis of substituent effect on thermochromism and ESR studies.
Self-Diffusion of Chloride Ions in Manganese Bichloride Crystallites
Authors: Sensui Yoshihiro
Published: July 2006

The self-diffusion of chloride ions in the powdery crystals of manganese dichloride was studied in the temperature range of 200–420°C by the use of the isotopic-exchange method. The activation energies for self-diffusion were determined to be 0.95 and 1.6eV in a lower and a higher temperature region respectively. From these, the activation energy for the migration of chloride ions and the formation energy of an anion vacancy or a pair of an anion and a cation vacancy were deduced.
Synthetic Reactions by Complex Catalysts XXVIII. Reaction of β-Propiolactone with Alkyl Halide Caused by Cu2O-Isonitrile Complex
Authors: Saegusa Takeo , Murase Ichiki , Nakai Michio , Ito Yoshihiko
Published: July 2006

Oligomerization of β-propiolactone (BPL) caused by the Cu2O-isonitrile complex in the presence of alkyl halide was studied, and an oligomeric mixture of acrylate derivatives 3 (n=1, 2 and 3 in Eq. (3)) was isolated in fairly high yields. The complex catalyst showed a distinguished catalytic activity for the oligomerization of BPL. The reaction mechanism involving an intermediate of organocopper(I) isonitrile 4, which is converted into copper (I) acrylate isonitrile complex 5 was presented.
The Photo-decomposition of 1-Azidopyrene in the Benzene Solution
Authors: Yamaoka Tsuguo , Kashiwagi Hiroshi , Nagakura Saburo
Published: July 2006

1-Nitrenopyrene (Py-N) was produced by the photo-decomposition of 1-azidopyrene (Py-N3) in the benzene solution at 77°K and at room temperature. At 77°K, Py-N was found to be stable, and its electronic absorption and ESR spectra were measured. The result shows that its ground state is triplet and the fine structure constant, D, is equal to 0.73 cm−1. At room temperature, 1-nitrenopyrene was found to be converted easily into 1,1′-trans-azopyrene (trans-Py-N=N–Py) in the oxygen-free benzene solution and into 1-nitropyrene (Py-NO2) in addition to Py-N=N-Py in the oxygen-containing benzene solution. The decay process of Py-N as a reaction intermediate and the formation processes of the reaction products were studied by the flash-photolysis technique, and from an analysis of the results, the rate constants at 23°C were determined to be 2.1×109lmol−1 sec−1 and 1.4×103sec−1 for 2Py–N→trans-Py-N=N–Py and for Py–N+O2→Py-NO2, respectively.
Studies on Aminosugars. XXXI. Synthesis of 3,4-Dideoxy-3-enosides and the Corresponding 3,4-Dideoxysugars
Authors: Umezawa Sumio , Okazaki Yasushi , Tsuchiya Tsutomu
Published: July 2006

As model experiments to prepare unsaturated and deoxy variants of complex aminoglycosidic antibiotics, methyl 3,4-dideoxy-α-d-erythro-hexopyranoside (8) and methyl 2,6-diamino-2,3,4,6-tetradeoxy-α-d-erythro-hexopyranoside (15) have been synthesized through the corresponding 3,4-unsaturated glycosides (6, 12), which were prepared from the corresponding 3,4-di-O-mesyl derivatives (5, 11) by treatment with sodium iodide and zinc dust in high yields. These are rare examples of 3,4-dideoxy and 3,4-unsaturated sugars.
Crystal and Molecular Structure of ω-Amino Acids, ω-Amino Sulfonic Acids and Their Derivatives. II. The Crystal and Molecular Structure of α-Form of 3-Aminopropane Sulfonic Acid, Homotaurine
Authors: Ueoka Sumiko , Fujiwara Takaji , Tomita Ken-ichi
Published: July 2006

