bluuebunny/crossref_metadata_2025 huggingface dataset:
An NMR Study of Proton Exchange in Alcohols. I. Oxygen Effects in Methanol
Authors: Fujiwara Shizuo , Fujiwara Yuzuru , Nagai Makoto
Published: July 2006

Molecular interactions between oxygen and organic molecules are investigated in detail. It was confirmed that the broadening of spectral lines due to oxygen is appreciable only with hydroxyl protons. This effect is attributed to the enhancement of the proton exchange of OH groups by oxygen. Detailed investigation was made with methanol-oxygen system. In relation with this, a new method is proposed which makes the measurement of heat of dissolution of oxygen in methanol possible.
Studies of the Formation of Condensed Phosphates Containing Alkyl-groups
Authors: Ueda Shiro , Tada Mitsuyasu
Published: July 2006

Alkyl ammonium polyphosphate (AAPP) was prepared readily by a thermal reaction of alkyl (ethyl, n-propyl, n-butyl) dihydrogen phosphate and urea at temperatures ranging from 120°C to 200°C. At the same time, a small amount of cyanuric acid was obtained as a by-product. 1) AAPP was confirmed, from a study of the data of infrared spectroscopy, paper chromato-graphy and chemical analysis, to have a long-chain structure possessing P–O–P linkage. The three types of AAPP were of almost the same form, according to the X-ray diffraction patterns. 2) AAPP was more or less hygroscopic, although the hygroscopicity of AAPP decreased with an increase in the carbon number of the alkyl group. 3) AAPP is reasonably stable, keeping a P–O–P linkage even upon degradation in an acidic aqueous solution.
Studies of Scandium in Various Solutions. I. An Ion-Exchange Study of Scandium(III) Chloride and Nitrate Complexes
Authors: Sekine Tatsuya , Hasegawa Yuko
Published: July 2006

The complex formation of scandium(III) with chloride and nitrate ions has been investigated at 25°C. Scandium-46 was employed in conjunction with a cation-exchange resin (Dowex 50W X-12, 100–200 mesh) in the H+-form and the ionic strength was maintained at 4.0 m with perchloric acid. The stability constants have been obtained graphically by a curve-fitting method and the following results were obtained.

(Remark: Graphics omitted.)
A Spectrophotometric Determination of Iron(III) with ω-Amino acetophenone-N, N-diacetic Acid Oxime
Authors: Ando Takeshi , Ueno Keihei
Published: July 2006

The oximes of aminoacetone-N, N-diacetic acid, ω-aminoacetophenone-N, N-diacetic acid, p-bromo-ω-aminoacetophenone-N, N-diacetic acid and 2-glycylthiophene-N, N-diacetic acid have been synthesized as the colorimetric reagents for iron(III). The most favourable result was obtained with the oxime of ω-aminoacetophenone-N, N-diacetic acid, which forms a stable orange red chelate with iron(III), showing an absorption maximum at 420 mμ. With the use of this reagent, 0–25 p. p. m. of iron(III) can be determined at pH 5.5. It should be noticed that this reagent is almost specific for iron (III); serious interferences were only observed for copper (II), vanadate, fluoride and phosphate ions.
The Chemical Equilibrium of the 2H2S+SO2=3S+2H2O Reaction in Solfataras of the Nasudake Volcano
Authors: Mizutani Yoshihiko , Sugiura Tsutomu
Published: July 2006

The stability of native sulfur in solfataras depends upon the temperature, the pressure, and the chemical composition of the solfataric gases with which native sulfur is in equilibrium. The equilibrium constant of the 2H2S+SO2=3S(s,1)+2H2O reaction may be expressed as:

K=\fracX2H2OX2H2SXSO2P,

where X is the mole fraction of the gaseous components in the system and where P is the total pressure on the system. By the use of this relationship, the equilibrium temperature of natural solfataric gases with respect to the reaction may be estimated, provided the theoretical value of K, the chemical composition, and the pressure of natural solfataric gases are known. The attainment of chemical equilibrium of the reaction in solfataric gases of the Nasudake Volcano has been examined by comparing the estimated equilibrium temperature with the observed outlet temperature of the solfataras. The results indicate that the native sulfur occurring in the solfataras is approximately in equilibrium with the solfataric gases. On this basis, an attempt has also been made to explain the behavior of hydrogen sulfide and sulfur dioxide in solfataric gases.
Preparation of cis- and trans-Dichlorobis(ethylenediamine)-Iridium(III) Chlorides
Authors: Kida Sigeo
Published: July 2006

Potassium tetrachloro(ethylenediamine)iridate(III) and cis-dichlorobis(ethylenediamine) iridium(III) chloride were obtained by the reaction of iridium(III) chloride and ethylenediamine in a weakly acid aqueous solution. The condition for the formation of each compound depends on the mole ratio of iridium to ethylenediamine and pH of the solution. Trans-dichlorobis(ethylenediamine)iridium(III)chloride was prepared from potassium tetrachloro(ethylenediamine)iridate(III) and ethylenediamine.

