bluuebunny/crossref_metadata_2025 huggingface dataset:
Solvent Effect on the Dielectric Properties of Nitroalkanes
Authors: Chandra Suresh , Nath Dina
Published: July 2006

Permittivity and dielectric loss of four nitroalkanes have been measured in solution in three solvents viz., n-heptane, benzene and cyclohexane at 9.8 GHz and 30°C. The variation of the relaxation time calculated from the data, with the viscosity of the solutions has been discussed. It has been found that the results cannot be explained on the basis of known relations between relaxation time and viscosity. It is expected that some other interactions such as proton-proton interaction are responsible for the relaxation time in cyclohexane lower than in benzene. The loss tangents are found to vary linearly with the concentration of the solution. Dipole moments have also been evaluated in all the three solvents and are in good agreement with the values in literature within experimental error.
Measurement of Negative Ions Formed by Electron Impact. VI. Negative Ion Mass Spectra and Ionization Efficiency Curves of Negative Ion of m/e 35 from Alkyl Chlorides
Authors: Tsuda Satoru , Yokohata Akira , Kawai Michihiro
Published: July 2006

The negative ion mass spectra of alkyl (methyl, ethyl, n- and iso-propyl) chlorides, with emphasis on their relative abundance to the positive ions under 80, 40, 20 and 15 eV electron energies, and the ionization efficiency (IE) curves of Cl− ions to the extent of 30 eV electron energies were measured. In every sample, the electron impacts of 80 eV and 40 eV gave almost the same distribution of m/e for negative ion mass spectra, in which, besides the intense peaks of m/e 35 and 37 (Cl−), a relatively strong peak of m/e 25 (C2H−) in ethyl chloride and n- and iso-propyl chlorides was characteristic. For 20 eV and 15 eV, Cl− ions predominated other negative ions. The ratio of the abundance of negative ions to positive ions was the order 102–103 for CH3Cl+/Cl−, C2H5Cl+/Cl−, C3H6+/Cl− and C3H7+/Cl− throughout the range of electron energies. Each onset value observed in IE curves was interpreted to correspond to the appearance of the following reactions, the reaction scheme for second process being tentative. For the first process RCl+e−→R+Cl−, for the second process CH3Cl+e−→H+CH2+Cl−, C2H5Cl+e−→H2+H+C2H2+ Cl−, C3H7Cl(n- or iso-)+e−→H+C2H4+CH2+Cl−. For the third process the possibility of ion pair formation was pointed out. For the fourth process in ethyl chloride a brief discussion was made in view of the overlapping phenomena of a complicated dissociative electron capture process with an ion pair formation.
The Crystal and Molecular Structure of Dimethyltin Chloride N,N-Dimethyldithiocarbamate
Authors: Furue Kenji , Kimura Toshihide , Yasuoka Noritake , Kasai Nobutami , Kakudo Masao
Published: July 2006

The molecular structure of dimethyltin chloride N,N-dimethyldithiocarbamate, [(CH3)2-SnCl(S2CN(CH3)2)], has been determined from three-dimensional X-ray diffraction data. The unit-cell dimensions are a=12.67, b=7.64, c=12.11 Å, and β=110.3°. The space group is P21/c. Four formula units are contained in a unit-cell. The structure was established by the heavy-atom method. The coordination around the tin atom is a distorted trigonal bipyramid with the following bond distances: Sn–C, 2.17(5) and 2.20(5) Å, Sn–Cl, 2.46(1) Å and Sn–S, 2.48(1) and 2.79(1) Å. Two methyl groups are both in equatorial positions.
The Visible Spectra of Alizarine Saphirol SE in Water-Dioxane Mixtures
Authors: Mitsuishi Masaru , Hashizume Mieko , Katayama Akira , Kuroki Nobuhiko
Published: July 2006

The visible absorption spectra of Alizarine Saphirol SE in water-dioxane mixtures were obtained, and the spectral changes were considered on the basis of the results of the conductance measurements of the dye. In the spectra of the dye in the mixtures containing less than 60% dioxane, the absorption was found to increase with an increase in the dioxane content. This spectral change was attributed to the decrease in the tendency of the dye to aggregate. In the spectra of the dye in the mixtures containing more than 70% dioxane, however, the absorption found to decrease with an increase in the dioxane content, i.e., with a reduction in the dielectric constant of the solvent. This spectral change was considered to be characteristic of the increase in the electrostatic interaction between the dye ion and the counter ion.
Temperature Dependence of the Heats of Solution of Poly(ethylene glycol) and of Related Compounds
Authors: Nakayama Haruo
Published: July 2006

The heats of solution of poly(ethylene glycol) and of related compounds (1,4-dioxane, tetra-hydrofuran, ethylene glycol, diethylene glycol, and several ethyl ethers of ethylene glycol and of diethylene glycol) have been measured as a function of the temperature. The change in the partial molar heat capacity of the solute molecule in the dissolution process, Δ\barCp2, is obtained from the temperature coefficient of the heat of solution. The Δ\barCp2 for poly(ethylene glycol) is 15 cal/deg per –CH2CH2O– chain unit. This value is in good agreement with those obtained for other low-molecular-weight compounds. The effect of the polar groups (the ethereal oxygen atom and the hydroxyl group) on the iceberg formation around the nonpolar residues has been discussed. From the results obtained, it seems likely that the iceberg formation around the –CH2CH2O– group is somewhat suppressed by the orientation-dependent interactions (hydrogen bond formation) between the ethereal oxygen atom and the water molecule.
Lattice Constants of Tetragonal Sodium Potassium Tungsten Bronzes
Authors: Utsumi Seiichiro , Fujieda Shuko
Published: July 2006