From ethanol aqueous solution, two forms of crystals of 3-aminopropane sulfonic acid (homotaurine) have been obtained in different crystal systems. The α-form is orthorhombic, space group Pmn21, with two molecules in a unit cell of the dimensions; a=7.059, b=5.492 and c=7.428 Å. The X-ray structure analysis was carried out by the application of usual heavy atom method and refined by three dimensional least-squares procedure. The final R-value is 0.059. In the crystalline state, homotaurine molecule has the zwitterionic structure, NH3+–CH2–CH2–CH2–SO3−, with trans-zigzag skeletal configuration, and non-hydrogen atoms except two oxygen atoms lie exactly on a mirror plane. Each molecule in the crystal is connected by three dimensional network of three NH···O hydrogen bonds.
Studies of Acenaphthene Derivatives. XXVI. The Thermal Cycloaddition of 2-Diazoacenaphthenone to Isocyanates
Authors: Tsuge Otohiko , Shinaki Ichiro , Koga Masahiro
Published: July 2006

Although 2-diazoacenaphthenone did not react with phenyl isocyanate or phenyl isothiocyanate on prolonged reflux in toluene, it reacted with strongly electrophilic benzoyl and p-chlorobenzoyl isocyanates and thiobenzoyl isocyanate to give the corresponding spiro[acenaphthenone-2,5′-oxazolin-4′-one] and the spiro-thiazolin-4′-one in good yields. On the other hand, the reaction of the α-diazoketone with benzoyl isothiocyanate gave 8-benzoylacenaphtho[1,2-d]isoxazolin-9-thione, which on catalytic hydrogenolysis over PtO2 gave the dihydro compound corresponding to reductive cleavage of N–O bond of the isoxazoline ring. Furthermore, the reaction of the α-diazoketone with benzenesulfonyl isocyanate gave two stereoisomeric bis-spiro-azetidinones. The mechanisms of these reactions are proposed.
The Exchange Reaction of Deuterium with the Hydroxyl Groups of Zeolite Catalysts
Authors: Imanaka Toshinobu , Okamoto Yasuaki , Takahata Kazunori , Teranishi Shiichiro
Published: July 2006

In order to estimate the reactivity of each hydroxyl group, the exchange reaction of deuterium with the hydroxyl groups on the surfaces of the HX, HY, and CaHX zeolites and aerosil was investigated kinetically by an infrared method. The hydroxyl groups appearing at 3660 cm−1 on the HX and HY zeolites were more readily exchanged with deuterium than were the other hydroxyl groups on the two zeolites. However, in the case of the CaHX, the order of activities of each hydroxyl group changed with the pressure of deuterium. The rate equation for the reaction is expressed by a Langmuir-type equation. This fact indicates the homogeneity of each hydroxyl group on zeolite. It was found that adsorbed water and carbon dioxide catalyzed the exchange reaction. Furthermore, a compensation effect between the apparent activation energies and the frequency factors occurs in this reaction.
Chemical Studies on Tuberactinomycin. IV. The Chemical Structure of γ-Hydroxy-β-lysine, A New Amino Acid Isolated from Tuberactinomycin A and N
Authors: Wakamiya Tateaki , Shiba Tetsuo , Kaneko Takeo
Published: July 2006

γ-Hydroxy-β-lysine is a new basic amino acid isolated from the hydrolyzates of antitubercular peptides, tuberactinomycin A and N as one of the composite amino acids. The chemical structure and stereochemistry of the amino acid were established on the basis of chemical reactions and physical measurements, i.e., IR, NMR, and ORD. One stereoisomer obtained in hydrochloric acid hydrolysis was determined as threo-γ-hydroxy-l-β-lysine (Ia), while the other one obtained in concentrated sulfuric acid hydrolysis as an erythro isomer (Ib).
Reduction of 7-Methylenebicyclo[3.3.1]nonan-3-one and Related Compounds: Structural Investigation of the Products
Authors: Kimoto Koichi , Imagawa Takeshi , Kawanisi Mituyosi
Published: July 2006

