bluuebunny/crossref_metadata_2025 huggingface dataset:
Excitation from Superexcitation of Hydrocarbons. Estimation of Their Yields by the Optical Approximation
Authors: Hatano Yoshihiko
Published: July 2006

A simple calculation has been made based on the so-called optical approximation to obtain the yields of excitation from superexcitation of the hydrocarbons, methane, ethane, propane, n-butane, n-pentane, ethylene, propylene, butene-1, butene-2, 1,3-butadiene, acetylene, and cyclopropane. Their dipole-matrix-elements squared for excitation from superexcitation, Md2, have been found to be directly proportional to the number of carbon atoms in the hydrocarbons, and the ratio of Md2 to Mi2, the dipole-matrix-element squared for ionization, is about 0.2. Thus, the yields, per 100 eV energy absorbed, of excitation from superexcitation are nearly equal to 0.8 for all the hydrocarbons described here.
Polymerization Catalyst of the Triethylaluminum-Chloral Hydrate System. II. Copolymerization of Acetaldehyde with Chloral
Authors: Saegusa Takeo , Fujii Hiroyasu , Tanaka Katsumi
Published: July 2006

It has been found that the AlEt3-chloral hydrate system induces the random copolymerization of acetaldehyde with chloral. The homogeneity of the product polymer was confirmed by a study of the infrared spectra and bv turbidimetric titration. The thermal stability of the copolymer was much better than that of homopolyacetaldehyde. The copolymer was soluble in chloroform, and films were cast from chloroform solutions.
Oxygen Exchange and Racemization Reactions of Sulfoxides in Acetic and Chloroacetic Acid
Authors: Oae Shigeru , Yokoyama Mikihiko , Kise Masahiro
Published: July 2006

Oxygen exchange reaction of sulfoxides has been performed mainly in mineral acids such as sulfuric acid, aqueous hydrochloric and hydrobromic acids. We have found that concurrent oxygen exchange and racemization reactions take place also in carboxylic acids such as acetic, mono- and poly-chloroacetic acids. The pseudo first order reaction rates of both oxygen exchange and racemization reactions of p-tolyl phenyl sulfoxide have been determined using both optically active and 18O-labeled p-tolyl phenyl sulfoxides in these acids. This reaction is found to be mainly dependent on the strengths of the acids; namely, the reaction velocity is faster in an acid of smaller pKa value. Together with the fact that k(rac.)/k(exch.) is unity and the substituent effect is small, the reaction is suggested to proceed through an unimolecular type S–O bond cleavage, probably involving radical cation intermediate (II).
Synthetic Studies of α-Tocopherol. I. Synthesis of α-Tocopheryl Acetate
Authors: Ichikawa Takehiko , Kato Tetsuya
Published: July 2006

Geraniol (III) was reacted with trimethylhydroquinone (II) in the presence of boron trifluoride in benzene. The product was then acetylated to give a mixture of 2,5,7,8-tetramethyl-2-(4-methyl-3-penten-1-yl)-6-acetyloxychromane (VI) and 2,5,7,8-tetramethyl-2,3-(4,4-dimethylbutano)-6-acetyloxychromane (Vb). The VI was ozonized and decomposed with zinc and acetic acid to give 2,5,7,8-tetramethyl-2-(2-formylethyl)-6-acetyloxychromane (VII). Pseudoionone (VIII) was reduced with sodium borohydride to give pseudoionol (IX), but in certain cases the dehydration of IX occurred during the distillation. VII was condensed with IX by a Wittig reaction to give 2,5,7,8-tetramethyl-2-(4,8,12-trimethyl-3,5,7,11-tridecatetraen-l-yl)-6-acetyloxychromane (X), which was then hydrogenated to give α-tocopheryl acetate (I).
Reaction of Oxymercurials. Synthesis of 6,6-Dimethyl-spiro[2,5]octan-4,8-dione
Authors: Ichikawa Katsuhiko , Itoh Osamu , Kawamura Takahisa
Published: July 2006

The reaction of oxymercurial of ethylene with dimedone in acetic acid containing perchloric acid, followed by treatment with sodium chloride, gave 2-(β-chloromercuriethyl)-5,5-dimethyl-cyclohexan-1,3-dione. Upon treating this mercurial with an equimolar amount of aqueous potassium hydroxide, 6,6-dimethyl-spiro[2,5]octan-4,8-dione was obtained. Oxymercurial of propylene reacted with dimedone to form a mixture of 4-oxo-2,6,6-trimethyl-2,3,4,5,6,7-hexahydrobenzofuran and 4-oxo-3,6,6-trimethyl-2,3,4,5,6,7-hexahydrobenzofuran under simultaneous demercuration; the mercurial corresponding to that in the case of ethylene could not be isolated.
The H/D Isotope Effect in the Conversion of the Electron into a Hydrogen Atom in Aqueous Acid Solutions at 300 and 77°K
Authors: Ohno Shin-ichi
Published: July 2006

