bluuebunny/crossref_metadata_2025 huggingface dataset:
An Interpretation of the Photochemical Behavior of a Dye-Reducing Agent-Oxygen System on the Basis of a Switch-over of the Primary Processes
Authors: Usui Yoshiharu , Koizumi Masao
Published: July 2006

An example is presented in which the complicated photochemical behavior of a system involving dye, a reducing agent, and oxygen is interpreted on the basis of the rate constants of the elementary reactions, which predict the change in mechanism from a D–D (or D–O) to a D–R mechanism. The dye chosen is eosine, and the reducing agent is EDTA. Investigations have been made of the quantity of oxygen consumed by the aerated aqueous dye solution, of the rate of oxidative photobleaching, and of the photochemical yield of hydrogen peroxide; the influence of the EDTA concentration on these quantities has been studied in particular. This influence was especially remarkable on the third phenomenon; the yield of hydrogen peroxide shows a sharp maximum at a certain EDTA concentration, ∼1×10−2  m for 1.0×10−3  m and 1.0×10−4  m of dye, and ∼6×10−2  m for 1.0×10−5  m of dye. To give a quantitative account of the above phenomena, the rate constants for the following elementary reactions have been determined tentatively by the flash technique:

(Remark: Graphics omitted.)

Although further evidence for the existence of D+···O2− and D+···D− would be desirable, the above data as well as those already reported by Lindqvist and by our group, are well correlated with the present results.
Alkylation of Benzene with Ethylene by the Metal Sulfate Supported on the Silica-Alumina Catalyst
Authors: Fukui Yukimasa , Takaoka Hideo , Ishii Jukichi , Hirai Kenji , Takahashi Toshiro
Published: July 2006

The vapor-phase alkylation of benzene with ethylene over the various metal sulfates supported on the silica-alumina (SA) catalysts has been studied by a flow method under a pressure of 30 kg/cm2 and within the temperature range of 230–450°C. The metal sulfate supported on the SA catalyst showed a relatively higher activity than the SA used as a carrier, and the activity of the metal sulfate as the modifier of SA is in the order of; manganous sulfate>zinc sulfate>chromic sulfate>cupric sulfate. Under the optimum conditions, in which benzene and ethylene were brought to reaction at the molar ratio of 2.5, a LHSV of benzene of 1.2 hr−1, under a pressure of 30 kg/cm2 and a reaction temperature of 300°C over the manganous sulfate supported on a SA catalyst (the weight ratio of manganese to SA is 1/10), the conversion of ethylene was 56.7% and the selectivity to ethylbenzene and diethylbenzene was 94.0%.
Molecular Orbital Calculations of Nuclear Spin Coupling Constants. I. Preliminary Results for Proton-Proton Coupling Constants
Authors: Yonezawa Teijiro , Morishima Isao , Fujii Mutsuo , Kato Hiroshi
Published: July 2006

Molecular orbital calculations of proton-proton coupling constants are made for simple hydrocarbons and some other compounds with heteroatoms using the equation proposed by Pople and Santry. In the present treatment, a molecular orbital is given by a linear combination of valence atomic orbitals. The calculations for protons separated by two and three bonds lead to positive or negative constants, nearly all of which are compatible with the experimental values.
Photoemission from Polycyclic Aromatic Crystals in the Vacuum Ultraviolet Region. II
Authors: Kochi Masakatsu , Harada Yoshiya , Inokuchi Hiroo
Published: July 2006

The external photoelectric effect of the molecular crystals in the vacuum ultraviolet region was observed. The ionization potential of tetrathiotetracene, indanthrone and perylene, as estimated by the threshold values of their spectral responses, were 4.55, 5.10 and 5.40 eV respectively. The band-gap energies, calculated on a band model, were 0.62, 0.68 and 1.72 eV respectively. These values were in fairly good agreement with those obtained from the temperature dependency measurements of their electrical resistivities. By analyzing the photocurrent-voltage relation for tetracene and pentacene, the kinetic energy distribution curves were obtained. From an analysis of those curves, it turned out that the one-electron process plays a dominant role in the emission processes and that illumination with a short-wavelength light (1200 Å—1500 Å) can excite electrons from the deeper levels of the valence band to a vacuum. The observed positions of the filled π-electron levels were almost consistent with the results obtained using the LCAO method; for tetracene the depths of lower levels in order from the uppermost one, were 1.52, 2.48, 2.96, 3.46 and 3.92 eV from the observations and 1.60, 2.34, 2.98, 3.32 and 3.89 eV from the calculations.
Equilibria in the V2O3-VO2 System at 1600°K
Authors: Katsura Takashi , Hasegawa Masahiro
Published: July 2006

Phase equilibria in the V2O3-VO2 system were established at 1600°K by varying the oxygen partial pressures from 10−13 to 10−3atm. The phases of V2O3, V3O5, V4O7, V5O9, V6O11 and VO2 are stable under these conditions. The only phases of V2O3 and V6O11 have extensive ranges of solid solution. The stability ranges of vanadium oxides with respect to the oxygen partial pressure were determined: V2O3, from 10−13 to 10−6.36atm; V3O5, from 10−6.36 to 10−4.90atm; V4O7, from 10−4.90 to 10−4.20atm; V5O9, from 10−4.20 to 10−4.04atm; and V6O11 from 10−4.04 to 10 −3.53atm, while VO2 is in equilibrium with V6O11 at the oxygen partial pressure of 10−3.53atm. The oxygen partial pressures were measured accurately by means of a solid electrolyte cell composed of (ZrO2)0.85(CaO)0.15; these pressures were then compared with the values calculated from the thermochemical data. On the basis of the equilibrium oxygen partial pressures, the standard free energies of oxidation of various vanadium oxides were calculated.
The Non-enzymatic Cleavage of Peptide Bonds. I. Deacylation of γ-Oxoacyl Amino Acids and Peptide by Hydrazines
Authors: Morishita Michiyo , Sowa Tsuneo , Sakiyama Fumio , Narita Kozo
Published: July 2006