Hydrogenation of 7-methylenebicyclo[3.3.1]nonan-3-one (1) over platinum oxide in acetic acid yielded 7α-methylbicyclo[3.3.1]nonan-3α-ol (2) as the sole product. Hydrogenation of (1) in ethyl acetate afforded 7α-methylbicyclo[3.3.1]nonan-3-one (3) as a reduced product and 7-methylbicyclo[3.3.1]non-6-en-3-one (4) as an isomerized product. Hydrogenation of 1 over palladium on carbon gave no reduced product but 4 in 100% conversion. Hydrogenation of 7-methylenebicyclo[3.3.1]nonan-3α-ol (7) and -3β-ol (8) over platinum oxide in acetic acid gave 2 and 7α-methylbicyclo[3.3.1]nonan-3β-ol (5), respectively. From studies based on NMR spectroscopy with use of a shift-reagent, it is concluded that the major conformer of 2 and 5 is of chair-boat form. By the equilibration experiment between 2 and 5 using aluminum isopropoxide in isopropyl alcohol at 110°C, the ΔG° value was found to be −2.2 kcal/mol.
Studies on Oxosulfonium Salts. I. Preparation and Physical Properties.
Authors: Kobayashi Michio , Kamiyama Kenji , Minato Hiroshi , Oishi Yukio , Takada Yoko , Hattori Yoshitaka
Published: July 2006

Methods for preparation and physical properties of oxosulfonium salts have been discussed. Optically active ethylmethylphenyloxosulfonium salts have been prepared and their absolute configurations have been determined.
Some Physico-chemical Properties of Vanadium Oxide Supported on Silica or γ-Alumina
Authors: Yoshida Satohiro , Iguchi Toshikatsu , Ishida Shingo , Tarama Kimio
Published: July 2006

The interactions between vanadium(V) oxide and carriers were investigated in the vanadium oxide catalysts supported on silica and γ-alumina by measuring X-ray diffraction patterns, ESR spectra, solubilities into 0.3 n ammoniacal solutions and reduction rates by benzene. A part of vanadium oxide on the carriers was insoluble in an ammoniacal solution, while unsupported vanadium oxide was easily soluble, and the reduction rates of the catalysts were remarkably affected by the carriers and the vanadium oxide contents. ESR spectra revealed that the vanadium oxide was stabilized by interaction with carriers as a square pyramidal one (VO5) and a tetrahedral one (VO4) on the surfaces of γ-alumina and silica, respectively. Massive vanadium(V) oxide crystals grew on these interacted layers with the increase of the oxide contents.
The Chemical Behavior of 64Cu Recoil Atoms in the Mixed System of Copper Phthalocyanine and Metal-free Phthalocyanine
Authors: Kudo Hiroshi
Published: July 2006

In order to elucidate the effect of the crystal structure on the chemical behavior of 64Cu recoil atoms in copper phthalocyanine, the author studied the mixed system of copper and metal-free phthalocyanine. It was found that the initial retention increased both in the mixed crystal and in the mixed-disk target. The addition of metalfree phthalocyanine sensitized the target to the thermal annealing reaction, and the rate of the reaction in the mixed crystal was faster than that in the unmixed crystal. The electron acceptor in the target was also found to increase the initial retention. The results were discussed in terms of the electrical properties of the target, which were changed by the change in the spatial arrangement of the molecules.
Kinetics and Mechanisms of the Reaction of Tl(III) with Variamine Blue, [N-(p-Methoxyphenyl)phenylenediamine] in Aqueous Perchlorate Media
Authors: Imamura Taira , Fujimoto Masatoshi
Published: July 2006

A stopped-flow apparatus was used to study the kinetics of the redox reaction of Tl(III) with Variamine Blue under nitrogen atmosphere in acid (0.2–0.6 m) perchlorate media of ionic strength μ=1.0 m. The observed second-order rate constant increases inversely with hydrogen ion concentration. The proposed mechanism involves the overall rate-determining steps