The geometrical configurations of the two isomers were determined by infrared spectra, and checked by ultraviolet spectra.
The Direct Introduction of an Ethoxycarbonyl Group by the Photolysis of Some Substituted Formates in Solution
Authors: Shigemitsu Yasuo , Tominaga Tamotsu , Shimodaira Takashi , Odaira Yoshinobu , Tsutsumi Shigeru
Published: July 2006

The direct introduction of an ethoxycarbonyl group by the photolysis of various substituted formates (RCO2C2H5) was carried out. Both ethyl cyanoformate and ethyl chloroformate effectively underwent ethoxycarbonylation by a hydrogen-donating solvent such as cyclohexane, with the yields of 19% and 15%, respectively. On the other hand, the photolysis of ethyl acetate, diethyl carbonate, and ethyl carbamate gives mainly carbinols and carbon monoxide instead of ethyl carboxylate. On the basis of these results, the effects of the substituent in the formate on the ethoxycarbonylation were considered. First, the electronic effect of the substituent R has an influence on the position of the bond fission of the formate. Cyano and chloro groups, which are the electron-withdrawing substituents, weaken the R-carbon bond in the formates. Second, the ability of the hydrogen abstraction of the radical R produced by the photolysis of the formate is very important in the ethoxycarbonylation. Thus, it is clear that there is a relationship between the electron affinity of the radical R and the yield of the ethyl carboxylate.
The Reaction of N-Acylurethans with Phenyl Glycidyl Ether Accompanying Acyl Migration
Authors: Iwakura Yoshio , Izawa Shin-ichi , Hayano Fusakazu
Published: July 2006

N-Acylethylurethans reacted with phenyl glycidyl ether to produce 3-acyl-5-phenoxymethyl-2-oxazolidones, 5-phenoxymethyl-2-oxazolidone and N-(2-acyloxy-3-phenoxypropyl)ethylurethans. The reaction mechanism involving acyl migration was discussed.
2-Oxazolidones from Glycidyl Ether Reactions with Acid Amides
Authors: Iwakura Yoshio , Izawa Shin-ichi
Published: July 2006

The reaction between acid amides and aryl glycidyl ethers was carried out using tertiary amine as the catalyst. 2-Oxazolidone derivatives were obtained by the reaction of trichloroacetanilide or trifluoroacetanilide with aryl glycidyl ether. Acyl migration occurred in the reaction of acetanilide with phenyl glycidyl ether.
The Solvent Effect on the Rates of Autoxidation of o-Cresol
Authors: Ogata Yoshiro , Morimoto Takashi
Published: July 2006

The effects of alcohols, carbonyl compounds and dimethyl sulfoxide on the pyridine-cuprous chloride-catalyzed autoxidation of o-cresol in benzene have been studied kinetically by estimating the consumption of oxygen. The rate is first-order in the concentration of o-cresol and one-half order in the partial pressure of oxygen at constant concentrations of pyridine and cuprous chloride in a solvent of methanol-benzene (20 : 80 in vol.). The reaction in a benzene solution is retarded by the addition of below 0.1 vol.%, methanol or ethanol; having passed through a minimum at ca. 0.1 vol.%, it is accelerated by the addition of alcohol more than 0.1 vol.%. The reaction in a benzene solution is retarded by the addition of carbonyl compounds. A probable mechanism which explains these solvent effects is discussed.
The Synthesis of an Etiojervane Analog of Progesterone
Authors: Masamune Tadashi , Orito Kazuhiko , Murai Akio
Published: July 2006

N-Acetyl-22, 27-iminojerva-5, 12-diene-3β, 23α-diol-11-one, prepared from jervine by Masamune et al. (J. Org. Chem., 29, 2282 (1964)), was submitted to a Birch reduction and then to a modified Wolff-Kishner reduction to yield 22, 27-iminojerv-5-ene-3β, 23α-diol. The compound was then degraded, according to the procedure by Johnson et al. (Tetrahedron Letters, 1963, 545), to a methyl ketone, which was then further oxidized by the Oppenauer method to give 17α-ethyletiojerv-4-ene-3, 20-dione.
The Chemistry of Polyazanes. VI. The Oxidation of ω, ω′-Dibenzoylcarbohydrazide
Authors: Minato Hiroshi , Hisada Ryuki , Tanaka Mitsugu
Published: July 2006

ω, ω′-Dibenzoylcarbohydrazide (DBC) was oxidized with sodium hypochlorite in an aqueous ethanolic solution at −70°C. At first the solution had a deep red color, but it gradually faded away. The products of the reaction isolated were benzoic acid, ethyl benzoate, carbon dioxide, 2-phenyl-1, 3, 4-oxadiazol-5-one, and N,N′-dibenzoylhydrazine. Then, DBG was oxidized with hypochlorous acid, the products of this reaction were not very different from those obtained with sodium hypochlorite. A plausible mechanism was presented, which assumed the formation of bis(benzoylimino)urea, which was then decomposed heterolytically by the nucleophilic attack of ethanol and water molecules.
Kinetic Studies of Ammonia Oxidation in Shock Waves. III. The Radiation of Excited OH Radicals
Authors: Takeyama Tetsu , Miyama Hajime
Published: July 2006

Mixtures of ammonia and oxygen in argon were heated by reflected shock waves to temperatures between 1600 and 2100°K, and the ultraviolet radiation from OH(2Σ+) was observed by means of monochromator and a photomultiplier. The radiation profiles showed two types of radiation: a strong spike which appeared after an induction period, and a weak and constant-level emission, which followed the spike and persisted for up to 500 μsec. The former emission was observed also in the oxidation of hydrogen, methane, and acetylene, but the latter emission was observed only in the oxidation of methane and acetylene. The temperature coefficients of the intensities of the latter emission divided by the sum of spectral emissivities were found, for the oxidation of ammonia, not large enough to be explained by the thermal excitation of the ground-state OH(2π) to the 2Σ+ state. Possible reaction processes for this chemiluminescence were proposed to explain the experimental results.
The Orientation Overgrowth of Metal-phthalocyanines on the Surface of Single Crystals. II. Vacuum-condensed Films of Copper-phthalocyanine on Alkali Halides
Authors: Ashida Michio
Published: July 2006