A few γ-oxoacyl amino compounds, such as N-levuloyl-l-phenylalanine, N-(3-benzoylpropionyl)-l-phenylalanine and -l-leucyl glycine, and N-α-N-δ-dibenzoylamino-γ-oxo-l-ornithyl-l-phenylalanine, were synthesized by the conventional method for peptide synthesis. The deacylation of the acyl group with hydrazines was studied in an attempt to establish the procedure for the second step in the newly-developed principle for the non-enzymatic cleavage of the C-tryptophyl and C-histidyl peptide bonds. The quantitative release of the amino group was accomplished by heating the γ-oxoacyl amino acid or peptide with the unsubstituted hydrazine in an acid solution. In this reaction the tetrahydropyridazone derivative was formed. The mechanism of the deacylation reaction was also considered.
A Proposal for Using Mild Bases in the Preparation of Optically Pure Peptides
Authors: Sakakibara Shumpei , Itoh Masumi
Published: July 2006

Base catalyzed racemization of N-carbobenzoxy-S-benzyl-l-cysteine p-nitrophenyl ester was studied with various tertiary amines; N, N-dialkylglycine esters and N-ethylmorpholine were found to induce less racemization than triethylamine. Furthermore, these mild bases were strong enough in many cases to liberate free amino acid or peptide esters from their salts. It was also confirmed that a mixture of an amino acid or peptide ester salt and such a mild base could be used in the place of a previously prepared free ester for peptide synthesis, and practically no racemization was observed during the coupling reaction with an acylamino acid active ester. Anderson’s racemization test was also carried out by the mixed anhydride procedure with these mild bases instead of triethylamine; the mild bases were found to give better results in optical purity.
Total Cross Sections for the Scattering of Potassium by Helium, Neon, Argon, Krypton, and Xenon
Authors: Kusunoki Isao
Published: July 2006

Total cross sections for the scattering of potassium by He, Ne, Ar, Kr, and Xe have been measured in the thermal energy range. The potassium beam and the scattering gases had Maxwellian velocity distributions. The angular resolution of the apparatus was 2.62 min of arc, so that quantum mechanical calculations could be applied. If a van der Waals potential, V=−C⁄r6, is assumed for the long range intermolecular forces, the total cross section may be related to the constant, C, as follows;(Remark: Graphics omitted.), where p is a constant. In the present experiments care was taken to avoid the pumping effect of a McLeod gauge in the measurement of the pressure in the scattering chamber. The Ga0 function denned by Berkling et al. was used to derive an absolute total cross section from a measured effective total cross section. The van der Waals constants calculated from the measured total cross sections were compared with the theoretical values. The present values were about 25 percent smaller than the theoretical values for the Ar, Kr, and Xe systems. The differences for the He and Ne were considerably larger, with the theoretical values larger than the experimental by a factor of two or three.
Dielectric Relaxation and Molecular Structure. IV. Intermolecular Interaction between Dichloroethane and Benzene
Authors: Chitoku Kazuo , Higasi Keniti
Published: July 2006

Dielectric relaxation times (τ) and dipole moments (μ) of 1,2-dichloroethane were measured in non-polar solvents with following results. Solvent: benzene τ 3.69 p. sec, μ 1.80D; p-xylene τ 4.53 p. sec, μ 1.63D; carbon tetrachloride τ 2.15 p. sec, μ 1.38D; cyclo-hexane τ 2.16 p. sec, μ 1.39D; and hexane τ 1.31 p. sec, μ 1.35D. High relaxation times in aromatic solvents indicate that rotation of the polar (gauche) isomers is hindered by interaction with solvent molecules. The effect of molecular interaction may be estimated by an increase in the activation free energy of rotation which amounts to 400–540 cal/mol. The gauche molecules appear to be more stabilized than the trans molecules in the medium of aromatic solvent. Weak interaction, believed to involve hydrogen bonding, occurs in the systems of benzene + 1,2-dichloroethane and p-xylene + 1,2-dichloroethane.
The Thermal Decomposition of Acetaldehyde in the Presence of Hydrogen Bromide
Authors: Imai Naomi , Toyama Osamu
Published: July 2006

The catalytic effect of hydrogen bromide on the thermal decomposition of acetaldehyde has been studied over the temperature range from 326 to 365°C. The experimental results are similar to those previously obtained for the hydrogen chloride catalysis: the reaction is 3/2 order in the aldehyde and is independent of the hydrogen bromide pressure when the [HBr]/[CH3CHO] ratio is sufficiently high. The most probable reaction scheme to explain this order is: CH3CHO+M→CH3+CHO+M(1), CHO→CO+H(2), H+HBr→H2+Br(3), CH3+HBr→CH4+Br(4), Br+CH3CHO→HBr+CH3CO(5), CH3CO→CH3+CO(6), and Br+Br+M→Br2+M(7). The overall rate resulting from this scheme is k11⁄2k5k7−1⁄2[CH3CHO]3⁄2; the application of this rate equation to the experimental results leads to the Arrhenius expression k11⁄2k5k71⁄2=1014.65 exp-(−44000⁄RT)mole1⁄2cc1⁄2sec−1, which is consistent with the expression for k1 reported previously and with those for k5 and k7 estimated from the literature. The catalytic efficiency of hydrogen bromide is greater than that of hydrogen chloride by a factor of about forty.
Polarography of Various Cations in Acetamide. II. Studies with Nickel(II), Cobalt(II), Manganese(II) and Zinc(II) in Acetamide
Authors: Jha S K , Srivastava S N
Published: July 2006

Polarographic behaviours of Ni(II), Co(II), Mn(II) and Zn(II) have been studied in varying concentrations of acetamide in aqueous medium with KCNS as the indifferent electrolyte. Complex formation is noticed in all the cases with an irreversible wave character. αna and rate constant (kf,h°) have been calculated in the case of Ni(II), Mn(II) and Zn(II). Cobalt gives a dip. The dip is eliminated in the presence of 0.0075% Triton X-100.
Copper and Nickel Complexes of Meso and Racemic 2,3-Diaminosuccinic Acids
Authors: Yoshikawa Yuzo , Yamasaki Kazuo
Published: July 2006