Tl3++(V.B.)\oversetk1\ightleftharpoonsTl++(V.B.)ox+2H+

TlOH2++(V.B.)\oversetk2\ightleftharpoonsTl++(V.B.)ox+H2O+H+

where (V.B.) and (V.B.)ox are a reduced form and an oxidized form of Variamine Blue respectively. The rate constants are evaluated to be k1≤102  m−1 sec−1, and k2=3.6×104  m−1 sec−1 at 25°C. The activation energy E2 for k2 is 11±0.8 kcal·mol−1.
The Reaction of Tris(acetylacetonato)cobalt(III) with Bromine in Dichloromethane
Authors: Nakamura Yukio , Gotani Mitsuru , Kawaguchi Shinichi
Published: July 2006

Dibromo(acetylacetone)cobalt(II), a new complex containing an acetylacetone molecule as the bidentate ligand, was formed by the reaction of tris(acetylacetonato)cobalt(III) with bromine in dichloromethane, and characterized by elemental and thermogravimetric analyses and electronic and infrared spectra. The same compound was also prepared by direct addition of acetylacetone to anhydrous cobalt(II) bromide. The radical nature of the redox step involved in the reaction pathway from the starting cobalt(III) chelate to the product cobalt(II) complex of acetylacetone was demonstrated by polymerization of methyl methacrylate and styrene remarkably enhanced by the reaction system.
Acidic Property and Catalytic Activity of TiO2·ZnO
Authors: Tanabe Kozo , Ishiya Chijiko , Matsuzaki Isao , Ichikawa Ichiro , Hattori Hideshi
Published: July 2006

A new type of mixed metal oxide TiO2·ZnO was prepared by either heterogeneous or homogeneous co-precipitation and the acidic property was measured by n-butylamine titration and by observation of infrared spectra of adsorbed pyridine. It was found that TiO2·ZnO containing about 7 or 57% of ZnO shows a very large acid amount of 0.5–0.9 mmol/g and a fairly high acid strength of H0≤−3, the acid sites being both Brönsted and Lewis type and the acid sites of high strength created by heterogeneous precipitation. The catalytic activity and selectivity of TiO2·ZnO were found very high for the hydration reaction of ethylene. The catalyst was active also for the alkylation of phenol by methanol and gave only monoalkylated products.
The Reaction of Bis(acetylacetonato)cobalt(II) with Bromine in Dichloromethane
Authors: Nakamura Yukio , Kanehisa Nobuko , Kawaguchi Shinichi
Published: July 2006

When bis (acetylacetonato)cobalt(II) is allowed to react with twice molar quantity of bromine in dichloromethane, cobalt(II) bromide and γ-bromoacetylacetone are produced ultimately. From a deep blue solution of an equimolar reaction mixture at 0°C an intermediary product was isolated and characterized to be dimeric bromo(acetylacetonato)cobalt(II) by means of elemental analysis and molecular weight determination. The structure of this compound was inferred to be tetrahedral from absorption spectra and magnetic data. Acetylacetonate groups were supposed to act as bridging ligands on the basis of IR data in the lower frequency region. Dibromobis(acetylacetonato)dicobalt(II) was also derived from dibromo(acetylacetone)cobalt(II) by the reaction with sodium acetylacetonate in acetylacetone at 0°C.
Reactions of Dibromoalkanes with Dimethyltin Bis(N,N-dimethylthioseleno and diselenocarbamates) and Related Compounds
Authors: Tanaka Koji , Tanaka Toshio
Published: July 2006

Dimethyltin-bis(N,N-dimethylthioselenocarbamate), (CH3)2Sn[SSeCN(CH3)2]2, dimethyltin-bis(N,N-dimethyldiselenocarbamate), (CH3)2Sn[Se2CN(CH3)2]2, and dimethyltin-bis(N-methyl-N-phenyldiselenocarbamate), (CH3)2Sn[Se2CN(CH3)(C6H5)]2, react with dibromoalkanes to give bis(1-thia-3-selenacycloalkyl-2-dimethylimminium)dimethyltin tetrabromide, (Remark: Graphics omitted.) (m=2, 3), 1,3-diselenacycloalkyl-2-dimethylimminium dimethyltin bromides, (Remark: Graphics omitted.) (n=1, m=2 and n=2, m=3), and 1,3-diselenacyclopentyl-2-methylphenylimminium bromide, (Remark: Graphics omitted.), respectively. The infrared and PMR spectra indicate that the positive charges of 1-thia-3-selena- and 1,3-diselenacycloalkylimminium ions are more delocalized in the higher homologs than in the lower ones.
Kinetics of the γ-Ray Induced Polymerization of Ethylene in 1,2-Dichlorotetrafluoroethane
Authors: Suganuma Fujio , Hagiwara Miyuki , Mitsui Hiroshi , Kagiya Tsutomu
Published: July 2006