Cleaved faces of KCl, KBr and NaCl crystals were used as substrates. When copper-phthalocyanine is vacuum-condensed onto either KCl or KBr, the films on it take a standing b-axis orientation, which shows a C4v symmetry. The major planes of symmetry coincide with those of KCl and KBr. The crystals on KBr show an azimuthal angular shift of about +12° or –12° in respect to the major symmetry axes, [010] and [100], of the substrate crystal. When the films have the standing b-axis orientation, the planar molecule in the crystal comes into parallel contact with the cleavage face of the substrate. It may be presumed that the bridge nitrogen atoms in a phthalocyanine molecule are placed on the potassium ions in the (001) planes of KCl and KBr. The films on KCl and KBr are composed of finely-divided rectangular crystals and dendrites; the former are concentrated at steps on the cleavage face to produce a decorative pattern, while the latter appear on the smooth surface. The formation in various types of crystals are interpreted in terms of the rate of nucleation and growth. The films vacuum-condensed onto NaCl are composed of laminar crystals which have a random orientation.
The Physical Properties and Crystal Structure of 2-Bromo-1,1,1-trichloro-2-methylpropane
Authors: Koide Tsutomu , Oda Tsutomu , Washio Osamu , Fujita Kazuo
Published: July 2006

2-Bromo-1,1,1-trichloro-2-methylpropane gives a plastic crystal, named by Timmermans (J. Chim. Phys., 35, 331 (1938)), which is optically isotropic and which has a density of 1.97 g./cc. at 25°C. The X-ray data can be interpreted with a body-centered cubic lattice, with 7.42 Å for the unit cell length containing two molecules. The symmetry interpretation gives a crystal structure of a disordered orientation of molecules. It was found, by means of optical measurements and differential thermal analysis, that there is a phase transition at about −62°C, below which the crystal is in a lower symmetry.
Szilard-Chalmers Reaction of Anionic Cobalt Complex Ions on Ion-Exchange Resins
Authors: Matsuura Tatsuo , Hashimoto Tetsuo
Published: July 2006

The recoiling behavior of [Co(C2O4)3]3−, [Co(NO2)6]3− and [Co(CN)6]3− ions on in anion-exchanger was studied both by the dynamic and the static methods under various conditions. As the stability of the complex decreases, the separable yield increased as a general trend, and the effectiveness of the dynamic method in obtaining higher yield than the static method was clearly demonstrated. On the other hand, specific activity increased with increasing stability of the complex, i. e., with decreasing G values. The increase of pH generally decreased the separable yield and increased the specific activity. The effects of mesh size of resin and preirradiation by gamma rays were also studied. Since the observed tendency that the separable yield decreased with increasing stability constant of the complex ion seems to be a general one, a theoretical interpretation for this relationship was attempted.
Stability Constants of Uranyl Chelates with Nuclear-Substituted Salicylic Acids
Authors: Rao J Mohan , Seshaiah U V
Published: July 2006

The formation of an orange-red coloured water soluble chelate between uranyl ion an p-aminosalicylic acid with maximum absorption at 460 mμ is reported. The colour of the complex is fairly stable and attains maximum intensity at a pH 4.5. The composition of the complex has been evaluated by Job’s and mole ratio methods employing absorbance data and has been found to be 1 : 1 with respect to metal and ligand. The stability constants of the uranyl chelates of certain nuclear substituted salicylic acids, such as, 3-nitrosalicylic, 5-sulpho-salicylic, β-resorcylic and p-aminosalicylic acids have been determined and the validity of the linear relationship between ligand basicity and the metal chelate stability studied. Based on pH and adsorption studies, tentative structures for the above uranyl chelates have also been proposed.
The Effects of the Temperature on the γ-Radiation-Induced Polymerization of Ethylene
Authors: Machi Sueo , Hagiwara Miyuki , Gotoda Masao , Kagiya Tsutomu
Published: July 2006

The gamma-radiation-induced polymerization of ethylene was carried out/over the wide range of temperature from 30 to 200°C at pressure ranging from 100 to 400kg./cm2 and at dose rates from 2×103 to 4×105 rad./hr. It was shown that the rate of polymerization is rapidly accelerated at 30°C, that the degree of acceleration decreases with an increase in the reaction temperature, and that above 100°C the rate is independent of the time. It was correspondingly shown that the molecular weight of the polymer increases with the reaction time, at 30°C, that its increment for a unit of time decreases with an increase in the temperature, and that the molecular weight is independent of the time above 100°C. By means of a kinetical discussion it was concluded that the rate of the termination reaction, which is almost eliminated at 30°C, increases with the temperature and attains a value comparable to that of initiation above 100°C. The dose rate exponents of the polymerization rate and molecular weight were shown to vary with the reaction temperature. Namely, the exponents were evaluated as 0.9 and 0 at 30°C, 0.8 and −0.1 at 100°C, and 0.7 and −0.2 at 140 and 200°C, for the polymerization rate and the molecular weight respectively. It was assumed from these high exponents that the termination may occur above 100°C in a first-order reaction to a considerable extent. Under a constant pressure, the polymer yield was shown to decrease with the temperature from 30 to 60–80°C, and then to increase at high temperatures from 80 to 200°C. On the other hand, the molecular weight of the polymer simply decreases with the temperature from 30 to 200°C. The chain transfer reaction is considered to be almost negligible at 30–70°C. The number of polymer chains for a constant reaction time and monomer concentration is independent of the temperature from 30 to 70°C, while it increases with the temperature from 70 to 200°C. The effects of pressure on the polymer yield and molecular weight were also investigated at 140°C.
Syntheses of Isomeric Methylpseudoionones and Isomeric Pseudoionones by Means of the Wittig Reaction
Authors: Sasaki Kazuhiro
Published: July 2006