The 1 : 1 and 1 : 2 complexes of copper and nickel with meso and racemic 2,3-diaminosuccinic acids were prepared, and their structures were studied by determining their magnetic moments and absorption and reflectance spectra. The 1 : 2 complexes have the following chemical compositions: Na2[Cu(m-das)2]·8H2O, Na2[Cu(r-das)2]·7\frac12H2O, Na2[Ni(m-das)2]· 4\frac12H2O and Na2[Ni(r-das)2]·7H2O, where “das” indicates a diaminosuccinate ion. In these complexes the ligand seems to be coordinated with the amino groups. The 1 : 1 complexes of both copper and nickel are coordination polymers. The reflectance spectra suggest that Cu-(m-das) might have a trans(N) and Cu(r-das), a cis(N) configuration.
The Oxygen Partial Pressure of the Magma from Mihara Volcano, O-sima, Japan
Authors: Shibata Kenji
Published: July 2006

After clarifying that the composition of the 1950–1951 lava flow of Mihara Volcano, O-sima, Japan, is completely in the liquid state above 1200°C and at oxygen partial pressures below 10−4 atm, the most probable oxygen partial pressure of the magma from Mihara Volcano was estimated to be 10−8.0 atm. On the basis of the present results as well as those available in the literature, the oxygen partial pressure of the typical tholeiitic basalt magma was deduced to be nearly 10−8 atm.
Study of Epoxy Compounds. XI. Solvent Effects in the Reaction of Benzoic Acid with Phenyl Glycidyl Ether by a Basic Catalyst
Authors: Kakiuchi Hiroshi , Endo Takeshi
Published: July 2006

The rates of reaction between benzoic acid and phenyl glycidyl ether in the presence of pyridine in toluene, nitrobenzene, various ethers, and mixed solvents as reaction solvents, are measured kinetically, and the following results obtained: (1) The rates are proportional to the concentrations of benzoic acid, phenyl glycidyl ether, and pyridine. (2) Plots of log A  vs. the concentration of benzoic acid give a linear relation in toluene-nitrobenzene, but not in nitrobenzene-dioxane. (3) The energies and entropies of the activation increase as dioxane increases in the mixed solvents, toluene-dioxane and nitrobenzene-dioxane. (4) This reaction follows the isokinetic relationship in the mixed solvents. (5) The plots of the rate constants, k3  vs. the pKb of the ethers indicate a straight-line relation. (6) Both the complex ion and the free ion participate in the reaction; the contribution of the free ion to this reaction is proportional to the dielectric constants of the solvents.
Studies of Cycloheximide-Related Compounds. III. A Novel Reaction of Aromatic Nitroketones with Aldehydes and Secondary Amines
Authors: Umezawa Sumio , Egawa Yoshiyuki
Published: July 2006

A novel reaction of aromatic nitroketones with aldehydes in the presence of a secondary amine is described. The products have been shown by degradation and infrared, NMR, and ultraviolet spectral studies to have a 2,3-dihydro-γ-pyran skeleton. The probable condensation path involves a new reaction of the Mannich type through the interaction of secondary amines with an aromatic nitroketone and a dimeric condensate of an aldehyde with an active methylene group, followed by an intramolecular dehydration to produce a 2,3-dihydro-γ-pyran ring. Mild hydrolyses of the products afford ketoaldehyde derivatives, which expectedly exhibit ring-chain isomerism, showing a cyclic hemiacetal nature. The scope of the reaction has been further defined.
On the Formation of Benzonitrile from Benzaldehyde and Ammonia. I. with Copper Catalysts
Authors: Misono Akira , Osa Tetsuo , Koda Seiichiro
Published: July 2006

The mechanism of the oxidative formation of benzonitrile from benzaldehyde with ammonia in a methanol solution catalyzed by some copper compounds is discussed, as well as the dependence of the activity on the basicity of the catalysts. On the basis of such kinetic data as the rate of nitrile formation related to the concentration of cupric hydroxide as a catalyst, the effect of the water added, and the effect of the sodium hydroxide added, benzilideneimine was confirmed to be an important intermediate. The rate of nitrile formation could be explained fairly quantitatively on the assumption that aldehyde and ammonia react to produce benzilideneimine, from which is produced the corresponding nitrile via the imine radical. Cupric hydroxide, cuprous chloride, and cupric chloride with sodium hydroxide or sodium methoxide are active catalysts, but cupric acetate and cupric chloride are not so active. This difference is found to be due to the basicity of the catalysts. Some other results are also discussed.
The Reaction of N,N′-Sulfinyl-bisdialkylamines
Authors: Mukaiyama Teruaki , Takei Hisashi , Shimizu Hideo
Published: July 2006

This paper describes reactions of N,N′-sulfinyl-bisdialkylamines (I) with alcohols, carboxylic acids and some electrophilic reagents. When I was refluxed in alcohols, corresponding dialkyl sulfites were obtained in good yields. The reaction of I with carboxylic acids gave N,N-dialkyl carboxylic amides (III), sulfur dioxide and dialkylamines. I reacts with acyl chlorides and carboxylic anhydrides to yield III and dialkylamine-Nsulfinyl chloride, and sulfur dioxide, respectively. On the other hand, I and aromatic aldehydes gave 1:1 adducts. Dialkylamino-nitriles were obtained by the subsequent treatment of the adducts with potassium cyanide.
Reaction between Diethylaluminum sec-Butoxide and n-Butyraldehyde
Authors: Saegusa Takeo , Hirota Kiwami , Hirasawa Eisaku , Fujii Hiroyasu
Published: July 2006