The γ-ray induced polymerization of ethylene in bulk or in solution in the presence of 26.9–67.3 g of 1,2-dichlorotetrafluoroethane (R-114) was carried out in a 100-ml reactor under a pressure of 210–400 kg/cm2 and at 30°C, with a dose rate of 1×104–9×104 rad/hr. The rate of the polymerization and the molecular weight of the polymer formed increased with the reaction time and the pressure. The rate also increased upon the addition of an appropriate amount of R-114. On the other hand, the molecular weight decreased with an increase in the amount of R-114. The dose-rate exponents of the rate and the molecular weight were found to be 0.8 and −0.2 respectively. These results were analyzed kinetically, and the rates and the rate constants of the initiation, propagation, transfer, and termination reactions were evaluated. Further, the roles of R-114 in the polymerization were discussed.
Syntheses of All Isomers of Naphthalenetricarboxylic Acids
Authors: Dozen Yasuhiko
Published: July 2006

All the fourteen isomers of naphthalenetricarboxylic acids have been synthesized by the oxidation of trimethylnaphthalenes, dimethylacetonaphthones, dimethylnaphthoic acids, methylnaphthalenedicarboxylic acids, β-(dimethylnaphthoyl)propionic acid, or β-(acenaphthoyl)propionic acids with aqueous sodium bichromate or potassium ferricyanide. Most of these naphthalenetricarboxylic acids, acid anhydrides, and trimethyl esters are new compounds.
The Constituents of Arthraxon hispidus Makino, Miscanthus tinctorius Hackel, Miscanthus sinensis Anderss, and Phragmites communis Trinius
Authors: Kaneta Makoto , Sugiyama Noboru
Published: July 2006

From the leaves and stems of Arthraxon hispidus Makino, aconitic acid, luteolin, luteolin-7-glucoside, and a new flavone, arthraxin, have been isolated. Luteolin, luteolin-7-glucoside, and arthraxin were also isolated from Miscanthus tinctorius Hackel, and tricin was isolated from Miscanthus sinensis Anderss and Phragmites communis Trinius.
The Reactions of Metal Acetylacetonates and Related Compounds with 2,2-Diphenyl-1-picrylhydrazyl
Authors: Uehara Kaku , Kamei Kiyohiro , Tanaka Makoto , Murata Niro
Published: July 2006

Some metal acetylacetonates (M(acac)n) were observed to react with the stable free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) in organic solvents. For the reaction of cupric 3-α-butenylacetylacetonate with DPPH in benzene and cyclohexane, the following rate equation was obtained: R=k[cupric chelate][DPPH]. The activation parameters of the reaction were remarkably dependent upon the nature of the substituent and the metal atom in M(acac)n, and upon the solvent. The results of the kinetic studies and the analytical work suggested that M(acac)n reacted with DPPH to yield 2,2-diphenyl-1-picrylhydrazine (DPPH-H) via the reduction of the central metal of the M(acac)n.
Stereochemical Studies of Monoterpene Compounds. XIV. The Rotational Conformation of the Acetyl and the Formyl Groups of Monoterpene α,β-Unsaturated Carbonyl Compounds
Authors: Suga Takayuki , Imamura Kiyoshi , Shishibori Tsuyoshi
Published: July 2006