Sodium potassium tungsten bronzes, NaxKyWO3, having various values of x and y were prepared by electrolytically treating a fused mixture of carbonates of the two alkali metals and tungsten-(VI) oxide. Lattice constants, a and c, of the tetragonal crystals were estimated by the X-ray powder method. Similarity of the crystal lattice of these bronzes to that of potassium tungsten bronzes, instead of to that of sodium tungsten bronzes, suggests that the lattice constants of the sodium potassium bronzes are by far more influenced by the potassium content than by the sodium content.
Studies of the Alkaline Earth Complexes in Various Solutions. V. Calcium(II) and Strontium(II) Complexes with Carbonate Ions in 1m Sodium Chloride Media
Authors: Hasegawa Yuko , Kawashima Hiroshi , Sekine Tatsuya
Published: July 2006

The complex formation of calcium(II) and strontium(II) with carbonate ions in 1m sodium chloride media at 25°C has been determined by a liquid-liquid distribution method. The metal ions in the aqueous phase were extracted with a mixture of benzoylacetone and tributylphosphate in hexane as adduct chelate complexes. The distribution ratio was determined by radiometry as a function of the carbonate-ion concentration in the aqueous phase. The decrease in the metal distribution caused by the addition of carbonate ions to the aqueous phase has been explained in terms of the complex formation, and the stability constants have been determined from these data by a “curve-fitting” method. It has been concluded from the results that the stabilities of these complexes are about the same magnitude of those of the sulfate complexes of these metal ions and that the concentration of the carbonate complexes in usual natural waters is probably negligibly small.
Amino Acids and Peptides. I. Syntheses of p-Methoxybenzyl p-Nitrophenyl Carbonate, p-Methoxybenzyl Carbazate, and p-Methoxybenzyloxycarbonyl Amino Acids with p-Methoxybenzyl Chloroformate
Authors: S\={o}fuku Sh\={o}suke , Mizumura Mitsuo , Hagitani Akira
Published: July 2006

A new method for the syntheses of p-methoxybenzyl p-nitrophenyl carbonate, p-methoxybenzyl carbazate, and p-methoxybenzyloxycarbonyl amino acids has been devised. These compounds were obtained in satisfactory yield from sodium p-nitrophenolate, 85% hydrazine hydrate, and several amino acids with p-methoxybenzyl chloroformate prepared from anisyl alcohol and phosgene in the presence of dimethylaniline in dry ether at −5–−10°C. This direct p-methoxybenzyloxycarbonylation of amino acid with the chloroformate is more convenient than the usual Weygand method.
Study on the Binding Nature of Acridine Orange to DNA by Means of Flow Dichroism
Authors: Takesada (née Yamagami) Hiroko , Saito (née Moriguchi) Etsuko , Fujita Hitoshi , Suzuki Kenshi , Wada Akiyoshi
Published: July 2006

The binding nature of acridine orange to DNA was studied by means of equilibrium dialysis and flow dichroism with spectrophotometric analysis. The adsorption isotherm of the acridine orange-DNA system was obtained by means of equilibrium dialysis. From the experiment, the binding constant (K) and the fractional amount of the binding site to the total number of nucleotides (f) were estimated for native- and heat-denatured DNA. Under a shear gradient, the acridine orange-DNA complex showed a negative dichroism in visible region as well as in the ultraviolet region. This implies that acridine orange is oriented on DNA rather perpendicularly to its main axis, like base pairs. The magnitude of the dichroism of the complex at 500 mμ, near the visible absorption peak of acridine orange, was larger than each value of the complex and that of the DNA itself (260 mμ). The transition moment corresponding to the absorption at 500 mμ may be oriented in a more orderly manner and/or more nearly perpendicularly to the main axis of DNA than that corresponding to 260 mμ.
Studies of Peptide Antibiotics. XVIII. The Synthesis of Tyrocidine E
Authors: Mitsuyasu Nobuo , Matsuura Shuji , Waki Michinori , Ohno Motonori , Makisumi Satoru , Izumiya Nobuo
Published: July 2006

The synthesis of cyclic decapeptide, cyclo-l-phenylalanyl-d-phenylalanyl-l-asparaginyl-l-glutaminyl-l-phenylalanyl-l-valyl-l-ornithyl-l-leucyl-d-phenylalanyl-l-prolyl, which has the amino acid sequence designated as tyrocidine E by Kurahashi, and the chemical and biological properties of the synthetic product, have been described. The degree of the activity of the synthetic product toward the Gram positive microorganisms is nearly the same as that of tyrocidine A. The results indicate that the l-tyrosine residue in the molecule of tyrocidine A can be replaced by l-phenylalanine without influencing activity.
A Deuteron and Proton Magnetic Resonance Study of Ammonium Oxalate Monohydrate
Authors: Chiba Takehiko
Published: July 2006

The quadrupole spectra of deuteron magnetic resonance were observed on single crystals of (ND4)2C2O4D2O. The quadrupole coupling tensors for stationary deuterons were determined at −110°C. eqQ⁄h and η are 163.7–172.8 kHz and 0.005–0.015 for the ammonium deuterons and 213.3 kHz and 0.090 for the water deuteron. The eqQ values and principal axis directions of EFG tensors are consistent with the structure deduced from the diffraction studies with the exception that the z principal axes of D in the ammonium ion deviate appreciably from the NH directions derived from neutron diffraction. From the change in the line-width with the temperature, the rate of the C3 reorientation of ammonium ions and that of the 180° flip of water molecules were estimated at various temperatures. The ammonium-ion reorientation is found to be quite isotropic. The temperature dependence of the proton T1 and T1ρ and the deuteron T1 were measured on (NH4)2C2O4H2O and (ND4)2C2O4D2O powers. The T1 values were then compared with the calculated values, assuming ammonium reorientation. The sharp drop of the proton T1ρ with the temperature above 50°C can be interpreted as being due to the 180° flip motion of water molecules through a relaxation mechanism of “slow motion.” The rates of motion derived from the relaxation-time measurements are consistent with those estimated from the line-width change.
Metastable Solid Solution with Nepheline-type Structure in the CaO–Al2O3–SiO2 System
Authors: Yoshioka Takashi
Published: July 2006