Reactions between diethylaluminum s-butoxide and n-butyraldehyde have been carried out at several temperatures from −65 to 40°C. The reaction mixtures were then treated with glacial acetic acid and subjected to vapor-phase chromatographic analysis (vpc). The products analyzed by vpc were methyl ethyl ketone, butanol-1, s-butyl n-butyrate, n-butyl n-butyrate, 2-ethyl-2-hexenal, and 2-ethyl-1, 3-hexanediol 1-n-butyrate. The last two compounds were formed only at reaction temperatures above 20°C, and methyl ethyl ketone was not formed below −40°C. The reaction of the ethylaluminum group with the aldehyde group was not observed. Finally, the interrelationship of the three reactions involving aluminum alkoxide and aldehyde, the Meerwein-Ponndorf-Verley reduction, the Tishchenko reaction, and the aldehyde polymerization, has been discussed.
The Rotatory Dispersion and Stereochemistry of Organic Compounds. XIV. Nitrobenzylidene Derivatives of Diethyl d-Tartrate
Authors: Tsuzuki Yojiro , Koyama Motoo , Tanabe Koko
Published: July 2006

Anomalous optical rotation has been observed not only with the ortho-nitrobenzylidene derivative of diethyl d-tartrate (Tsuzuki, Bull. Chem. Soc. Japan, 14, 35 (1939); Sci. Pap. I. P. C. Res. (Tokyo), 35, 425, 466 (1939)), but also with some acetylated ortho-nitrophenyl glycosides of the β-type (Capon et al., J. Chem. Soc., 1961, 5172; Montgomery et al., J. Am. Chem. Soc, 64. 690 (1942); Snyder et al., ibid., 75, 1758 (1953); Tsuzuki et al., Bull. Chem. Soc. Japan, 40, 1208 (1967)). To investigate this anomalous effect of the ortho-nitro group the authors have made rotatory dispersion studies on several derivatives of diethyl d-tartrate as well as its alkylidene derivatives. Of these compounds examined, the compound (I) with a nitro group in the ortho-position of the phenyl group shows a positive Cotton effect at about 340 mμ, and it has been found that the nitrophenyl group is optically active. Furthermore, in order to inquire into this anomaly the authors have observed the CD, UV and NMR spectra of these compounds, from which it is concluded that the conformations of the acetal rings of all the compounds are nearly equal, and the anomalous dispersion of the compound I at about 340 mμ, is assumed to be due to the n→π* transition of the nitro group with a slight shoulder appearing at 325 to 350 mμ. In view of these facts it is considered that the ortho-nitro group is twisted from the plane of the benzene ring caused by the steric hindrance of the bulky acetal ring.
Primary Processes in the Photoreduction of Acridine in Various Alcohols
Authors: Koizumi Masao , Ikeda Yoshinori , Yamashita Hiroshi
Published: July 2006

The effect of the addition of biacetyl on the quantum yield of photoreduction of acridine in methanol, ethanol, n- and iso-propanol has been studied under the aerated and deaerated conditions. From the analysis of the results, the quantum yields for four mechanisms ΦMS(S means that a reactive state is singlet excited states, S*, and M denotes a molecular mechanism), ΦMS (R denotes a radical mechanism), ΦMT (T indicates that a reactive state is a state other than S* and T(π–π*), most likely T(n–π*) and ΦRT have been decided, assuming that oxygen does not deactivate T(n–π*). The values are

5&for methanol, & &Φ_M^S(0.027) & &Φ_R^S(0.039) & &Φ_M^T(0.006) & &Φ_R^T(0.057)

&for ethanol, & &Φ_M^S(0.043) & &Φ_R^S(0.067) & &Φ_M^T(0) & &Φ_R^T(0.019)

&for n-propanol, & &Φ_M^S(0.030) & &Φ_R^S(0.036) & &Φ_M^T(0) & &Φ_M^T(0.022)

&for isopropanol, & &Φ_M^S(0.03) & &Φ_R^S(0.058) & &Φ_M^T(0) & &Φ_R^T(0)

The quenching constants of biacetyl on the fluorescence of acridine have been found to agree with the ones on the reaction at S* in all alcohols; the rate constants approximate diffusion controlled. In addition it has been confirmed by a flash method that biacetyl does not attack the T(π–π*) nor the semi-reduced acridine; this justifies the present method of analysis.
Phase Changes in Crystalline and Glassy-Crystalline Cyclohexanol
Authors: Adachi Keiichiro , Suga Hiroshi , Seki Syûzô
Published: July 2006

It has been known that cyclohexanol has low-temperature form (crystal-II) and high-temperature form (crystal-I) and that the supercooled crystal-I shows in its heat capacity curve an anomalous jump resembled to that associated with glass transition. In order to clarify whether this anomaly arises from relaxation phenomenon or not, we have reinvestigated the heat capacity of this substance from 14°K to 320°K and obtained the values of 8827 J/mol, 265.31°K, 1782 J/mol and 299.09°K for heat of transition, transition point, heat of fusion and melting point respectively. Comparing the ideal gas entropy of cyclohexanol calculated from thermal data and that from statisticalmechanical data, we have estimated that the residual entropy of the crystal-II is of zero and that the potential barrier of internal rotation of OH group is 7.0 kj/mol. From these results, the residual entropy of the supercooled crystal-I amounts to 4.72 J/(mol deg K). We have discussed the glass transition of this crystal and proposed a new term glassy crystal. We have also studied the heat capacity of metastable phase (crystal-III) and obtained the results 244.8°K and 8640 J/mol for transition point and heat of transition. The residual entropy of the crystal-III has determined to be zero.
Infrared Spectra of Crystalline CHCl3 and CDCl3
Authors: Kimoto Arata , Yamada Haruka
Published: July 2006

The infrared spectra for the fundamental absorption bands, ν1, ν2, ν4 and ν5, of CHCl3 and CDCl3 have been measured in polycrystalline films. For the C–H or C–D bending band a triplet has been observed in the pure crystal. The spectra of a mixed crystal (CHCl3: CDCl3) have also been studied over the entire concentration range. The space group of crystalline chloroform has been determined to be D2h16. The intensity of the band changes, going from the gas to the solid, depending on the symmetry species to which the vibrational mode belongs; the A1 bands increase in intensity, while the E bands decrease. The C–H stretching band shows an especially remarkable increase.
Manganese(II) and Mercury(II) Complexes Containing a Thio Derivative of Acetylacetone
Authors: Furuhashi Akiko , Watanuki Kunihiko , Ouchi Akira
Published: July 2006