Four isomeric methylpseudoionones and two isomeric pseudoionones were separately synthesized by the Wittig reaction of citral a or citral b with the corresponding phosphonates. Two isomeric pseudoionones were also synthesized by the Wittig reaction of citral a or citral b with 2-oxopro-pylidenetriphenylphosphorane. The configurations and the conformations of the dienone systems in four methylpseudoionones and two pseudoionones were discussed on the basis of the infrared and ultraviolet absorption data.
Studies of Poly-β-benzyl-l-aspartate Helix. I. The Synthesis and Rotatory Dispersion of Copolymers of β-p-Methyl, Chloro, Cyano, or Nitrobenzyl-l-aspartate with β-Benzyl-l-aspartate
Authors: Hashimoto Masahisa , Aritomi Jiro
Published: July 2006

β-p-Methyl, chloro, cyano and nitrobenzyl-l-aspartates were synthesized, and the respective homopolymers and copolymers of these β-(p-substituted benzyl)-l-aspartates with β-benzyl-l-aspartate were prepared. The introduction of a methyl, chloro, or cyano group into the para position of the aromatic ring in the side chain of poly-β-benzyl-l-aspartate (PBLA) also causes a reversal from the left- to the right-handed in the helical sense of the polypeptide in a chloroform solution, as in the case of the nitro group. The residue of the copolymers where the transition takes place contained: nitro, 20–30; cyano, 40–50; chloro, ca. 50; and methyl group, ca. 70mol.-%. These values may indicate the relative stabilities between the PBLA helix and poly-β-(p-substituted benzyl)-l-aspartate helices. These series of copolymers had no absorption band in the longer wavelength region except for a nitrobenzyl series, which had an absorption band at around 330 mμ. The absence of an absorption band resulted in a normal b0 value. The results suggest that the factors which determine the helical sense of the PBLA helix are not very simple and that the left-handed helix of PBLA is much less stable.
A New Method for the Phosphorylation of Alcohols by Means of Bromine and Dibenzylhydrogen Phosphite
Authors: Mukaiyama Teruaki , Kouda Hajime , Kodera Kyoko
Published: July 2006

Various alkyldihydrogen phosphates were obtained in good yields by reacting alcohols, dibenzylhydrogen phosphite, and bromine in the presence of triethylamine, followed by catalytic hydrogenation. When benzyl alcohol and diethyl phosphite were used in the above reaction, only the oxidation of the latter took place, giving diethylhydrogen phosphate in an excellent yield. These results suggest that the above phosphorylation of alcohol proceeds through a quaternary phosphonium salt, i. e., dibenzyloxyalkyloxyhydroxy phosphonium bromide, which is then converted into an alkylbenzylhydrogen phosphate. The effect of tertiary amines on this type of phosphorylation was also examined.
Organic Sulfur Compounds. XIV. The Reactions of Sulfinic Esters and Related Compounds with Hydrazine
Authors: Kobayashi Michio , Yamamoto Asami
Published: July 2006

Anhydrous hydrazine reacted with sulfinic esters under mild reaction conditions to give disulfides, which were in turn, upon prolonged heating, reduced by hydrazine to mercaptans. Aromatic thiolsulfonates and sulfonyl chlorides were also reduced by hydrazine, whereas aromatic sulfoxides and sulfinic acids were not reduced under comparable reaction conditions. A mixture of hydrazine with a sulfinic ester or another of the reducible sulfur compounds described above can hydrogenate carbon-carbon double bonds and triple bonds. A mechanism involving the intermediate formation of diimide is proposed.
Studies of the Hydrocracking of Lignin. I. The Hydrocracking of Desulfonated Sulfite Waste Lignin
Authors: Oshima Motoyoshi , Kashima Kan , Kubo Teruo , Tabata Haruro , Watanabe Hiroshi
Published: July 2006

The raw material for the hydrocracking was prepared by treating alcohol fermented sulfite waste liquor with lime, desulfonating the thus-prepared slurry by heating, and deashing the precipitate with sulfur dioxide. The hydrocracking was run with a high-boiling fraction of lignin-hydrogenated oil as the solvent (pasting oil) and with Fe-promotor-sulfur as the catalyst. The yield of monophenols was 24% (based on klason lignin) with a 100% recovery of the pasting oil under reaction conditions of a temperature of 430°C, an initial hydrogen pressure of 130 kg./cm2, and a catalyst dosage of 3% (based on the lignin). The higher reaction pressure resulted in a slight increase in the yield of monophenols. The formation of non-volatile pitch decreased with the increase in the initial pressure up to 130 kg./cm2 but a further increase of the pressure exerted no effect. The higher reaction temperature gave more hydrogen absorption and a higher yield of monophenols, and less pitch formation and pasting oil recovery. However, it is essential to select reaction conditions where the highest yield of monophenols is obtained with a 100% recovery of the pasting oil.
Twinning in Electric Furnace-fused Corundum
Authors: Yamaguchi Goro , Kubo Yasushi , Ogawa Hiroshi
Published: July 2006

In an investigation into the fracture properties of thin-sectioned corundum crystals, it was noticed that microcracks in electrically-fused corundum obey a hexagonal symmetry in spite of the rhombohedral symmetry of the corundum structure. This fact suggests that the corundum crystals consist of several twins, which have the same optical direction and which cannot be distinguished microscopically. The X-ray Laue back-reflection and etching techniques were applied to commercial 16-mesh grains of electric furnace-fused alumina abrasives. Corundum crystals grown over the crystal size of hundreds of μ to 1 mm. in electric-furnace fusions were found to be generally composed of several penetration twins with a twinning plane (0001). The twins are considered to be growth twins arising in the cooling process. The impurity composition and heat treatment have no marked effect on twinning. The twin junction is highly stable both mechanically and chemically. Cleavage cracks generated in individual crystals are stopped at the twin boundary.
Kinetic Studies of Solvolysis. XI. The Steric Course of the Phenolyses of Optically Active α-Phenylethyl Chloride in Mixtures of Various Phenols and Organic Solvents—A Mechanism for the SN1 Reaction with a Net Retention of Configuration
Authors: Okamoto Kunio , Yamada Hiroto , Nitta Issei , Shingu Haruo
Published: July 2006