The isotope effect in the formation of hydrogen atoms as a result of the reaction of the photo-chemically-produced electron in an acidified solution of hexacyanoferrate(II) has been investigated in both the liquid and solid phases. The magnitude of the effect (H/D) in the liquid phase, determined by a mass-spectrometric analysis of the hydrogen gas evolved from CH3OH-containing solution, ranges from 3 to 4, and it depends on the temperature. The corresponding H/D ratio in acidic ices (at 77°K), determined by comparing the relative intensities of the ESR signals of the H and D atoms, is rather low (∼1.5). Possible mechanisms by which the electron is converted into a hydrogen atom in aqueous acid solutions in both phases are discussed.
Thermodynamic Properties of Solutions of m-Terphenyl in Benzene. I. The Vapor Pressures and the Related Thermodynamic Functions at 30 and 50°C
Authors: Takagi Sadao , Furukawa Katsuya , Fujishiro Ryoichi
Published: July 2006

Vapor pressures of solutions of m-terphenyl in benzene were measured for the concentration less than 0.23 in mole fraction x of terphenyl at 30 and 50°C. Vapor pressures P mmHg obtained are represented by log10P(30°)=2.076970–0.4343x–0.06569x2–0.4340x3 and log10P(50°)=2.432100–0.4343x–0.14654x2–0.3412x3. Chemical potentials observed were reproduced by the quasi-lattice theory for mixtures of molecules of different sizes. The Miller-Guggenheim expression (r=3, z=6–8) gives w⁄k=100±5°, and the Flory-Huggins expression (r=molecular volume ratio) gives χ=0.272±0.004 (30°) and χ=0.243±0.006(50°). Partial molar heats of mixing are rather fitted by the regular solution theory similarly to the case for benzene+biphenyl, and the Flory-Huggins expression gives a concentration-dependent enthalpy parameter, χH=(0.772+1.716φ)×102⁄T, where φ means a volume fraction of terphenyl. The average value of χH, 0.39 agreed with a theoretical estimate from solubility parameters.
Electron Spin Resonance Study of the Radiolysis of Monocarboxylic Acids Adsorbed on Silica Gel
Authors: Miura Masaji , Hasegawa Akinori , Yamada Yoshio
Published: July 2006

Electron spin resonance measurements were carried out on γ-irradiated monocarboxylic acids (formic, acetic, and propionic acids) adsorbed on silica gel. In the case of formic acid, the spectrum assigned to the CO2− radical was mainly observed, but also observed was the signal caused by the defects of γ-irradiated silica gel, whereas for the acetic acid a quartet due to the methyl radical was obtained. These spectra, however, were not found in the frozen acids alone. As regards propionic acid, ethyl radicals were produced in both the adsorbed and frozen states. It was concluded from these results that the characteristic radiolysis of monocarboxylic acids on the adsorbed state is to be attributed to interaction between the acids adsorbed on silica gel as monomers and the surface. On the basis of these spectra, the adsorbed state of the acids and the stability of the radicals have been discussed.
Studies on Hydroxy Amino Acids. I. A New Synthesis of Aziridine Derivative from β-Hydroxy α-Amino Acid
Authors: Okawa Kenji , Kinutani Teiji , Sakai Katsunobu
Published: July 2006

N-Tosyl-3-methyl-2-aziridinecarboxylic acid anilide was obtained by the β-elimination reaction of N,O-ditosyl-l-threonine anilide. The ethyleneimine ring of this compound was readily cleaved by acetic acid in the presence of boron trifluoride and N-tosyl-O-acetyl-l-threonine anilide was obtained. Formaldehyde also reacted with this compound in the presence of the same catalyst and gave 1,3-oxazolidine and 1,3-oxazine derivatives.
Syntheses of Heterocyclic Compounds from Benzamidine, Aldehydes, and Hydrogen Cyanide
Authors: Haruki Eiichi , Imanaka Hiroshi , Imoto Eiji
Published: July 2006