New compounds of the type M(C5H7S2)2Cl4, where M is Mn(II) or Hg(II), were obtained by passing hydrogen chloride and hydrogen sulfide through ethanol solutions containing acetylacetone and metal chlorides. Such adducts seem to be isostructural to iron compounds, and are stable in the solid state. They seem to decompose when brought into contact with such solvents as water, methanol and dimethylformamide. Their magnetic susceptibilities show that these compounds are all bivalent. The infrared spectra and electronic spectra resemble those of the dithioacetylacetonato iron compound.
Electric Conductance and Density of Molten Salt Systems: I2+SbI3, SbBI3+SbI3, and SbCl3
Authors: Saito Kenji , Ichikawa Kazuhiko , Shimoji Mitsuo
Published: July 2006

Measurements of electric conductance as a function of temperature have been made for the pure liquids; I2, SbCl3, SbBr3 and SbI3, and the mixtures ; I2+SbI3 and SbBr3+SbI3, from 100 to 250°C. Furthermore, measurements of density by a pycnometric method as a function of temperature have also been made for these mixtures, from 100 to 300°C. The conductivities of these liquids lie in the range from 5×10−4 to 1×10−5 ohm−1 cm−1, and are about 10−4 times lower than those of alkali halide melts. In these poorly-conducting pure liquids, the molecules may be considered as constituting a solvent in which slightly dissociated ions are contained. The negative temperature coefficient of conductivity for iodine is in marked contrast to the antimony halide melts, and may be interpreted in terms of the ionic conduction and electron hopping mechanism rather than the metallic one.
Bromine to Chlorine Ratios in Igneous Rocks
Authors: Sugiura Tsutomu
Published: July 2006

Samples were decomposed by fusion with Na2O2 and benzoic acid in a Parr-bomb, then halogens were separated from other elements by distillation and determined colorimetrically; chlorine by the thiocyanate method and bromine by the rosaniline method. The chlorine and bromine contents of rocks cover a very wide range with no relation to the type of rock. The Br/Cl ratio, however, is in a relatively narrow range from 1×10−3 to 16×10−3 by weight, mostly from 1×10−3 to 6×10−3, and evidently lower than those reported by previous investigators. The average Br/Cl ratio is (3±2)×10−3, about one-seventh of the value generally accepted for igneous rocks. The halogen content of quartz and feldspar is usually so small that it was not usually determined. The Br/Cl ratio in biotite seems to be rather small and Qertainly is smaller than 3×10−3 on the average. The Br/Cl ratios in volcanic rocks are similar to those in volcanic gases for any one volcano studied.
Metal Ion-catalyzed Glycolysis of Terephthalonitrile
Authors: Ikeda Takashi , Kitabatake Michitoshi , Ito Masatomo , Noguchi Yoshitaka
Published: July 2006

The effects of various metal compounds on the glycolysis of terephthalonitrile were studied in the presence of water at 185°C. The catalytically-active species were found to be metal ions. Their catalytic activities were correlated with the acid ionization constants, pKa, of metal ions. The active catalysts were limited to the metal ions with pKa values larger than 7. The study of the reaction mechanism suggests that, while one group of metal ions accelerates the formation of glycol and hydroxyl anions, the other involves catalytic acceleration through the coordination of metal ions. The metal ions with pKa values of less than 7 showed no catalytic activities. These results were interpreted in terms of the tendency of the metal ions to form too stable coordination intermediates. Most of these metal compounds also served to inhibit the reactions. For a series of salts derived from a given metal, the catalytic activities were found to decrease with a decrease in their solubilities in water. On the other hand, metal oxides and hydroxides had high catalytic activities.
Stereochemical Studies of Monoterpene Compounds. VI. The Stereochemistry of 2-Hydroxypinocamphone and Its Reduction Products
Authors: Suga Takayuki , Shishibori Tsuyoshi , Hirata Toshifumi , Matsuura Tamon
Published: July 2006

The stereochemical structure of (+)-2-hydroxypinocamphone (II), which was obtained from (−)-α-pinene (I) by the permanganate oxidation, was examined by a combination of physicochemical methods. It was thus found that the C-2 methyl group is trans with respect to the C-6 bridge and that the preferred conformation is V having an axial hydroxyl group. In addition, the preferred conformation of cis-α-pinene glycol (IX) and trans-α-pinene glycol (X), which were produced from II by the lithium aluminum hydride reduction, was found to be IXa and Xa respectively.
Preparation of Acetylene-Alcohol Dicobalt Hexacarbonyls and Their Reactivity towards Acid
Authors: Kim Pu-Jun , Hagihara Nobue
Published: July 2006

A series of acetylene-alcohol dicobalt hexacarbonyls was prepared from acetylene-alcohols and dicobalt octacarbonyl. The reactivity towards aqueous sulfuric acid in boiling methanol was investigated. From the ethynyl carbinol complexes, R1R2C(OH)C≡CH·Co2(CO)6, trinuclear cobalt complexes, R1R2CHCH2CCo3(CO)9, were obtained accompanying the reduction of C-OH to a C-H moiety. On the other hand, from the butynediol complexes, R1R2C(OH)C≡CC(OH)R1R2·Co2(CO)6, binuclear cobalt complexes, R1R2CHC≡CCHR1R2·Co2(CO)6, or 1,1,4,4-tetraphenyl-1,3-butadiene were obtained. The structures of all these compounds have been confirmed by analytical measurements and by a study of their absorption spectra.
Effect of the Counter-Electrode Material on the Emission Spectrochemical Determination of Silicon and Manganese in Steel
Authors: Suzuki Takanori , Kambara Tomihito
Published: July 2006