The SN1 phenolyses of optically active α-phenylethyl chloride in binary mixtures of organic solvents and certain substituted phenols (i. e., phenol, p-cresol, p-chloro- and p-nitro-phenol) proceed in the presence of aniline and of triethylamine to give the corresponding α-phenylethyl substituted-phenyl ethers with a predominantly-retained configuration. In binary mixtures of benzene and various phenols, the extents of retention for the ethers are slightly reduced at the higher base concentrations. However, in binary solvents of acetonitrile and certain phenols, the optical purities of the ethers with retained configurations decrease continuously with the base concentrations, while at the higher concentrations (∼0.4 m) the steric courses change to the inverted course. The C-alkylated (α-phenylethylated) derivatives of these phenols, isolated along with the phenyl ethers, have inverted configurations, irrespective of the configurations of the corresponding phenyl ethers. These results are all consistent with a mechanism in which a molecule of the phenol reacts with the SN1 ion-pair intermediate of the phenolysis to give a phenyl ether with a retained configuration, probably by SNi-like four-center substitution, whereas the reaction of a phenoxide anion with the SN1 intermediate proceeds predominantly by the Walden inversion mechanism yielding a phenyl ether and α-phenylethylated phenols with inverted configurations.
Studies of the Chemical Reactions of Uranium Iodide with Oxygen and Iodine at High Temperatures
Authors: Handa Muneo
Published: July 2006

Uranium tetraiodide is oxidized to triuranium octoxide through three intermediates, which are deposited on silica powder heated to temperatures of about 400, 300 and 200°C respectively. The intermediates are produced by the action of oxygen contained in small amounts in a helium stream (1/100–1/10000 atm.) on uranium tetraiodide. The intermediates are considered to be compounds consisting of uranium, iodine and oxygen. Chemical analysis, the measurement of the melting point and X-ray analysis show that the compound deposited at the temperature of 400°C is uranium triiodide, while the compounds deposited at 300 and 200°C are both uranium tetraiodides. Three hypotheses have been formulated to interpret the above phenomenon, in which the reaction of uranium iodides with iodine has been studied.
The Electron Spin Resonance and Electronic Spectra of 4-Substituted Pyridinyl Radicals
Authors: Itoh Michiya , Nagakura Saburo
Published: July 2006

The ESR and electronic absorption spectra have been measured with the 1-methyl-4-carbo-methoxy-, 1-methyl-4-carbamido-, 1-methyl-4-acetyl- and 1-methyl-4-cyanopyridinyl radicals. From the analysis of their ESR spectra by the aid of a spectrum accumulator, we have been able to determine the nitrogen and hydrogen hyperfine splitting constants of these pyridinyl radicals, from which the spin distributions have then been evaluated. These radicals except for the 1-methyl-4-carbamidopyridinyl radical, have been found to show three absorption bands, at 300–350 mμ, at about 400 mμ and at about 600 mμ. From the results of the ESR and electronic absorption spectra, the electronic structures of these pyridinyl radicals have been concluded to be similar to those of the 4-substituted pyridine anion radicals. The preparation of 1,2,6- and 1,3,5-trimethyl-4-substituted pyridinyl radicals has been attempted. The latter radicals, except for the 1,3,5-trimethyl-4-cyanopyridinyl radical, were not detected by the ESR and electronic absorption spectra, because the steric hindrance of the methyl groups at the 3 and 5 positions prevents them from achieving the resonance stabilization due to the 4-substituent.
Kinetic Studies of the Solution Polymerization of Trioxane Catalyzed by BF3·O(C2H5)2. V. The Effect of the Solvent and of the Polymerization Temperature
Authors: Miki Tetsuro , Higashimura Toshinobu , Okamura Seizo
Published: July 2006

The effect of the polarity of solvents in the solution polymerization of trioxane catalyzed by BF3·O(C2H5)2 has been studied. While the molecular weight of the resulting polymer is almost independent of the kind of solvent, the rate of polymerization in a polar solvent is large at a high initial monomer concentration. At a low monomer concentration, however, the rate of polymerization in a non-polar solvent is larger than that in a polar solvent. This fact can probably be explained by observing that, at the low monomer concentration, the initiation species produced from the catalyst is solvated by the solvent molecule rather than by trioxane because of the small basicity of trioxane. The activation energies of the over-all polymerization rate as determined in ethylene dichloride, nitroethane and nitrobenzene are all about 16 kcal./mol. The decrease in the molecular weight of the resulting polymers caused by raising the temperature is very small.
Studies of Poly-2-vinylpyridine. I. Suspension Polymerization and Molecular Weight Distribution
Authors: Arichi Shizuo , Mitsuta Seiji , Sakamoto Noriyuki , Murata Hiromu
Published: July 2006

2-Vinylpyridine has been polymerized by the suspension method. A stable suspension has been obtained using a mixture of sodium butylnaphthalene sulfonate and gelatine as a stabilizer in the concentration ranges of 0.025–0.75 per cent (for the former) and 0.75–1.0 per cent (for the latter) in water. The molecular weight of polymers thus obtained from this stable suspension system could be controlled by varying the concentration of azo-bis-isobutyronitrile and the temperature. The Mw/Mn ratios of the polymers obtained by the above method are relatively large; from 3.5 to 5. Precipitation fractionation has been carried out for a polymer obtained using ethyl methyl ketone as a solvent and ligroin as a precipitant at a constant temperature. Three kinds of molecular weight distribution curves have been obtained by applying the data of fractionation to (1) Tung’s method, (2) exponential-type and (3) logarithmic normal-type molecular weight distribution functions. By comparing the average molecular weights, Mw and Mn calculated from each curve with the experimental values, it was found that the molecular weight distribution of the fraction can be well represented by the function 2 or 3.
Studies of Poly-2-vinylpyridine. II. Solubilities in Various Solvents
Authors: Arichi Shizuo , Matsuura Hiroatsu , Tanimoto Yoshio , Murata Hiromu
Published: July 2006

