bluuebunny/crossref_metadata_2025_split huggingface dataset:
Oxidation of Propylene over Vanadium and Molybdenum Oxide Catalysts
Authors: Wakabayashi Katsuhiko , Kamiya Yoshio 
Published: July 2006

Abstract
The oxidation of propylene with a large amount of propylene has been studied over vanadium and molecule oxide catalysts in a flow system. The relation temperature was 470°C; the partial pressure of oxygen was kept at 0.1 atm, while that of propylene was varied from 0.1 to 0.8 atm. The main oxidation products were carbon monoxide, carbon dioxide, and acrrolein. In the oxidation with a pure vanadium oxide catalyst, the yield of acrolein increased with the proplene partial pressure, and the selectivity to acrolein was about 30% at the propylene partial pressure, and the selectivity values of the selectivity to various reaction products at the contact time of 0 sec did not change even though the propylene partial pressure was changed from 0.1 to 0.8 atm. X-ray patterns of the catlyst used (free of carriers) show the presence (of V2O4 or a mixture) of V2O4and V2O3 according to the partial pressure of propylene. It is concluded that acrolein undergoes a secondary reaction more severly when a vanadium oxide catalyst is in the higher oxidative state, that is, when it is richer in V2O4. In the system of vanadium-molybedenum oxides, the three mixed catalysts, containing 10, 18 and 30 mol% moO3, acted in a similar way and raised the selectivity to acroline to some extent in coparison with a pure vanadium oxide catalyst, whatever was partial pressure of propylene. In the mixtures containing more than 50 mol% MnO3, MoO3 had a dilution effect on the catalytic activity. A pure molybenum oxide catalyst scarcely oxidized propylene at all 470°C. It has thus been found that the catalytic cativity of this system is closely related with the formation of solid solutions MoO3 in V2O5.
The Acid Strength and the Catalytic Activity of Solid Catalysts in the Oligomerization of Propylene
Authors: Misono Makoto , Yoneda Yukio 
Published: July 2006

Abstract
The reaction activities and the reaction products of the oligomerization of propylene on several acidic solid catalysts, e. g., silica-alumina, sodium-exchanged silica-alumina and some other acidic catalysts, have been investigated in a circulation system in the range of 130–300°C and 100–600 mmHg. The acid strength and the acid contents of catalysts were qualitatively measured by amine titration, using several indicators, over the range from 1.5 to −12.8 in H0 function. Correlations between the reaction activity of the oligomerization of propylene and the acid strength as well as the acid content of the catalysts were demonstrated. The activation energies, the pressure dependency of the rate, and the reaction products were correlated with the acid strength as well. The high activity of some catalysts due to very strong acid sites was deactivated by coke formation in the initial stage of the reaction process. On the basis of an analysis of the reaction products, the major reaction at the stationary stage was ascertained to be the trimerization of propylene, which seemed to occur on moderately strong acid sites. The acid types responsible for the activity were discussed by the aid of “added back water.”
Chloranilate Complexes of Iron(III) and Nickel(II)
Authors: Cabbiness Dale K , Amis Edward S 
Published: July 2006

Abstract
Nickel(II) and iron(III) have been found to complex with chloranilic acid in 1 : 1 and 1 : 2 ratios, respectively. The complexes were studied spectrophotometrically by the method of continuous variations in aqueous solutions at an ionic strength of 0.15 and at different values of pH and temperature. Formation constants and other thermodynamic properties have been determined. It is proposed that these complexes are chelates.
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

Abstract
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

Abstract
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&gt;zinc sulfate&gt;chromic sulfate&gt;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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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.