The metastable nepheline-type solid solution in the CaO–Al2O3–SiO2 system shows the best crystal development upon devitrification on the CaAl2O4–CaAl2Si2O8 join. The crystallization occurs through the devitrification of glass at relatively low subsolidus temperatures, around 1000°C in the air. The X-ray powder diffraction patterns of the solid solution can be indexed on the basis of a hexagonal unit cell of the nepheline structure without exception. The cell parameter a of the solid solution is similar to that of nepheline, while its parameter c is smaller than that of nepheline and corresponds to that of high-temperature tridymite. When the cell parameters of the solid solution on the join are plotted against the composition, there is a break in the slope at Ca6Al12Si4O32, though the cell volume varies continuously. The nepheline-type solid solution on the join may be expressed as Ca8−(1⁄2)x\Box(1⁄2)xAl16−xSixO32, where \Box means the interstitial vacant site. The relationship between the cell parameter and the composition suggests that there should be two kinds of Ca-sites in the structure of the present solid solution, and that these kinds correspond to the alkali sites of two different sizes in the nepheline structure.
Polarographic Behaviors and Potentiostatic Determination of Kinetic Parameters for the Electrode Reaction of trans-1,2-Cyclohexanediaminetetraacetatochromate(III) Complexes
Authors: Tanaka Nobuyuki , Tomita Takeshi , Yamada Akifumi
Published: July 2006

The polarogographic behaviors of trans-1,2-cyclohexanediaminetetraacetatochromate(III) complex have been studied. The complex is reduced reversibly at the dropping mercury electrode in the solution which contains 0.4 m sodium chloride, 0.1 m acetate buffer and 2×10−6  m polyoxyethylene lauryl ether. The kinetic parameters of this oxidation-reduction process have been determined from the potentiostatic measurements at 25°C. The measured parameters are: the standard potential (E0)ms=−1.198Vvs. SCE, the standard rate constant (ks)ms=2.9×10−2 cm sec−1, the transfer coefficient for cathodic process (αc)ms=0.33 and that for anodic one (αa)ms=0.67. The Frumkin correction for the electrical double layer has been applied to these parameters and the corrected values thus obtained are: (E0)corr=−1.198Vvs. SCE, (ks)corr=−0.93 cm sec−1, (αc)corr=0.40 and (αa)corr=0.57.
The Separation of Gold, Platinum, and Palladium by Reversed-phase Partition Chromatography
Authors: Akaza Ikuko , Kiba Toshiyasu , Kiba Tomoe
Published: July 2006

For the separation of gold, platinum(IV), and palladium, and for the isolation of gold from other metals, the reversed-phase partition chromatography has been used as a column process in which TBP is adsorbed on Daiflon(polytrifluorochloroethylene moulding powder) as the stationary phase and hydrochloric acid, as the mobile phase. The separation of the above three noble metals was successfully achieved by carrying out the elution with 3–4 n HCl, and the isolation of gold was attained well of itself by virture of the fact that gold is tightly retained on the column and is only released by letting concentrated HNO3 flow through the column. The concentration and separation of gold from various solutions, such as in the presence of a large amount of iron(III) or in the presence of 19 common metals and the above three noble metals, was achieved only by allowing gold to be retained on the column and allowing ther others to flow down with a 1 n HCl eluting solution. The behavior of the three noble metals in batch extraction was also examined under the same condition as in the partition chromatography employed here; a similarity was observed between the column and the batch extraction. The principal extracted species of the noble metals might be assumed to be a hydrated and solvated ion pair, such as H(H2O)nTBP6+·HPtCl6−.
The Adsorption of 2,2′-Bipyridine and Its Ferrous Complex on the the Dropping Mercury Electrode
Authors: Sawamoto Hiromiti
Published: July 2006

The adsorption of 2,2′-bipyridine and its ferrous complex [Fe(bip)3]2+ onto the electrode has been studied both by the electrocapillary method and the impedancebridge method. Electrocapillary curves were obtained by the drop-time method. A peculiar shape was observed in the electrocapillary curve of [Fe(bip)3]2+, which was corrected for in the further thermodynamic treatment by taking into account the data obtained with an impedance bridge. It was found that 2,2′-bipyridine is adsorbed flat in the more positive region. At more negative potentials, the adsorption is also flat at low concentrations of 2,2′-bipyridine, but becomes perpendicular beyond 2×10−3  m. The [Fe-(bip)3]2+ adsorption can be accounted for by a Langmuir isotherm. However, the isotherm for 2,2′-bipyridine adsorption varies with the potential, which can be explained in terms of the change in the adsorption structure.
Reactive Species in the Explosion of Silver Acetylide. II. Reaction with Olefins
Authors: Taki Ko
Published: July 2006

The reaction of the reactive species in the explosion of silver acetylide with olefins was investigated. The main produst is acetylene. On the basis of the results of experiments on the effects of the pressure and the distance from the explosion position, the C3 and C4 products in the reaction with ethylene may be considered to be produced from a common precursor. The C4 products consist mainly of vinylacetylene and diacetylene. The formation processes of the products may consist of the decomposition of the adducts of the C2 species. The reaction with C4 olefins gives benzene, cyclopentadiene, and other products.
Polyamides and Polyureas Containing s-Triazine Rings
Authors: Yuki Yasuo , Sakurai Shoji , Kakurai Toshio , Noguchi Tatsuya
Published: July 2006

Several new aromatic diamines containing s-triazine rings were prepared by the reaction of the related dinitro-compounds prepared from biguanide derivatives and carboxylic acid chlorides. Polyamides and polyureas containing amino-s-triazine were synthesized by the polycondensation of these diamines with dicarboxylic acid chlorides and diisocyanates respectively. Their preparations and physical properties are described.
Sulfilimine. II. IR, UV and NMR Spectroscopic Studies
Authors: Tsujihara Kenji , Furukawa Naomichi , Oae Shigeru
Published: July 2006