The viscosity and osmotic pressure of a fraction of poly-2-vinylpyridine have been measured in various solvents, and the parameters concerning the solubility of this polymer, that is, the osmotic second virial coefficient, A2, the polymer-solvent interaction parameter, μ, and the solubility parameter, δ2, have been obtained. From the values of these parameters, the following conclusions have been obtained: poly-2-vinylpyridine has a solubility parameter of ca. 10.4 (cal./cc.)1⁄2 and acts as an electron donor. As a result of the specific interaction between a solvent and the pyridine nitrogen of this polymer, the solvent power is greater in an acidic solvent and smaller in a basic than would be expected from the solubility parameter alone. An especially strong interaction between poly-2-vinylpyridine and aliphatic alcohols, chloroform and nitroethane has been observed and its nature has been discussed.
Studies of Poly-2-vinylpyridine. III. Intrinsic Viscosity and Molecular Weight
Authors: Arichi Shizuo
Published: July 2006

The viscosity, osmotic pressure and light-scattering of a series of 14 fractions of poly-2-vinylpyridine in various solvents have been measured. The following results have been obtained: The constants, Kw′ and v, in the Mark-Houwink equation have been determined for the solutions of: (a) 92.01 weight per cent ethanol, (b) methanol, (c) dimethylformamide, (d) benzene and (e) dioxane as follows:

(a) [η]=1.22×10−4Mw0.73 (d) [η]=1.70×104Mw0.64

(b) [η]=1.13×104Mw0.73 (e) [η]=3.09×104Mw0.58

(c) [η]=147×10−4Mw0.67

The molecular weight of the polymers ranged from 3.4×104 to 93×104, while the viscosity was measured at 25±0.01°C. The constant, K′ in the Mark-Houwink equation in the case of a homogeneous molecular weight has been calculated assuming the exponential- and logarithmic normal-type molecular weight distribution functions for each fraction. The Flory constant, K, defined as [η]θ=KM1⁄2 has been found by the method of Fixman and Krigbaum to be: (8.7±1.0)×10−4 at 25°C. The K value has also been found to be (9.1±1.1)×104 by measuring the intrinsic viscosity in benzene at the θ-point, 16.2°C. The short range interactions of this polymer have also been discussed.
The Rheological Study of Aqueous Solutions of Polyvinyl Alcohol at Ultrasonic Frequencies
Authors: Arakawa Kiyoshi , Takenaka Nobuo
Published: July 2006

The ultrasonic velocity and the absorption have been measured over the 5–45 Mc./sec. frequency range for aqueous solutions of polyvinyl alcohol by means of an ultrasonic pulse technique which was similar in principle to that used by Pinkerton (Proc. Phys. Soc. B62, 286 (1949)). The temperature varied over the 3–70°C range. The velocity-versus-temperature curves have been found to be convex upwards, like that of pure water, but the peak shifts upwards and to the lower-temperature side with an increase in the concentration. The ultrasonic absorptions of aqueous solutions of partly-saponified polyvinyl alcohol have been found to be larger than those of perfectly-saponified alcohol at the same concentrations. Two relaxation mechanisms have been found for each sample. For the solutions of the perfectly-saponified sample, the first relaxation frequency, f1, is 35 Mc./sec. at 12°C, while the second relaxation frequency f2 is 40 Mc./sec. at 60°C, for example. On the other hand, these values have been found to be nearly equal for the solutions of the partly-saponified sample. The activation energy, ΔH2, obtained from the temperature dependence of f2 is about 4 kcal./mol., irrespective of the quantity of resuidal acetate groups, and the ΔH1 value forf1 is of the order of 10 kcal./mol.
The Infrared Spectra of Artificial Coal made from Submerged Wood at Uozu, Toyama Prefecture, Japan
Authors: Tsukashima Hiroshi
Published: July 2006

The infrared spectra of artificial coal prepared from Submerged Wood were observed and compared with those of lignin and cellulose. The artificial coalification seems to proceed in three stages, characterized by the corresponding infrared spectra, i. e., a cellulose-like spectrum, a lignin-like spectrum, and a spectrum resembling that of natural coal. The infrared spectrum of artificial coal is generally similar to that of natural coal with a little higher carbon content, suggesting that the degree of coalification is more advanced in artificial coal than in natural coal. The background absorption in the infrared spectra of artificial coal of a low coalification is weak, while that in the infrared spectra of artificial coal of a high coalification is strong.
The Infrared Absorption Spectra of the Condensation Products of Formaldehyde with Hydrazine
Authors: Mashima Mitsuo
Published: July 2006

The infrared absorption spectra of tetraformaltrisazine and formalazine have been obtained in the solid state. From a tentative assignment of the bands observed, it has been shown that a molecule of tetraformaltrisazine has the bicyclic structure proposed by Hofmann and Storm, while formalazine is a polymer with a four-membered heterocyclic ring.
The Temperature Dependence of the Radio-Frequency Polarographic Wave Height
Authors: Kambara Tomihito , Watarai Shogo
Published: July 2006