The reactions of benzamidine with several aldehydes in the presence of hydrogen cyanide were studied, using an aqueous methanol as a solvent. When formaldehyde or acetaldehyde was used as an aldehyde component, α-hydroxyalkyldiphenyl-s-triazines were obtained, while when benzaldehyde, p-chlorobenzaldehyde, or furfural was used, the corresponding 4-arylmethylidenamino-2,5-diphenyloxazoles were obtained. However, under the same reaction conditions, m-nitrobenzaldehyde afforded dimethyl azoxybenzene-3,3′-dicarboxylate.
Total Synthesis of Nepseudin
Authors: Fukui Kenji , Nakayama Mitsuru
Published: July 2006

The Hoesch reaction of 6-hydroxy-2,3-dihydrobenzo[b]furan with 2,3,4-trimethoxyphenylacetonitrile yielded 6-hydroxy-5-(2,3,4-trimethoxyphenylacetyl)-2,3-dihydrobenzo[b]furan. The cyclization of the dihydrobenzofuran with ethyl orthoformate-pyridine-piperidine gave dihydrodehydronepseudin, an isoflavone. The dehydrogenation of the above isoflavone with N.B.S. or Pd-G yielded dehydronepseudin. Nepseudin was derived by the reduction of dehydronepseudin with sodium borohydride and by subsequent oxidation with the chromium trioxidepyridine complex.
Perchloro-compounds. IV. anti-Perchloro-(3,4,7,8-tetramethylenetricyclo[4.2.0.02,5]octane), a Dimer of Perchloro-(3,4-dimethylenecyclobutene)
Authors: Mano Koichi , Kusuda Kousuke , Fujino Akira
Published: July 2006

The structure of the first of the four thermolytic dimers of perchloro-(3,4-dimethylenecyclobutene) was characterized as anti-perchloro-(3,4,7,8-tetramethylenetricyclo[4.2.0.02,5]octane) (II). This structure elucidation was principally based on: (a) the permanganate oxidation of II to perchloro-(dimethylenesuccinic) acid; (b) the two-step reduction of II to 1,2,3′,4′,5,6,7′,8′-octachloro-3,4,7,8-tetramethylenetricyclo[4.2.0.02,5]octane and 1,2,5,6-tetrachloro-3,4,7,8-tetra-methyltricyclo[4.2.0.02,5]octa-3,7-diene (VII), and (c) the hydrogenation of the ozonized product from VII to two tetraacetylcyclobutanes (XVII and XVIII). The physical and chemical properties of II and of those substances derived from II and VII were discussed in detail. The stereochemical configurations of II and XVII were estimated to be anti and all-trans respectively.
Alternating Current Polarography of Peroxodisulfate and Ferricyanide Ions in the Absence of Supporting Electrolytes
Authors: Tamamushi Reita , Matsuda Kiyoshi
Published: July 2006

The admittance and its phase angle of the polarographic reduction of peroxodisulfate and ferricyanide ions in solutions containing no supporting electrolytes were measured at very low frequencies. The series resistance components, measured at 30 cps, of these systems gave anomalously small values at the electrode potentials where the falling-off of the cathodic current was observed on the direct current polarograms. This anomaly in the alternating current polarization behavior was attributed to the negative charge-transfer resistance due to the double layer effect on the charge-transfer process.
The Coprecipitation and the Spectrophotometric Determination of Uranium as Dibenzoylmethane Chelate
Authors: Shigematsu Tsunenobu , Tabushi Masayuki , Matsui Masakazu , Munakata Megumu
Published: July 2006

The coprecipitation and direct-photometric method was applied to the uranium β-diketonate system; uranyl ion was coprecipitated as dibenzoylmethanate with o-phenylphenol and determined spectrophotometrically after the precipitate was dissolved in butyl acetate. The effect of ligand concentration on the per cent coprecipitation-pH curve was studied and the curve was not affected by the ligand concentration in the range from 2×10−2 to 4×10−4  m. Over the 200 mg of o-phenylphenol, an almost quantitative coprecipitation was obtained, though the absorbance slightly decreased with the increase in the coprecipitant amount (about 2% per 1g o-phenylphenol). As many diverse ions interfered with the determination of uranium, the solution of calcium EDTA chelate was used as a masking agent. When a small amount of alkylamine was added, the recovery of uranium became more complete. The effect of alkylamine was probably caused by the adduct formation of uranium chelate with alkylamine.
Spectrophotometric Determination of Cyanide Ion with Mercury(II)- Methylthymolblue Complex
Authors: Nomura Toshiaki
Published: July 2006