The physical properties of several N-p-tolylsulfonylsulfilimines were studied by means of infrared, ultraviolet and NMR spectroscopic determinations. Four characteristic infrared absorption bands due to both sulfonyl and sulfilimino groups are observed and those due to both N–S(IV) and N–S(VI) stretching vibrations appear at nearly the same positions and overlap with each other. The ultraviolet spectra suggest that the sulfilimino group is not an electron donor but an electron acceptor group when conjugated with a phenyl ring and could be used to measure the pKa value of methyl-p-methoxyphenyl derivative. The NMR chemical shift of methyl protons attached to the S atom of S-methyl-S-p-tolyl derivative appears at 2.81 ppm, whereas the shifts of the corresponding sulfoxide and the sulfone groups appear at 2.69 and 3.04 ppm, respectively. From these results, it seems that the N–S(IV) bond of N-p-tolylsulfonylsulfilimine is of semipolar character while the charges on the S(IV) atom and the N atom are delocalized substantially with strong dπ conjugation into S(IV)–N–S(VI) bondings.
The Reactions of 1-Tropylazulenes with Phosphorus Pentachloride
Authors: Toda Takashi , Yamanouchi Akira
Published: July 2006

The reactions of three 1-tropylazulenes—ethyl 2-acetamido-3-(cycloheptatrien-7-yl)azulen-1-carboxylate (I), 2-chloro-1-(cycloheptatrien-7-yl)azulene (II) and ethyl 3-(cycloheptatrien-7-yl)-azulen-1-carboxylate (III)—with phosphorus pentachloride were investigated. The reactions of I and II gave ethyl 2-acetamidoazulen-1-carboxylate and 1,2,3-trichloroazulene respectively. On the other hand, III afforded ethyl 3-chloroazulen-1-carboxylate (IV) and (3-ethoxycarbonylazulen-1-yl)tropylium perchlorate (V). The thermal isomerization of III formed ca. 2:3 mixtures of ethyl 3-(cycloheptatrien-3-yl)azulen-1-carboxylate (IV) and ethyl 3-(cycloheptatrien-1-yl)azulen-1-carboxylate (VII), but not ethyl 3-(cycloheptatrien-2-yl)azulen-1-carboxylate. The treatment of the above mixtures with phosphorus pentachloride raised the yield of V; however, IV was also obtained. The sodium borohydride reduction of V gave ca. 2:3 mixtures of VI and VII.
On the Study of Various Reductions of 2-Benzoylcyclopentene-1-carboxylic Acid
Authors: Ohkata Katsuo , Hanafusa Terukiyo
Published: July 2006

It was found that the Clemmensen reduction of 2-benzoylcyclopentene-1-carboxylic acid (2a) did not give rise to 2-benzylcyclopentene-1-carboxylic acid (1), but to a mixture of cis- and trans-2-benzylcyclopentane-1-carboxylic acid (6a and 7a) contrary to the description in literature. Unsaturated acid (1) was obtained as a major product by the Wolff-Kishner-Huang-Minlon reduction of 2a accompanied with 1-carboxy-6-phenylbicyclo[3.1.0]hexane (8). The reduction of 2a with zinc dust in acetic acid and the reduction of the methyl ester (2b) by way of its thioketal were also investigated.
Cationic Arylation. III. Comparison of Phenylation of Naphthalene with Phenyl Cation and Phenyl Radical
Authors: Kobori Nobumasa , Kobayashi Michio , Minato Hiroshi
Published: July 2006

Naphthalene was phenylated with phenyl cation (from PhN2BF4) or phenyl radical (from PhN2BF4+NaNO2) in dimethyl sulfoxide. Partial rate factors for phenyl radical were somewhat larger than those reported with the phenyl radical generated from N-nitrosoacetanilide. Partial rate factors for phenylation with phenyl cation were smaller than those for free radical phenylation and those for common electrophilic substitution reactions. These small partial rate factors for phenyl cation were not compatible with the reaction scheme involving an ordinary σ-complex, and a mechanism involving a spiro cation appeared to be plausible.
A New Crystal with Kalsilite-type Structure on the CaAl2O4-SiO2 Join
Authors: Yoshioka Takashi
Published: July 2006

A new crystal phase with a kalsilite-type structure has been found in devitrified glass with compositions close to CaAl2O4 on the CaAl2O4-SiO2 join. The crystal can be synthesized as a nearly pure phase by heating the glass for 5 to 20 min at 1000°C. After prolonged heating, the crystal easily decomposes into an assemblage of the stable compounds, CaAl2O4, CaAl4O7, and Ca2Al2SiO7(gehlenite). Most of the X-ray powder diffraction lines of the kalsilite-type phase can be indexed on the basis of a hexagonal unit cell with a=5.0 Å and c=8.1 Å. In addition to these reflections, some weak ones which cannot be indexed on the basis of this unit cell are also present. The kalsilite-type phase reacts with water, resulting in heat liberation and hardening.
Magnetic Circular Dichroism of [Fe(CN)6]3−
Authors: Kobayashi Hiroshi , Shimizu Masayuki , Kaizu Youkoh
Published: July 2006

Magnetic circular dichroism (MGD) of [Fe(CN)6]3− was measured in aqueous solution and in a polyvinylalcohol film. The use of the polyvinylalcohol (PVA) film made it possible to measure the MCD and the absorption spectrum of an electrolyte such as K3[Fe(CN)6] at dry ice - methanol and liquid nitrogen temperatures, since the film was still optically transparent at lower temperatures. From a comparison between the observations at 300°K, 195°K and 77°K, the magnitude of an angular momentum due to the orbital motion of a hole in the ground state 2T2g (t2g5) was calculated to be 0.04–0.07 Bohr magneton (β). The observed reduction of the angular momentum was interpreted to be due to partial quenching of the orbital motion by the Jahn-Teller distortion, and also to the delocalization effect between the iron dπ orbital and the antibonding π molecular orbitals of the coordinating CN− ions. The B term in [Fe(CN)6]3−, which had been ignored, was predicted to be non-zero and was estimated as −2.4×10−3 β/cm−1 at the band I and 0.97×10−3 β/cm−1 at the band II.
Mössbauer Spectra of Iron Tetraphenylporphins
Authors: Kobayashi Hiroshi , Maeda Yutaka , Yanagawa Yasuo
Published: July 2006