When the radio-frequency polarographic current, iRF, is regarded approximately as the difference between the Fournier current and the ordinary DC polarographic current, iDC, one can elucidate the temperature dependence of iRF. It may be theoretically predicted that the relative temperature coefficient of iRF for the completely-reversible system is less by 0.66% than that of iDC. The plot of log(iRF·T2) against 1/T, where T is the absolute temperature, gives two straight lines which join each other at a knick, coresponding to the transition from a completly reversible process to a less reversible one. Experiments with thallium(I) and zinc(II) ions in various supporting electrolytes reveal the essential validity of the present theory.
Phenazine Complexes. Their Preparation and Their Electrical Conductivity
Authors: Inoue Hiroo , Tamaki Kentaro , Kida Yoshihiro , Imoto Eiji
Published: July 2006

The photo-reduction of phenazine was carried out in isopropyl alcohol in the presence of ferric chloride or stannic chloride. In the course of the photo-reduction, a metal chelate precipitated. The metal chelate was composed of unstable black needle crystals; it was presumed, from the results of the elementary analysis, the visible and the infrared absorption spectra and the ESR spectra, to be Fe2+- or Sn2+-chelate of N-monohydrophenazyl. On the other hand, the reduction of phenazine with stannous chloride and hydrochloric acid gave a phenazhydrin - stannic chloride-complex, which was more stable than the photo-reduction products. Their resistivities at 20°C had low values of from 105 to 108 ohm-cm.
The Absorption Spectra of Dyes. XI. A Note on the Color Change in Some Azobenzene Dyes with Variation in the Acidity
Authors: Tanizaki Yoshié , Kobayashi Tadashi , Hoshi Toshihiko
Published: July 2006

The absorption spectra of azobenzene and its para hydroxy, amino or dimethylamino derivative, and their sodium salts have been determined above 220 mμ in mixed solutions of water and ethanol (7 : 3 in volume) at various acidities. All the samples show characteristic changes in spectra with increase in the acidity, and the respective spectral changes keep well-defined isosbestic points, indicating a binary system spectrally. The wavelengths of the color band peaks and the corresponding spectral species have been determined. Consequently, the following order of the substitution effect has been obtained;

(Remark: Graphics omitted.)
Metal Complexes of Amino Acids. II. The Absorption Spectra of Geometrical Isomers of Copper(II) Complexes
Authors: Yasui Takaji , Shimura Yoichi
Published: July 2006

The geometrical structures of bis(α-amino-acidato)copper(II) complexes have been determined from the data of diffuse reflectance spectra (α-amino-acid = glycine, l- and Dl-α-alanine, l- and Dl-valine, l- and Dl-threonine, l- and Dl-isoleucine and α-aminoisobutyric acid). It has been shown that pairs of cis(N) and trans(N) isomers exist in glycinato and valinato complexes. It has been clarified that the other amino-acidato complexes studied exist either only in the cis(N) form or only in the trans(N) form; that is, the needle and the scaly complexes of Dl-alanine, the complexes of Dl- and l-threonine, and the complex of α-aminoisobutyric acid exist only in the trans(N) form, while the complexes of l- and Dl-isoleucine exist only in the cis(N) form.
The Rheological Behavior of Suspensions of Ion-exchange Resin Particles
Authors: Sen\={o} Manabu , Yamabe Takeo
Published: July 2006

The flow properties of the suspensions of ion-exchange resin particles, the highly-crosslinked polyelectrolyte gel particles, were examined, especially in relation to their charged state. The steady viscosities and the dynamic viscoelasticities of these suspensions were measured, and the results were interpreted in terms of the dispersion state of the suspended particles. The flow system of the highly-charged particles, such as Na-form resin particles, exhibits a high viscoelasticity and is in a well-dispersed state. On the contrary, the flow system of the lower-charged particles, such as Ba-form particles, is not viscoelastic, but viscous and dilatant. This behavior may be attributed to the variation in the electrical double layers around the suspended particles.
The Formation Conditions and the Properties of Copper, Zinc, Ammonium Sulfites
Authors: Omori Keiichi , Okuwaki Akitsugu , Suzuki Takahiro , Ito Hiroshi , Okabe Taijiro
Published: July 2006

On the reaction of an ammonium sulfite solution with a mixed solution of cupric sulfate and zinc sulfate, ten or more complex sulfite salts have been identified by chemical analysis and X-ray diffraction, and their formation regions have been shown with equilateral triangle coordinates. Their crystallographic properties have been examined through optical observation and X-ray diffraction. Usually some of them are formed simultaneously, but sometimes only one of them is formed, depending on the reaction conditions. The newly-found compounds are as follows:

Cu2SO3·7(NH4)2SO3·9H2O Tetragonal

Cu2SO3·ZnSO3·6(NH4)2SO3·10H2O Tetragonal

Cu2SO3·2ZnSO3·5(NH4)2SO3·12H2O Monoclinic

Cu2SO3·4ZnSO3·3(NH4)2SO3·12H2O Hexagonal
Organic Sulfur Compounds. I. Reactions of Arylsulfinic Acids with Alkyl Chlorosulfites
Authors: Kobayashi Michio , Terao Miki , Yamamoto Asami
Published: July 2006

The salts of arylsulfinic acids were found to react with alkyl chlorosulfite to form alkyl sulfinates. p-Toluenesulfinic acids-18O was synthesized and treated with ethyl chlorosulfite to give ethyl p-toluenesulfinate-18O, which retained half of the oxygen atoms existing in the original sulfinic acid. A mechanism for this novel reaction was proposed.
The Magnetic Properties of Several Pseudo-Jahn-Teller Nonbenzenoid Aromatic Hydrocarbons
Authors: Nakajima Takeshi , Kohda Susumu
Published: July 2006