Cyanide ion reacted with mercury(II)-methylthymolblue (Hg-MTB) complex to form a mixed ligand complex. Since the resulting mixed ligand complex had a considerable absorption at 615 mμ, the spectrophotometric determination of cyanide ion was performed by measuring the increase in absorption of mercury (II)-methylthymolblue complex caused by formation of this mixed ligand complex. After excess MTB methanol and mercury (II) nitrate solutions were added to a cyanide sample solution which was adjusted to a definite pH value between pH 7.3 and 7.6 with phosphate buffer solution, it was diluted to exactly 50 ml with water. After standing for about 25 min, the absorbance of this solution was measured at 615 mμ against the reagent blank solution. Beer’s law was obeyed in the concentration range of cyanide ion from 5 to 80 μg per 50 ml, and the molar extinction coefficient was found to be about 5100. Taking 55.0 μg of cyanide ion, the standard deviation and variation coefficient of absorbances in the mean value of 10 runs were 0.0019 and 0.90%, respectively. The molar ratio of cyanide ion to Hg-MTB in the mixed ligand complex was found to be 1 : 1.
Cationic Polymerization of Formaldehyde in Liquid Carbon Dioxide. III. Thermal Stabilization of the Resulting Polymer
Authors: Yokota Hisao , Kondo Masatsune , Kagiya Tsutomu , Fukui Kenichi
Published: July 2006

We investigated the acetylation of the endgroups of the polymer chain resulting from the polymerization of formaldehyde in liquid carbon dioxide in the presence of acetic anhydride. The thermal stability and the toughness of the resulting polymer were examined. All of the endgroups of polymer chains were satisfactorily acetylated by means of heating, between 140 and 150°C, the solid polymer, which was separated by discharging the unreacted monomer and carbon dioxide after polymerization. The acetic anhydride which was added in the beginning of the polymerization at a concentration of 5 mol% per monomer, was sufficient to stabilize the polymer thermally. On the acetylating of the polymer, the presence of air or acetic acid in the amount used to initiate the polymerization had no effect on the properties of the acetylated polymer. A simplified purification procedure for the acetylated polymer was presented.
Aminobutadienes. XIII. Anion-exchange Resins from Imidobutadiene Polymers
Authors: Murata Kenichi , Terada Akira
Published: July 2006

A method of preparing new-type anion-exchange resins from 1-phthalimido-, 1-succinimido-, and 2-phthalimido-1,3-butadiene polymers is shown. The procedure consists of two steps, the hydrolysis of the imido groups into free amine, followed by heating with hydrochloric acid to make the amino groups into the hydrochloride, and N-methylation by the Schotten-Baumann method. The anion-exchange resins obtained from the former two polymers show high exchange capacities, such as 5.85 and 7.21 meq/g of dry resin respectively. However, their salt-splitting capacities are not high. The mechanisms of their crosslinking on hydrolysis and of their heat-aging are also discussed.
A Relation between Ion-exchange Selectivity Coefficient and Degree of Distribution for Model Compounds in Solvent Extraction
Authors: Kenjo Tadao , Ito Takuji
Published: July 2006

An analogy of solvent extraction to ion-exchange was taken to explain anion affinities to anion-exchangers. Distributions of the model compound whose cation was the ionogenic group of an anion-exchanger and whose anion the counter ion, between water and an organic solvent, were investigated. The degree of distribution of the model compound for a solvent layer was expected to increase with increasing anion affinities to the corresponding anion-exchanger. Cobalticinium, benziltrimetylammonium and benzildimethylamine salts were employed as model compounds for the polymeric olygomethylene cobalticinium anion-exchanger, the strong base anion-exchange resin and the weak base anion-exchange resin, respectively. The distribution sequences in solvent extraction were essentially identical with the ion affinity series in anion-exchange. From these correlations, the selectivity coefficient for an anion was explained as the affinity of an anion to an ionogenic group with the use of an ion-pair concept. Some differences between ion-exchanges and solvent extractions were discussed.
Studies of the Aggregation of Dyes. A Spectrophotometric Method of Determining the Aggregation Numbers of Dyes
Authors: Hida Mitsuhiko , Yabe Akihiko , Murayama Hiroko , Hayashi Masako
Published: July 2006