The line intensities of Si and Mn appear much more strongly in the spectrochemical analysis of high-carbon low-alloy steels when a low-voltage spark is employed. Considering the change in the line intensity with the time under various excitation conditions with graphite and zinc counter-electrodes, the present authors have established an improved method for the spectrochemical determination of Si and Mn. The effect of the heat-treatment on the metallurgical structure has been investigated by means of an electron-probe microanalyzer, and the results compared with the spectrochemical data.
Studies of Poly-2-vinylpyridine. VI. Thermodynamic Data on Solutions of Poly-2-vinylpyridine in Various Solvents
Authors: Arichi Shizuo , Tanimoto Yoshio , Murata Hiromu
Published: July 2006

The viscosities of dilute solutions of several fractions of poly-2-vinylpyridine have been measured in methanol, isopropanol, chloroform, benzene, dioxane, and methyl ethyl ketone at different temperatures, ranging from 15 to 65°C. The osmotic pressures of dilute solutions of fractions of the polymer have been measured in dioxane at 10, 25, 40, and 65°C. The data have then been analysed using the theories of Flory and Fox and of Kurata and Stockmayer. The results obtained are as follows: (1) the entropy parameters, ψ1, for the solutions of poly-2-vinylpyridine in methanol and isopropanol are negative, while the critical miscibility temperatures, θ, are positive and extraordinary high; (2) ψ1 is positive and θ is negative in chloroform; (3) These parameters behave regularly in benzene and dioxane. Qualitatively the same results have also been obtained with the poly-4-vinylpyridine fraction in several solvents, including methanol and chloroform. These results show that in alcohols and chloroform the temperature coefficient of the solubility of polyvinylpyridines is negative, and indicate the presence of strong interaction between segments and solvents, probably due to hydrogen-bond formation.
Microwave Spectrum of Cyclohexanone
Authors: Ohnishi Yoshitake , Kozima Kunio
Published: July 2006

The microwave spectrum of cyclohexanone has been investigated in the frequency region from 7.7 to 23.4 Gc/sec. The R- and Q-branches for both the a- and the c-type have been assigned for the vibrationally ground state. The rotational constants obtained are A=4195.30 Mc/ sec, B=2502.57 Mc/sec, and C=1754.49 Mc/sec. From these values it can be concluded that the molecules have the chair form. The value of the component of the dipole moment |μa| is 2.74±0.03 D, and that of |μc| is 0.86±0.03 D. The value of the total dipole moment is 2.87±0.04 D, a value which is in agreement with that obtained by Debye’s method. For the structural parameters Romers’ data obtained by the electron diffraction seems to be nearly correct.
Synthesis of Chelating Agents. VI. Chelating Behavior of 1,2,3-Triaminopropanehexaacetic Acid with Divalent Metal Ions
Authors: Moriguchi Yoshiki , Miyazaki Mitsumasa , Ueno Keihei
Published: July 2006

The chelate stability constants of 1,2,3-triaminopropanehexaacetic acid (TAPHA) with alkaline earth metals, cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) were determined at 25°C and an ionic strength of 0.1 (KNO3). The stability constants of monoprotonated mono nuclear-, dinuclear- and mixed metal dinuclear chelates as well as normal mononuclear chelate were determined. The structure and chelating behavior of TAPHA in an aqueous solution were discussed by refering to those of the other complexanes of related structure. The crystalline metal chelates of TAPHA were also prepared and their structures were proposed on basis of the results of elementary analyses and infrared spectra.
The Thermal Decompositions and Mass Spectral Studies of the Cyclic Anhydrides of Some β-Sulfocarboxylic Acids
Authors: Nishitomi Katsuhiko , Nagai Toshikazu , Tokura Niichiro
Published: July 2006

The thermal decompositions of the cyclic anhydrides of β-sulfopivalic acid (III) and β-sulfoisobutyric acid (IV) have been studied. The pyrolysis of III without a solvent gave pivalic acid, isobutene, isobutane, water, and a mixture of trimers of isobutene, while the pyrolysis of IV resulted in the formation of methacrylic acid and acetone. In the case of III, the evolution of sulfur dioxide and carbon dioxide occurred mainly. On the contrary, in the case of IV, the carboxylic acid derivative was the predominant product. These results might be interpreted in terms of a decomposition mechanism in which the compound (IV) having α-hydrogen to a carbonyl group undergoes thermal decomposition via a concerted mechanism. In the case of IV, it should be noted that acetone was formed. This paper will also be concerned with the mass spectra of III and IV and with the cyclic anhydride of β-sulfopropionic acid.
Nitration of Thenyl Derivatives. II. Preparation of Three Isomeric Mononitro Derivatives of 2-Thenyl Chloride and 2-Thenyl Acetate
Authors: Sone Tyo , Matsuki Yasuo
Published: July 2006

In connection with the investigation of the products of the nitration of 2-thenyl chloride (I) and 2-thenyl acetate (II), three isomeric mononitro derivatives of I and II were prepared, and it was shown by NMR spectral study that, as in the case of I, the product obtained in the nitration of II by nitric acid in acetic anhydride consisted of all three isomeric mononitro derivatives. The isomer distribution of the mononitro derivatives of II, as determined by infrared spectroscopy, indicated 77% of the 5-, 9% of the 4-, and 14% of the 3-nitro isomer.
Intramolecular Energy Transfer in Europium Chelates Due to Excitation of the Triplet State
Authors: Matsuda Yoshihisa , Makishima Shoji , Shionoya Shigeo
Published: July 2006

The purpose of this paper is to clarify whether intramolecular energy transfer in europium chelates occurs via the triplet state of the ligand. It is attempted to excite the triplet state of europium dibenzoylmethide (EuD) by utilizing intermolecular triplet-triplet energy transfer from lanthanum dibenzoylmethide (LaD). In mixed solutions of EuD and LaD, the intensity and decay time of the ligand phosphorescence of LaD decreases with increasing molar fraction of EuD at liquid nitrogen temperature. Nearly in proportion to this, the intensity of the europium emission of EuD is enhanced, veryfying the occurrence of energy transfer from LaD to EuD. This fact is taken as clear evidence that intramolecular energy transfer takes place via the triplet state.
Group Interactions in Polyelectrolytes. I. Amination Kinetics of Chloromethylated Polystyrene
Authors: Kawabe Hiroshi , Yanagita Masaya
Published: July 2006