The effect of bond length alternation on the magnetic properties of several Pseudo-Jahn-Teller nonbenzenoid aromatic hydrocarbons with 4ν carbon atoms will be investigated. The magnetic moment and the susceptibility of a cyclic polyene will first be formulated in terms of the bond alternation parameter. Appropriate cross-links for forming nonbenzenoid aromatic hydrocarbons, such as pentalene and heptalene, will then be treated as perturbations. It will be shown that the anomalously large paramagnetic susceptibilities of these molecules predicted by Pullman et al. (“Les Théories Electroniques de la Chimie Organique,” Masson, Paris (1952), p. 527) arise mainly from the neglect of the bond alternation inherent in them. It will then be concluded that the magnetic susceptibility is a very sensitive indicator of the bond alternation, and that the diamag-netically-induced ring currents in these molecules are very much impeded.
The Attempted Cationic Polymerization of 1,1-Dimethylcyclopropane and Phenylcyclopropane
Authors: Aoki Shuzo , Harita Yoshiyuki , Otsu Takayuki , Imoto Minoru
Published: July 2006

1,1-Dimethylcyclopropane and phenylcyclopropane gave the oligomer by aluminum bromide-catalyzed polymerization in n-hexane or in methylene chloride at 0°C. The polymerization reactivity of 1,1-dimethylcyclopropane was lower than that of styrene, and the content of cyclopropane units in their copolymers was decreased by a lowering of the temperature. The polymerization of 1,1-dimethylcyclopropane in the presence of polystyrene gave a graft polymer by chain transfer reaction. The polymerization of the cyclopropanes by a coordinated catalyst, C2H5AlCl2/TiCl3, in n-heptane at room temperature gave polymers with molecular weights of above 1200. The results are discussed in comparison with those of the polymerization of the corresponding vinyl monomers.
The Chemiluminescence of Acyl Luminols
Authors: Omote Yoshimori , Miyake Takeo , Ohmori Seiya , Sugiyama Noboru
Published: July 2006

From a study of the chemiluminescence spectra of acyl luminols (e.g., 3-acetylaminophthalhydrazide, 3-propanoylaminophthalhydrazide and 3-undecenoylaminophthalhydrazide) and of the corresponding fluorescence spectra of the reaction products, it is tentatively assumed that the emitting species of the chemiluminescence of acyl luminols in dimethylformamide-water (3:1 in vol.) is the corresponding 3-acylaminophthalate ion in the excited state.
Radical Yields in the Radiolysis of Neutral Aqueous Solutions
Authors: Sawai Takeshi
Published: July 2006

The determination of the yields of the two reducing species and the OH radical in the radiolysis of neutral aqueous solutions was undertaken, using deaerated 2-propanol aqueous solutions containing potassium nitrate or hydrogen peroxide as electron scavengers. Irradiation was carried out with 60Co γ-rays, and the hydrogen, nitrite ion, acetone, hydrogen peroxide and pinacol so produced were analyzed. The hydrogen yield decreases upon the addition of hydrogen peroxide or nitrate ions. The yield of hydrogen atoms is found to be 0.61±0.03 by subtracting the molecular yield of hydrogen from the total hydrogen yield in the solutions containing enough scavengers. The yield of nitrite ions increases with an increase in the concentration of nitrate ions, and decreases with an increase in the concentration of acetone and with a decrease in the pH value. The acetone yield increases sharply with an increase in the quantity of nitrate ions and reaches a plateau value in the concentration range of nitrate ions higher than 1×10−2m. In the presence of potassium nitrate of 1×10−2m, pinacol is not formed, and the yield of hydrogen peroxide is less than the molecular yield of hydrogen peroxide. On the basis of these results, radiolysis mechanisms are elucidated and the yields of the hydrated electron and the OH radical of a neutral solution are found to be 2.77±0.03 and 3.0 respectively. The relative rate constants, kH+NO3−⁄kH+(CH3)2CHOH and ke−aq+(CH3)2CO⁄ke−aq+NO−3, are found to be 0.18 and 0.78.
Organic Sulfur Compounds. II. The Formation and Thermal Decomposition of Carboxylic Sulfurous Anhydrides
Authors: Kobayashi Michio , Yamamoto Asami
Published: July 2006

Mixed anhydrides of carboxylic acids and monoalkyl sulfites have been prepared, and their thermal decomposition has been studied. Some of these mixed anhydrides can be distilled without decomposition. Disproportionation to carboxylic anhydride and dialkyl sulfite is the main pathway of the thermal decomposition.
The Separation of Alkaline Earth Metals as Their TTA-Complexes by Reversed-Phase Partition Chromatography
Authors: Akaza Ikuko
Published: July 2006

The author’s preceding work, the liquid-liquid extraction of alkaline earth metals with TTA-MIBK, has now been extended to a reversed-phase partition chromatography in order to attain a good separation of the metal ions. The method was carried out with relatively large amounts of the metals through a column of Kel-F on which the organic phase of 1.5 m TTA-MIBK was supported. Elution was performed with 0.5 m buffer solutions, of various pH values, consisting of acetic acid, ammonium acetate and aqueous ammonia. The actual separation of each metal ion from the mixture of alkaline earth metals was achieved; the results are shown in several figures. The dependence of the distribution ratio on the pH of the solution and on the concentration of TTA in the stationary phase was examined from the elution curves; it might be considered that the same relation held as in the case of the liquid-liquid extraction system. Other experiments were then carried out in order to clarify the behavior of the TTA-chelates in the presence of a large amount of TTA; it was found that all of the TTA in the system participated in the effective extraction of the metal ion. The steps in the formation of the higher TTA-chelate in the column are depicted by the break-through curve of the chromatographic process.
SORPTION OF GAS BY THE POROUS MATTER
Authors: Sameshima Jitsusaburo
Published: July 2006

The mechanism of the sorptions of gases by charcoal, silica gel and chabazite etc. are discussed. The author’s theory for these cases is as follows: The gas molecules enter into the molecular cavities in the solid body and form a homogeneous solid solution.