Mössbauer spectra were measured for a series of the central iron in Fe(II)- and Fe(III) complexes of tetraphenylporphin. The electronic structure of the central iron in the complex was modified by the axial ligand field. The Mössbauer spectra assigned the most probable electronic configurations to various iron states in the iron porphins.
Photochemical Reactions of Uranyl Ions with Organic Compounds. II. The Mechanism of the Photo-Oxidation of Alcohols by Uranyl Ions
Authors: Sakuraba Shukichi , Matsushima Ryoka
Published: July 2006

Quantum yields were measured under various conditions for the photo-oxidation of aliphatic alcohols by uranyl ions in aqueous solutions and kinetic treatments were made. The measurements of uranyl fluorescence quenching by the alcohols showed that a complex formation between uranyl ions and alcohol molecules prior to the photolysis is not likely to be involved. The temperature effect on the quantum yield is strong evidence for a collisional energy transfer from the excited uranyl ions to the alcohol molecules. The relative rates of the photolysis of four isomeric butyl alcohols, and the isotope effect on the photo-reactivity by using alcohols labeled with deuterium, showed that the alcohol molecules are attacked on the α-hydrogen atom as a primary photochemical act.
Electron Spin Resonance of Oxidized ZnO at −195°C
Authors: Setaka Morio , Fujieda Shigeaki , Kwan Takao
Published: July 2006

An asymmetric ESR spectrum of ZnO at the g value of 1.96 was found to split into g=1.957 and 1.963 components at −195°C provided that ZnO was pretreated with oxygen. Temperature dependence of these two signals as well as the effect of doping Al3+ or Li+ on their intensities were investigated to qualify these signals. It was suggested that the g=1.957 signal is correlated with conduction electrons while the g=1.963 signal is ascribable to electrons trapped at interstitial zinc ions. The ZnO sample also gave rise to another signal at g=2.013 at −195°C. The signal was attributed to holes in the bulk.
Physical Chemistry of Binary Plastic Crystals. II. Dielectric Constant of the System, Carbon Tetrachloride and t-Butyl Chloride
Authors: Kotake Kayako , Nakamura Nobuo , Chihara Hideaki
Published: July 2006

Careful measurements of the dielectric constant of a binary system of t-butyl chloride and carbon tetrachloride were made in the entire composition range and in three different phases, the liquid, the fee solid, and the rhombohedral phases. The simple Debye theory applies to the liquid and the fee solid, giving an effective dipole moment of t-butyl chloride of 2.11±0.01 D whereas in the rhombohedral phase, it was 2.00±0.03 D. Molecular polarization shows no discontinuity between the vapor, the liquid, and the fee solid but there is a jump between the fee and the rhombohedral solids. The molecular rotation in the plastic rhombohedral phase is more hindered by 450 cal/mol than in the liquid or the fee phase. The 1:1 solid solution data were examined on the basis of the Onsager theory.
Titanium and Zirconium in Hydrothermally-altered Rocks from the Tateyama Jigokudani Hot Springs, Toyama, Japan
Authors: Imahashi Masayuki
Published: July 2006

Hydrothermally-altered rocks and muds collected from the Tateyama Jigokudani hot springs were analysed for titanium and zirconium. In order to estimate the acidity of the thermal waters which contributed to these altered rocks, the concentration factor of the elements relative to SiO2 was used for convenience. The titanium and zirconium contents of the alteration products are approximately equal to those of the fresh rocks. This seems to indicate that most of these elements remain in the rocks during the alteration under acidic conditions. The muds are characterized by high values of the concentration factors and the factors proved to be dependent on the acidity of the mud-suspending waters. From the relation between the concentration factors and the pH’s of the waters, we could estimate the acidities of the thermal waters which attacked the altered rocks in the earlier stages.
Complexes Coordinated by 2,2′-Bipyridine Negative Ion. I. Synthesis of Sodium 2,2′-Bipyridinetetracarbonylchromium
Authors: Kaizu Youkoh , Kobayashi Hiroshi
Published: July 2006

Bipyridinetetracarbonylchromium was reduced by sodium metal in tetrahydrofuran. The first stage product of the reduction which showed a spectrum similar to that of sodium bipyridine (Na+bipy−) was isolated. The complex was identified as Na[Cr(CO)4bipy] by elementary analysis. On the basis of the electronic absorption spectrum and the electron spin resonance, the complex formed in the reduction was concluded to be complex coordinated by mononegative ion of bipyridine and should be named sodium 2,2′-bipyridine(1−)-tetracarbonylchromium(0).
Syntheses of Organic Phosphates. II. 3-Hydroxy-2-pyridylmethyl, 6-Methyl-2-pyridylmethyl, 3-Pyridyl and 8-Quinolyl Phosphate
Authors: Murakami Yukito , Sunamoto Junzo , Sadamori Hiromi , Kondo Hiroki , Takagi Makoto
Published: July 2006

The phosphorylation of 3-hydroxy-2-pyridylmethanol and 6-methyl-2-pyridylmethanol was carried out with pyrophosphoric acid. 3-Pyridinol and 8-quinolinol were phosphorylated in pyridine by using five- to ten-fold molar amount of phosphoryl chloride at room temperature or below. The chromatographic elution of the reaction mixtures on a column of cation-exchange resin, with water as an eluent, was found to be effective for separation and purification of the products in most cases, while 8-quinolyl phosphate was obtained directly from the concentrated reaction mixture. These phosphates, with the exception of 3-hydroxy-2-pyridylmethyl phosphate, follow acid dissociation processes similar to the case of pyridylmethyl phosphates. The effect of the 3-hydroxy group in 3-hydroxy-2-pyridymethyl phosphate on its acid dissociation processes was discussed. A symmetric pyrophosphate ester was also isolated in the course of phosphorylation of 3-pyridinol.
Reaction of P-N Compounds with Alkylating Reagents such as Alkyl Benzenesulfonates and Dialkyl Sulfates
Authors: Koketsu Jugo , Ishii Yoshio
Published: July 2006