Chloromethylated polystyrene is quantitatively aminated by n-butylamine or n-dibutylamine in dioxane, but the plot of the logarithmic term in the simple second-order rate equation against the time is not represented by a single straight line, but is divided into two lines which intersect nearly at the half-amination point. These results are interpreted in terms of the step-by-step amination resulting from the steric effect of the already-aminated neighbors which have bulky alkyl groups. By assuming two distinct reactivities of chloromethyl groups according to their neighboring environment, rate equations for two separate steps are derived; these equations give k1, the rate constant in the first step, and k2, that in the second step. In the presence of a large excess of amine, the over-all kinetics can be expressed by:

dx/dt=[ab/(2k_1-k_2)][2k_1-(k_2)e^-2k_1at+k_1-k_2e^-k_2^at],

where x is the concentration of chloride ions at time t; a is the initial concentration of amine, and b, that of the chloromethyl group. The equation is found to be substantially valid for the values of k1 and k2 computed by the equations for the individual steps.
Studies on the Delayed Fluorescence by Means of a Flash Technique
Authors: Kikuchi Koichi , Kokubun Hiroshi , Koizumi Masao
Published: July 2006

It has been shown that the delayed and normal fluorescence can be measured accurately by a usual flash apparatus. Such measurements, combined with that of T–T absorption, have enlarged the potentiality of a flash technique to a large extent. As an example, a simple method of differentiation between E-type and P-type delayed fluorescence has been presented. Detailed studies have been made on the T–T annihilation process of anthracene (A) and the probability for Process AT+AT→A+A*, has been decided. The value obtained is 0.077±0.005. E-Type delayed fluorescence of eosine and proflavine have been studied and the value of kt·φST (kt, the rate constant of Process, T\ightharpoonupS*; φST, the probability of the intersystem crossing) have been evaluated, to be 3.36 and 2.78 sec−1 respectively. Some advantages of the present method over the sector method have been discussed.
The Preparation of Optically Active Trimethylcyclododecatriene by the Resolution of Racemic Oligomers and the Asymmetric Oligomerization
Authors: Furukawa Junji , Kakuzen Tsuneo , Morikawa Hiroyuki , Yamamoto Ryuzo , Okuno Osamu
Published: July 2006

Trimethylcyclododecatriene was prepared by the oligomerization of pentadiene, using the diethylaluminum chloride-titanium tetrabutoxide system as a catalyst. The resulting oligomer was fractionated by vapor-phase chromatography into geometrical (cis and trans) and structural (head-to-tail and head-to-head) isomers with respect to the pentadiene units involved. The structures of these isomers were proposed on the basis of infrared and NMR spectra of the oligomers and their hydrogenated products. The results of the oxidative degradation of the oligomers were compatible with the proposed structures. Further, the existence of stereoisomers was shown by resolution and asymmetric oligomerization. The resolution of d- and l-enantiomers was carried out through the asymmetric hydroboration of the oligomers, while the asymmetric oligomerization was achieved using the titanium menthoxide-diethylaluminum chloride system as a catalyst.
Anomalous Effect of the Concentration of Metal-salt Catalysts in the Liquid-phase Oxidation of p-Xylene and Toluene
Authors: Kagami Kanekichi
Published: July 2006

By studying the relation between the concentration and the oxidation activity of various metal catalysts, mostly naphthenates, oleates, linoleates, and caprates of manganese, cobalt, and nickel salts, as well as mixed catalysts of two kinds, it has been established that, in general, there is an anomalous effect of the catalyst concentration-namely, the catalytic activity disappears above a certain point in the concentration of the catalyst. The anomalous concentration effect of a catalyst is observed in the oxidation of toluene and p-xylene with all the catalysts, but chromium naphthenate is a lone exception in the oxidation of p-xylene. It has been shown that the anomalous effect is due to the association of the catalyst in the hydrocarbon solvent to be oxidised, and that the associated catalyst does not act to promote oxidation. The association is reversible, being dependent on the concentration of the catalyst, so the anomalous concentration effect of a catalyst disappears on dilution.
Studies of the Organic Reactions of Metal Carbonyls. XIII. The Reduction of Olefin Oxides with Potassium Iron Carbonylates
Authors: Takegami Yoshinobu , Watanabe Yoshihisa , Mitsudo Takeaki , Kanaya Isao , Masada Hiromitsu
Published: July 2006

The reaction between potassium iron carbonylates (KHFe(CO)4, K2Fe(CO)4, and K2Fe2(CO)8) and olefin oxides has been studied. Styrene oxide reacts readily with these carbonylates and with carbon monoxide under an atmospheric pressure and at 30°C. As the reaction products, styrene, ethylbenzene, and α- and β-phenylethyl alcohol are obtained. The major product is styrene or β-phenylethyl alcohol for the reaction of K2Fe(CO)4 or KHFe(CO)4 and K2Fe2(CO)8 respectively. The effects of solvents and additives are examined. Further, propylene oxide and epichlorohydrin are found to react with K2Fe(CO)4 and carbon monoxide to give not only carbonylated products, but also propylene. The results indicate that olefin oxides are generally reduced with K2Fe(CO)4 and carbon monoxide to give the corresponding olefins and carbon dioxide.