The aggregation of dyes in an aqueous or alcoholic solution has been studied spectroscopically by a method named the “maximum slope method.” The method can ascertain the molar absorptivity and formation constant of dye aggregate when a simple equilibrium model between a monomer and an n-mer is assumed to be operative, and when the absorptivity of monomer is given. Further, the molar absorptivities of the monomer and the polymers and the formation constants of the polymers are adjusted, in order to minimize the mean deviation, by an other method, named the “minimum deviation method.” Using the latter method, the parameters of an equilibrium system including a monomer and several polymers can also be calculated. Aggregations of Benzopurprine 4 B and Sky Blue FF in aqueous salt solutions were studied by the above two methods. Aggregations of these dyes in aqueous alcoholic solutions were also discussed.
Infrared Studies of Transition-Metal Nitrosyl (14NO and 15NO) Complexes—Nitrosylruthenium(III), Nitrosylchromium(II) and Nitrosylcobalt(II) Complexes
Authors: Miki Eiichi
Published: July 2006

For K2[RuX5(NO)] (X=Cl and Br), K3[Cr(CN)5(NO)]·H2O, [Cr(NH3)5(NO)]X2 (X=Cl and ClO4) and black-[Co(NH3)5(NO)]Cl2, it was attempted to determine the coordinating atom of the nitrosyl group to the metal atom and to assign the skeletal vibrations between the metal and the nitrosyl group by measuring the effect of the nitrogen isotope 15N on infrared spectra. The isotopic shifts for the 15NO-complex to the 14NO-complex were calculated for two kinds of a linear three-body model, M–N–O and M–O–N (M=metal atom), and the calculated shifts were compared with the observed ones. For nitrosylruthenium and nitrosylchromium complexes, the M–N–O arrangement was found, and of the two absorption bands in the region 530–620 cm−1, the higher wave number was assigned to the M–N stretching vibration and the lower one to the M–N–O bending vibration. For black-[Co(NH3)5(NO)]Cl2, the Co–O–N arrangement was found.
Distribution of Thenoyltrifluoroacetone and Its Scandium Chelate in Ketone Solvent System
Authors: Wakabayashi Toshiki , Takaizumi Katsuko , Seto Kunio , Suzuki Nobuo , Akiba Ken-ichi
Published: July 2006

The distribution equilibria of thenoyltrifluoroacetone (TTA) and its scandium chelate between aqueous solutions with an ionic strength of 0.1 and ketones at 25°C have been studied. The distribution of TTA was correlated with the solubility parameters of the ketones and the correlation between the distribution coefficients of TTA and those of scandium chelate was confirmed. The characteristic properties of ketones were discussed in comparison with those of other oxygen containing solvents.
Reactive Monomers Derived from p-Vinylbenzoic Acid
Authors: Iwakura Yoshio , Uno Keikichi , Nakabayashi Nobuo , Kojima Takakazu
Published: July 2006

Reactive monomers derived from p-vinylbenzoic acid have been prepared which have both a vinyl group and another functional group for addition reaction or condensation reaction. The radical polymerization of these monomers gives high polymers. Monomer reactivity ratios in relation to styrene were obtained for three of these monomers. Plots of Alfrey-Price’s e value vs. Hammett’s σ value show a linear relationship in the case of substituted styrenes. σ values are then estimated by this relation, using e values based on the monomer reactivity ratios. The σ constants assumed for the COCl, (Remark: Graphics omitted.), and NCO substituents are 0.71, 0.64, and 0.27 respectively. These σ values are confirmed by other supporting facts.
Magnetic Moments and d–d Bands of N-n-Propanolsalicylaldiminato-copper(II)
Authors: Kato Michinobu , Muto Yoneichiro , B. Jonassen Hans , Imai Kyoko , Harano Akiko
Published: July 2006

The reaction of cupric acetate with the reaction mixture of γ-aminopropyl alcohol and substituted salicylaldehydes in ethanol gave dimeric copper(II) complexes. The postulated structure of these complexes makes it possible to test the substituent effect transmitted to the coordinating atoms which are not in the superexchange pathway between copper-(II) ions in a pair. The magnetic moments observed at room temperature were corrected for the temperature variations to those at 25°C by graphic method based on Bleaney and Bowers’ equation. The observed substituent effect on the relation between μeff25°C and λmax is different from that observed for dimeric cupric halides complexes of substituted pyridine N-oxides. In these complexes the substituent effect transmits to the bridging oxygen atom in the superexchange pathway. As compared with the parent complex (H), methyl, chloro and benzo groups weakened the magnetic interaction but nitro group strengthened it. An interpretation of the substituent effect is given based on the idea of the mutual influences on the coordinate bonds.
Nitroalkenylferrocene. I. Preparation of 2-Nitro-1-ferrocenylalkenes
Authors: Shiga Mikio , Kono Hiromichi , Motoyama Izumi , Hata Kazuo
Published: July 2006