The reaction of N,N′-dialkyl-diphenylphosphinous amides (I) with alkyl benzenesulfonates (III) or dialkyl sulfates (IV) took place exothermally, giving phosphonium salts (V). When phosphonium salts (V) were heated at 100°C for 5–10 hr, asymmetric phosphine oxide (VI) and N,N′-dialkyl-benzenesulfonamides (VII) or polymeric materials were obtained. In the case of diphenyl dialkylphosphoramidites (II), no quaternization was observed at room temperature. However, diphenyl alkylphosphonates (VIII) and N,N′-dialkylbenzenesulfonamides (VII) or the same polymeric materials were obtained through intermediate phosphonium salts when the mixture was heated.
Cyclizations of Thioureas with a Hydroxy Group at the β-Position of the N-Substituent. II. Oxidation with Thionyl Chloride to Benzothiazoles
Authors: Iwakura Yoshio , Kurita Keisuke
Published: July 2006

The reaction of N′-alkyl and N-phenyl substituted thioureas with a hydroxyl group at the β-position of the N-substituent with thionyl chloride gave benzothiazole derivatives by an oxidative cyclization reaction; no other products, such as thiazolines or oxazolines, were formed. The structure was confirmed by the various spectral and chemical data.
Conformations of the Ester Group
Authors: Oki Michinori , Nakanishi Hiroshi
Published: July 2006

In some esters of formic acid which carry bulky alkyl groups (e .g, t-butyl formate, 1,1-diethylpropyl formate, and triphenylmethyl formate), the presence of s-cis conformer has been confirmed by various spectroscopic techniques. The dipole-moment measurements also support the conclusion drawn from the spectroscopic data.
Thermal Demercuration Reactions of Organomercurials
Authors: Inamoto Naoki , Yoshifuji Masaaki
Published: July 2006

Thermal demercuration reactions of organomercurials (RHgX) alone or with mercuric salts (HgY2) were performed (where R=n-butyl, s-butyl, cyclohexyl, benzyl, phenyl, and p-tolyl; X,Y=Cl, Br, CN, SCN, and OAc). Alkyl chlorides were obtained in good yields in the cases of alkylmercuric chlorides. The results in the reactions of cyclohexylmercuric halides with mercuric salts suggested the exchange reaction between them. Thermal demercuration reactions of aryl-mercurials gave the corresponding aromatic hydrocarbons as main product, and their mechanisms which involve generation of aryl radicals were discussed. General mechanisms of demercuration reaction of organomercurials alone were also discussed, and the importance of intermolecular interaction between organic group and chlorine was suggested in the cases of aliphatic organo-mercuric chlorides.
Reactions of Aziridines with Acetyl Chloride and Related Compounds
Authors: Okada Itaru , Takahama Toshio , Sudo Rokuro
Published: July 2006

When aziridines (1) were treated with acetyl compounds, such as acetyl chloride, acetic acid, acetic anhydride, and thioacetic acid, the corresponding acetamide derivatives were obtained in good yields. In the case of acetyl chloride, some derivatives of N-(2-chloroethyl)acetamide (5) were found to be unstable in the face of moisture; they were easily hydrolyzed to give N-(2-hydroxyethyl) acetamide hydrochlorides (3). The NMR spectrum of N-(2-mercaptoethyl)-N-benzylacetamide (12) was discussed.
Studies on Associated Solutions. II. Heat of Mixing of Methanol with Aliphatic Amines
Authors: Nakanishi Koichiro , Touhara Hidekazu , Watanabe Nobuatsu
Published: July 2006

The heat of mixing has been measured at 25.00°C and 45.00°C for binary mixtures of methanol with n-butylamine, diethylamine and triethylamine. A twin-type conduction calorimeter was used. All the systems exhibit large negative enthalpies of mixing, which become slightly less negative as the temperature increases. From the present results and vapor-liquid equilibrium data, the excess free energy and entropy of mixing at 25.00°C have been calculated for each system. The sign and magnitude of the excess functions were as follows: HM<TSE<GE<0 for methanol with n-butylamine and diethylamine, GE>0, TSE<HM<0 for methanol with triethylamine. These facts were interpreted in terms of steric effects and specific solvation in the hydrogen bonding between hydroxyl group and amino bases.
The Electronic Nature of Paramagnetic Oxygen Species Combined with Metal Ions at Surface and in Solution
Authors: Setaka Morio , Kwan Takao
Published: July 2006

ESR spectra of adsorbed oxygen species were investigated on cadmium, cerium and uranium oxides supported on alumina. The principal g values, gx, gy and gz of the oxygen species were computed and compared with those on the other metal oxides. It was pointed out that the principal g values observed on cerium and uranium oxides are interpretable by a peroxy-like model rather than an O2− radical. ESR spectra due to radicals formed on mixing solutions of VO2+ or UO22+ (containing Ti3+) with H2O2 were also investigated by a rapid-mixing flow technique. The g value of the radicals was very close to the isotropic one of the peroxy-like species adsorbed on the corresponding metal oxide. The electronic nature of the interaction of oxygen species with metal ions at surface and with those in solution was comparatively discussed.
Radiation Chemical Studies with Cyclotron Beams. II. The Radiolysis of an Aqueous Ferrous Ammonium Sulfate Solution with Carbon- and Nitrogen-Ion Radiations
Authors: Imamura Masashi , Matsui Masao , Karasawa Takashi
Published: July 2006

The yield of ferric ions in the radiolysis of an aqueous ferrous ammonium sulfate solution has been determined in the very high LET (linear energy transfer) range. The radiations used were ions of carbon-12 and nitrogen-14, which were accelerated by means of the IPCR cyclotron and which had energies (Es) of 31–77 MeV for C-ions and of 17–78 MeV for N-ions; the LET ranges for water were 24–46 eV/Å and 26–85 eV/Å respectively. From the plot of G(Fe3+)Es  vs.  Es, the value for G(Fe3+) at an infinite LET was found to be in the vicinity of 2.9. It has also been shown that there is a substantial difference in the instantaneous yield (Gi) between the two ion radiations of the same LET; this may be ascribed to the differences in the track structures of the heavy-ion radiations.
Fluorescence Quenching Reactions due to the Intermolecular Electron Transfer Process in Solution
Authors: Okada Tadashi , Oohari Hiroo , Mataga Noboru
Published: July 2006