Temperature-dependent circular dichroism measurements in the n−π* transition enabled us to predict the preferred rotational conformation of the acetyl and the formyl groups of such monoterpene α,β-unsaturated carbonyl compounds as (+)-1-acetyl-4-methylcyclohexene (1), (−)-perillaldehyde (2), (+)-1-acetyl-2,4-dimethyl-cyclohexene (3), and(−)-myrtenal (4).
Studies on Mannan and Related Compounds. I. The Purification of Konjac Mannan
Authors: Sugiyama Noboru , Shimahara Hideo , Andoh Tetsuo
Published: July 2006

The preparation of pure konjac mannan is described. Its properties and purity are also studied.
Stereochemical Studies of Monoterpene Compounds. XV. A Conformational Study of Carvomenthone Derivatives by Means of Temperature-dependent Circular Dichroism
Authors: Suga Takayuki , Watanabe Satoru
Published: July 2006

The conformations of (1R:4R)-(−)-p-menth-8-en-2-one (1) and of diastereoisomeric pairs of (+)-1-hydroxy-p-menth-8-en-2-one, (2) and (3), (+)-1-hydroxy-p-menthan-2-one, (6) and (7), and (+)-1-hydroxy-8-bromo-p-menthan-2-one, (10) and (11), were examined by a combination of infrared spectra and temperature-dependent circular-dichroism (CD). Explanations are given mainly with regard to the epimeric pair, (2) and (3). It is demonstrated that α-hydroxyketone (2) exists in a conformational equilibrium among 2a, 2b, and 2c. The 2a conformer predominantly exists in a polar medium and at low temperatures, whereas the 2b conformer is more stable than 2a in a nonpolar medium. On the other hand, the epimer (3) exists preferentially in the 3a conformation in both polar and nonpolar media and at low temperatures. The CD curves of compounds 6 and 7 exhibited the exactly same behavior as those in compounds (2) and (3) respectively. These results are interpreted in terms of the competition of the steric factor and the intramolecular hydrogen bonding.
A New Steroid with an Unnatural Configuration: 8α,14β-Progesterone
Authors: Mukawa Fumikazu , Nagata Wataru
Published: July 2006

A modified Wolf-Kishner reduction of certain 5α,8α,14β-11-oxo steroids gave the corresponding 11-deoxy steroids with the same stereochemistry, and the introduction of a double bond at C4–C5 leads to 8α,14β-progesterone. The structure and configuration of this compound are discussed on the basis of its physical properties. Its unnatural backbone stereochemistry was established by transformations from the 8α,14β-1,4-diene derivative to the known 8α,14β-estrone.
Studies on Geometrical Isomerism by Nulear Magnetic Resonance. V. Stereochemistry of 5-Substituted 4-Alkoxycarbonyl-2-carbamoylimino-1,3-oxathiolanes
Authors: Hayashi Toshio , Akano Makiko , Yokono Tetsuro , Uzawa Jun , Kambe Satoshi , Midorikawa Hiroshi
Published: July 2006

An equimolar reaction of thiocyanoacetic esters with aldehydes in the presence of potassium fluoride or carbonate leads to a stereoisomeric mixture of cis and trans isomers of 5-substituted 4-alkoxycarbonyl-2-carbamoylimino1,3-oxathiolanes. Several of them were separated into two isomeric forms, whose geometrical configurations were determined by means of nuclear magnetic resonance technique. The vicinal coupling constant between the 4-and 5-protons is consistently larger for the cis forms than for the trans. In the case of the 5-aryl derivatives, the signals of the alkoxycarbonyl group appear at higher field for the cis isomers than for the trans. The composition ratios of cis and trans isomers of the oxathiolanes prepared are determined. Infrared data of the cis and trans oxathiolanes are also reported.
Reactions of 5N-(1,2,3-Triazol-1-yl)tropolones
Authors: Horino Hiroshi , Toda Takashi
Published: July 2006