(Remark: Graphics omitted.)
Reactions of Dimethylaniline with Some Resonance-stabilized Radicals
Authors: Okazaki Renji , Inamoto Naoki
Published: July 2006

Reactions of dimethylaniline with some resonance-stabilized radicals were studied. 2-Cyano-2-propyl radicals and 2-methoxycarbonyl-2-propyl radicals reacted to give N-methyl-N-(3,4-dicyano-3,4-dimethylpentyl) aniline and the corresponding 3,4-dimethoxycarbonyl derivative, respectively, while benzyl radicals and α-methoxycarbonylbenzyl radicals did not give reaction products with dimethylaniline. Mechanism of these reactions was proposed and it was pointed out that electron transfer from dimethylaniline to radicals was an important stage in these reactions.
Analysis of Vapor Pressure of Some Molecular Crystals
Authors: Chihara Hideaki , Nakamura Nobuo
Published: July 2006

Vapor pressure equations of the form logPTn⁄2=a⁄T+b were derived, using high temperature Thirring expansion, which are applicable to crystals of polyatomic molecules. The exponent n is determined by the type of motion of molecules in the crystal, libration or rotation. If combined with the heat capacity data, the method of analysis may be used to derive such vibrational propoerties as static energy, zero point energy, geometric mean frequency, and molecular libration frequency. Examples of the analysis of existing vapor pressure data are given for solid iodine, iodine monochloride, and high temperature modifications of nitrogen, hydrogen chloride, and methane.
The Crystal Structure of the 1 : 1 Complex of 1,2,4,5-Tetracyanobenzene and Hexamethylbenzene
Authors: Niimura Nobuo , Ohashi Yuji , Saito Yoshihiko
Published: July 2006

The crystal structure of the 1 : 1 complex formed between hexamethylbenzene and 1,2,4,5-tetracyanobenzene has been determined by X-rays. The crystal is monoclinic, with two formula units of the complex in a cell of dimensions ; a=15.07, b=8.92, c=7.41 Å and β=104.9°. The space group is P21⁄n. The structure was deduced from a three-dimensional Patterson synthesis, and refined by block-diagonal least-squares method. The constituent molecules are stacked alternately in infinite columns along the c-axis. The relative configuration of the donor and acceptor molecules is consistent with the theoretical calculation.
Cationic Effect on the Polarographic Reduction of Nickel(II) in Acetonitrile
Authors: Ikeda Shigero , Itabashi Eiki
Published: July 2006

The polarographie behavior of nickel(II) acetate salts dissolved in acetonitrile solvent containing small quantities of acetic acid has been investigated in various natures and concentrations of supporting electrolytes. A single reduction wave is observed in the solutions of lithium perchlorate or sodium perchlorate. The limiting current has an intermediate nature of both diffusion- and kinetic controlled polarographic current. A double wave, on the other hand, is observed in the solutions of tetraalkylammonium perchlorate supporting electrolyte such as (CH3)4NClO4, (C2H5)4NClO4 or (n-C4H9)4NClO4. The limiting current of the first step exhibits an intermediate nature of both diffusion and kinetic currents, and that of the second step is kinetic in nature. The effect of the nature and concentration of electrolyte on the visible absorption spectra of acetatonickel(II) complexes in acetonitrile containing small quantities of acetic acid are also discussed. On the basis of evidence, a mechanism which involves a substitution reaction of acetatonickel(II) complexes with the supporting electrolytes is proposed. The substitution reaction in tetraalkylammonium perchlorate solutions is thought to be the rate-determining step. The first step of a double wave is also thought to be due to the inhibition of charge transfer process by the weakly absorption of tetraalkylammonium cations of supporting electrolytes on the DME.
Organic Syntheses by Means of Noble Metal Compounds. XXXVII. Carbonylation of Allene-Palladium Chloride Complexes
Authors: Susuki Tosaku , Tsuji Jiro
Published: July 2006

The reaction of allene with palladium chloride and a carboxylate anion gave di-μ-chloro-bis(2-acyloxy-π-allyl) dipalladium which was converted into an acetoacetate by carbonylation. Carbonylation of allene in ethanol in the presence of palladium chloride produced ethyl itaconate. The carbonylation of di-μ-chloro-bis(2-chloro-π-allyl) dipalladium in ethanol formed 3-chloro-3-butenoate. 4-Hydroxy-3,4-dimethyl-2-pentenoic acid γ-lactone, 3-isopropylideneglutarate and 3-(ethoxycarbonylmethyl)-4-methyl-3-hexenedioate were isolated by the carbonylation of di-μ-chloro-bis[2-(1-(chloromethyl)vinyl)-π-allyl] dipalladium. The mechanisms of these reactions are discussed.
Hydrogen Produced by the Hot-Atom-Process in the Radiolysis of Ethane
Authors: Inoue Masao , Uno Taiko , Sato Shin , Shida Shoji
Published: July 2006

The mechanism of the formation of “molecular” hydrogen in the ethane radiolysis at 300 Torr has been studied with ethane-ethane-d6-ethylene mixtures. The G-value of the hydrogen has been found to be 3.3. The addition of electron and positive ion scavengers scarcely affected the formation of the hydrogen at all. From the isotopic composition of the hydrogen, it was demonstrated that most of the hydrogen is formed by molecular detachment from the ethane molecule, while the rest is formed by the abstraction of a hydrogen atom from the ethane molecule by a hot hydrogen atom, the G-value being estimated to be 0.6.
Syntheses of trans-Isoflavan-4-ols
Authors: Yamaguchi Shozo , Ito Shoei , Suzuki Ikuko , Inoue Naoto
Published: July 2006

The reaction of nitrous acid and three 4-aminoisoflavan hydrochlorides (III, IV, and V) obtained by the catalytic hydrogenation of isoflavanone oximes, and the hydroboration of three isoflavenes (XII, XIII, and VIII), were investigated in the hope of finding a general method of synthesizing trans-isoflavan-4-ols. The reaction of III and IV with nitrous acid afforded the corresponding trans-4-ols, though in a poor yield, but that of V produced no expected compound, the corresponding isoflavene (VIII) being obtained instead. The hydroboration of XII, XIII, and VIII afforded the corresponding trans alcohols (VI, VII, and XIV) in good yields. In addition, it became clear that 4-aminoisoflavans obtained by the catalytic reduction of the oximino compounds possess the 3,4-cis configuration.