Mechanisms of the intermolecular electron transfer process in the electronically excited states of solute molecules have been studied in relation to the fluorescence quenching reactions in solution, employing pyrene as a fluorescer and some aromatic amine and cyano compounds as quenchers. The quenchers showed various strengths of the quenching actions which were classified and discussed on the basis of a new theoretical model of electron transfer process in excited state. Tetracyanoethylene showed a quite strong quenching action which was interpreted in terms of a long range electron transfer from excited pyrene to tetracyanoethylene. The relation between the exciplex formation, the electron transfer reaction due to the short range interaction and that due to the long range interaction have been discussed.
Radiolysis of Aqueous Solution of Potassium Periodate
Authors: Bhattacharyya S N , Bardhan D K
Published: July 2006

Aqueous solutions of potassium periodate in neutral medium were irradiated with X-rays and with Gobalt-60 gamma rays. It was observed that the periodate on radiolysis is reduced only to iodate and no other reduction product was detected. A mechanism for the radiation induced reduction of periodate in aqueous solution is proposed and discussed. Effect of methanol on the course of radiolysis has also been studied.
The Copolymerization of Dimethallylidenepentaerythritol and Dicrotylidenepentaerythritol with Maleic Anhydride
Authors: Ouchi Tatsuro , Oiwa Masayoshi
Published: July 2006

Dimethallylidenepentaerythritol (DMAPE) and dicrotylidenepentaerythritol (DCPE) have been copolymerized with maleic anhydride (Manh), using benzoyl peroxide as an initiator. From the results of the UV spectrum concerning the rate of copolymerization, it was found that the copolymerization might proceed on the pseudo-terpolymerization of the charge transfer complex-allylidene group-Manh. The following functional group reactivity ratios were calculated at 60°C in these systems:

& DMAPE(M_1)-Manh(M_2)

& r_1cK=0.77, r_2cK=0.058

& r_1=O.05, r_2=0.025

& DCPE(M_1)-Manh(M_2)

& r_1cK=0.89,  r_2CK=0.057

& r_1=0.02, r_2=0.020
Studies of Unnatural Amino Acids and Their Peptides. IV. The Syntheses of Dl-β-(5-Cytosinyl)-α-alanine Peptides
Authors: Shimada Mitsuhisa , Takeuchi K\={o}ji , Asai Yoshiya , Kuwata Shigeru , Watanabe Hiroshi
Published: July 2006

Dl-β-(5-Cytosinyl)-α-alanine and its dipeptides with glycine were synthesized. The benzyloxycarbonylation of this amino acid afforded the α-N-substituted derivative, but all attempts to obtain the diacylated derivative were unsuccessful. The condensation of the benzyloxycarbonyl derivative with glycine ethyl ester by the carbodiimide method afforded the expected dipeptide, though the yield was low (18%); it was accompanied by a large amount of a bicyclic compound, a lactam produced by an intramolecular acylation. The ethyl ester hydrochloride of this amino acid could not be obtained in a pure state, probably because of its ready cyclization to the same lactam structure under weakly acidic conditions. This complication could be avoided by using the tertiary butyl in place of the ethyl ester. Benzyloxycarbonylglycine p-nitrophenyl ester was condensed smoothly with this ester, affording the expected dipeptide in a 53% yield. The carbodiimide method could also be used, but it was less effective.
Photoinduced Reactions. XLI. Stereochemical Course in the Photochemistry of a 2,5-Cyclohexadienone
Authors: Ogura Katsuyuki , Matsuura Teruo
Published: July 2006

Mechanism for the photochemical transformation of a 2,5-cyclohexadienone into a bicyclo[3.1.0]hex-3-en-2-one (so-called lumiketone) was discussed. Photolysis of 2,4,6-tri-t-butyl-4-methoxy-2,5-cyclohexadienone (VII) gave only one stereoisomer (VIIIa) of the corresponding lumiketones. This fact and the prediction by the Woodward-Hoffmann rule indicate that a biradical-like excited state XI with 3,5-bonding gives rise to a direct rearrangement to lumiketone Villa as shown in Path B (Scheme II).
Formation and Cycloaddition Reactions of Substituted N-Ethoxycarbonyl-1(1H)-azepine Derivatives
Authors: Sasaki Tadashi , Kanematsu Ken , Kakehi Akikazu
Published: July 2006

The formation of substituted N-ethoxycarbonyl-1(1H)-azepine derivatives is reinvestigated in the thermal reactions of benzene derivatives with ethyl azidoformate. The rate-determining step in these reactions is determined by kinetic experiments to be the decomposition of the azide. The (4+2) π cycloadducts of these azepine derivatives are obtained by thermal reactions with tetracyanoethylene (TCNE) as a dienophile. The formation of compounds 22, 23, 24, 25, 26, and 27 is confirmed by the spectral evidence.
The Synthesis of Benzoyl-l-arginine-p-nitroanilide
Authors: Nishi Norio , Tokura Seiichi , Noguchi Junzo
Published: July 2006