The chemical properties of 5N-(l,2,3-triazol-1-yl)tropolones are investigated. The reactions of 5N-(4′-ethoxycarbonyl-5′-methyl-1,2,3-triazol-1-yl)tropolone methyl ether (I) with malononitrile and ethyl cyanoacetate gave the corresponding azulene derivatives, but with ethyl acetoacetate the reaction afforded a 1-oxaazulan-2-one derivative. The methoxyl group of I is replaced by aliphatic amines to form 2-aminotropone derivatives. Also, the reaction of I with guanidine and o-phenylenediamine gave a 1,3-diazaazulene derivative and a quinoxaline derivative respectively. The brominations of triazolyltropolones afforded the corresponding 3,7-dibromotropolone derivatives, while reactions with thionyl chloride gave 2-chlorotropone derivatives.
Structural Effects on the Properties of Nonionic Surfactants. I. The Synthesis and Some Surface Activities of Acetal Type Homogeneous Nonionics
Authors: Kuwamura Tsunehiko , Takahashi Hideo
Published: July 2006

Higher aliphatic aldehydes (C8–C16) were treated in the presence of mineral acid with several pure polyoxyethylene glycols (m : 2–6), to give the corresponding acetals (AG types) with a general formula RCH[O(C2H4-O)mH]2. These AG types are soluble in water, fairly stable in neutral and weakly basic aqueous solutions, and they exhibited the characteristic properties of nonionics. The hydration of the geminal polyoxyethylene (POE) chains are discussed on the basis of the data of unexpectedly low cloud points. Surface tension measurements on the aqueous solutions of AG types indicated that the critical micelle concentration (CMC) value decreases with an increment of oxyethylene units (m), and that the molecular area does not depend so greatly on m and is significantly smaller than that predicted from the data of conventional nonionics (S types) having one hydrophobic and hydro-philic chain each. For the gross effects of AG types, it has been found that the foam stability is considerably low and the dependence of the wetting power for canvas discs on m is larger than that of S types. The results are discussed on the basis of structural characteristics related to the unfavorable hydration and restricted configuration of the geminal POE chains. The acid-catalyzed hydrolysis of AG types in the micellar solution was significantly slower than that of acetaldehyde diethylacetal in water.
Electron Spin Resonance Studies of Bis (acetylacetonato)copper(II) Adsorbed on X-Type Zeolite. II. The Substitution Reaction of Ligands with Pyridine
Authors: Yamada Yoshio
Published: July 2006

The interaction of bis(acetylacetonato)copper(II) (Cu(acac)2) adsorbed on X-type zeolite of the sodium form with pyridine was investigated by means of ESR. When a pyridine vapor was introduced to Cu(acac)2 on the zeolite, the spectral lines of the perpendicular g component for Cu(acac)2 were replaced by those consisting of a superhyperfine structure, which arises from the ligand nitrogen atoms. The observed spectrum was assigned to [Cu(pyridine)4]2+. Such a characteristic substitution reaction of Cu(acac)2 with pyridine was not, however, observed on silica gel nor in ordinary solvents. It is pointed out, on the basis of these results and of the considerations described in a preceding paper, that the reaction involves the following mechanism: the interaction of quasi-π-electrons in Cu(acac)2 with an electrostatic field originating from the cation on the zeolite lowers the stability of Cu(acac)2, and the complex is attacked by two adsorbed pyridine molecules and two pyridinium ions which are formed by the combination with protons on acid sites, resulting in the substitution reaction. In addition, [Cu-(pyridine)4]2+ was produced on other cation-exchanged zeolites and silica-alumina. The substitution reaction was also found when α-, β-, or γ-picoline was used instead of pyridine.
Interaction of Metal Porphyrins with Molecular Oxygen in Solutions
Authors: Yamamoto Kenichi , Kwan Takao
Published: July 2006

The oxidation of divalent metal tetraphenylporphin complexes by molecular oxygen has been investigated in solutions. It was found that the one-electron oxidation of low-spin iron(II) complexes to yield high-spin iron(III) does not take place, while a low-to-low conversion proceeds with ease. It is suggested that the ready oxidation is due to the delocalization of the dπ electrons of iron(II) to the vacant π-orbital of the porphin ligand. Oxidative mechanisms of manganese(II) and cobalt(II) tetraphenylporphins were also discussed.