Benzoyl-arginine-p-nitroanilide (BAPA) is a synthetic substrate for trypsin, papain, and other enzymes, but it has not yet been prepared in the active l-form, although the preparations of Dl-form and d-form by the trypsin digestion of the Dl-form have been reported. The optically active l-BAPA was prepared by the following route; Nα-carbobenzyloxy-Nω-nitro-l-arginine-p-nitroanilide was prepared from Nα-carbobenzyloxy-Nω-nitro-l-arginine and p-nitrophenyl isocyanate, and the subsequent decarbobenzyloxylation and the benzoylation of this compound gave Nα-benzoyl-Nω-nitro-l-arginine-p-nitroanilide. The removal of the nitro group was followed by Sakakibara’s method using hydrogen fluoride. The l-BAPA shows the same melting point and the same reversal optical rotation as those of d-BAPA. When Nα-benzoyl derivatives of l-arginine were used as starting materials in the preparation of BAPA, Dl-BAPA was always obtained with complete racemization; when Nα,Nω,Nω′-tricarbobenzyloxy-l-arginme as the starting material reacted on p-nitrophenyl isocyanate, the product had no racemization, but the desired l-BAPA was not obtained because one of the carbobenzyloxy groups on the guanido group was extraordinally stable to reagents and could not be removed completely.
Photochemistry of Non-enolizable β-Diketones Containing Cyclopropane Ring in Conjugation
Authors: Okada Taiiti , Kamogawa Koiti , Kawanisi Mituyosi , Nozaki Hitosi
Published: July 2006

Irradiation of bicyclo[3.1.0]hexane-2,4-diones affords isomeric enol lactones retaining the cyclopropane ring. In contrast, photoreaction of 6,6-dimethylspiro[2.5]octane-4,8-dione in ethanol results in the formation of an isomeric benzofuran derivative and dimedone-acetaldehyde condensation product. Cleavage of the cyclopropane ring is characteristic of the behavior of the latter β-diketone.
The Cyclization of Ethyl Cyanoacetate and Salicylaldehyde or 3-Methoxysalicylaldehyde with Ketones by Means of Ammonium Acetate
Authors: Sakurai Akio , Midorikawa Hiroshi , Hashimoto Yasuo
Published: July 2006

Various substituted benz[f]isoquinolines were readily prepared by the condensation of ethyl cyanoacetate and salicylaldehyde or 3-methoxysalicylaldehyde with aliphatic ketones (acetone, diethyl ketone, methyl pentyl ketone, methyl isopentyl ketone, etc.) or aromatic ketones (acetophenone, o-hydroxyacetophenone, m-nitroacetophenone, propiophenone, etc.) in the presence of ammonium acetate. On the other hand, condensation with cyclic ketones such as cyclopentanone and cyclohexanone gave benz[f]cyclopent[c]isoquinolines and benzo[k]phenanthridines respectively.
The Synthesis of a Series of N-t-Amyloxycarbonyl-oligo-l-proline
Authors: Miyoshi Muneji , Kimura Terutoshi , Sakakibara Shumpei
Published: July 2006

A series of N-protected l-proline oligomers, the di-, tri-, tetra-, penta-, hexa- and octamer, were synthesized by conventional methods. The proline imino-group was protected by the t-amyloxycarbonyl (Aoc) group, and the carboxyl group was protected as the benzyl ester during the synthesis. These Aoc-oligoprolines were valuable in elucidating the relationship between the conformation and the degree of polymerization of the polyprolines. The Aoc-protecting group was useful in purifying the intermediates and in obtaining crystals of the final compounds.
Studies on Nylon Monolayers. I. Pressure-Area Curves for Nylon Monolayers on Water
Authors: Seimiya Toshiko
Published: July 2006

The conditions under which nylon monolayer spread on water exhibits a reproducible and well-defined F-A curve favorable for detailed investigation of the surface chemical properties of nylon were studied. For this purpose monolayers of Nylons 6 and 8 were spread from such solvents as methyl alcohol, methyl alcohol saturated with calcium chloride, aqueous solution of 90% formic acid and the mixture of phenol and benzene in 1 : 3 volume ratio. The effects of the nature of these solvents, the volume of spreading solution, surface aging and substrate pH on the properties of spread film were studied. It was found that the monolayers can be classified into two different types of film, A and B, according to the behavior of F-A curve against compression. The type A film appeared usually at the first compression of the spread film. F-A curve of A film varied according to the nature of the spreading solvent and the film was unstable. It readily underwent change to type B by being allowed to stand after the film was compressed to a certain extent, by increasing the volume of the spreading solution or merely by compressing film A to a sufficiently high surface pressure. F-A curve of type B film obtained was almost independent of the nature of the spreading solvent and repetition of compression and expansion of the film.
Ionic Dissociation. I. A Hückel Molecular-Orbital Treatment of the Dissociation of Carboxylic Acids and Several Azine Compounds
Authors: Yamabe Hiroko , Yonezawa Teijiro , Kato Hiroshi
Published: July 2006

The relationship between the pKa value and the change in the electronic energy, ΔE, in the course of the dissociation, and the electronic structure of various mono-carboxylic acids and several azine compounds are discussed on the basis of the calculation by Hückel methods for σ and π electron systems. The parallelism between the pKa and the calculated ΔE of the acids is observed. The σ electron densities of the –COOH proton and the O− lone pair, which is constituted by the released electron on the dissociation, run parallel with the pka′s. The delocalizability of the lone pair for the electrophilic reaction, and that of the proton for the nucleophilic reaction, have a linear relationship with the pka′s. Similar relations are seen in several azine compounds. Therefore, it may be said that the protonation will take place by means of the electrophilic attack at the lone pair, and that the deprotonation occurs by means of the nucleophilic attack at the proton.
The Electron Spin Resonance of the Mn2+ Ion in Aqueous Surfactant Solutions
Authors: Hasegawa Akinori , Michihara Yasuyoshi , Miura Masaji
Published: July 2006

The ESR spectrum of the Mn2+ ion in an aqueous solution of a surfactant is affected by its concentration. Sodium dodecyl sulfate and sodium decyl sulfate were employed as surfactants in this study. The linewidth of the Mn2+ ion is independent of the concentration of the surfactant in the low-concentration range, but it increases over a certain concentration range and then becomes constant. Two values of CMC were observed by measurements of the conductivity corresponding to the concentrations, where the linewidth of Mn2+ changed abruptly with the concentration of the surfactant. The linewidth broadening above the first CMC was interpreted as being due to the formation of an outer-sphere complex of the Mn2+ ion with a surfactant micelle. The interaction between the counterion and micelle was also investigated on the basis of the ESR spectra of the Mn2+ ion with regard to the effects of the kind of surfactant, the temperature, foreign electrolytes, etc.