A wide variety of nitroalkenylferrocenes and their derivatives were synthesized by the condensation of formylferrocene and nitroalkanes. As a condensing agent, either sodium methoxide or a cyclic amine, such as piperidine, pyrrolidine and morpholine, was employed. Condensation using a cyclic amine, which is analogous to the Mannich reaction in nature, gave better results than that using sodium methoxide. The mechanism of the Mannich-type reaction has been discussed, and the formation of a molecular complex between formylferrocene and piperidine has been proposed as an intermediacy.
Novel Reduction of Various Organic Compounds with Water in the Presence of Precipitated Metals
Authors: Sakai Koji , Ishige Masayoshi , Kono Hiromichi , Motoyama Izumi , Watanabe Ken-ichi , Hata Kazuo
Published: July 2006

It was found that various organic compounds were reduced in good yields by refluxing them with precipitated metals in water. Water was proved to be indispensable as a hydrogen donor. The reduction of compounds which are insoluble in water was facilitated by using a mixture of dioxane and water. It is of interest that the reduction of nitriles with this catalyst afforded the hydrochlorides of the corresponding primary amines. The results imply the participation of the chloride ion on the ppt-metal catalyst. A selective reduction of C=C was observed in some α,β-unsaturated ketones, such as mesityl oxide and 1,3-diferrocenyl-2-buten-1-one. The relative activity of the various precipitated metals depends not only upon the kinds of the metals but also upon their combination. It is assumed that the surface of the ppt-Ni is acidic as a result of the coexisting chloride ion, which might participate in the catalytic reaction.
The Chemiluminescence of Indole Derivatives. IV. Correlation between Chemiluminescence and Structure of 2,3-Dimethylindoles
Authors: Sugiyama Noboru , Yamamoto Hiroshi , Omote Yoshimori , Akutagawa Masamoto
Published: July 2006

Four 5-substituted and three 6-substituted 2,3-dimethylindoles and unsubstituted 2,3-dimethylindole were synthesized and their light emission was measured in the presence of atmospheric oxygen and potassium t-butoxide in dimethyl sulfoxide. It was found that the Hammett equation was applicable to their chemiluminescent reaction with ρ value of −1.24. For the 6-position of indole nucleus σp was used, and for the 5-position σm was used. Also, four hydroperoxides of 2,3-dimethylindole bearing substituents at the 5- or 6-position, which emitted light in the presence of potassium t-butoxide in dimethyl sulfoxide, gave linear Hammett plots with ρ value of −2.04. The relationship between the Hammett equation and the chemiluminescence of these inole derivatives has been discussed further.
Macrocyclic Dilactone. II. The General Synthesis of Macrocyclic Dilactone
Authors: Sugiyama Noboru , Maruyama Hiroaki , Gasha Taketoshi , Kashima Choji
Published: July 2006

One previous papar reported the synthesis of 7-hydroxyoctanoic acid dilactone through the dimeric ester. This paper will describe how the dilactone of 12-hydroxystearic acid is synthesized by this method. The dilactone from two kinds of hydroxy alkanoic acid, 7-hydroxyoctanoic acid and 12-hydroxystearic acid, is also otained. From these results, it seems that this new method can be of general use in the synthesis of various kinds of dilactones.
Anionic Copolymerization of Styrene and trans-Stilbene with n-Butyllithium
Authors: Yuki Heimei , Kato Masahiko , Okamoto Yoshio
Published: July 2006

The anionic copolymerization of styrene (M1) and trans-stilbene (M2) by n-butyllithium was investigated, trans-stilbene, which can not homopolymerized by itself, could be copolymerized with styrene in tetrahydrofuran and in benzene by an anionic catalyst. The copolymerization in tetrahydrofuran proceeded with a chain transfer to trans-stilbene, while that in benzene seemed to proceed without the chain transfer. The monomer reactivity ratio, r1 was obtained from the copolymer composition at the complete consumption of M1 assuming that the rate constant, k22, is zero. The r1 values were 2.3 in tetrahydrofuran at 0°C and 18 in benzene at 30°C. The color of the solution changed from red to purple in tetrahydrofuran, while in benzene no change occurred.
Constituents of Leaf Oil from Japanese Pepper
Authors: Kusumoto Shoichi , Ohsuka Akio , Kotake Munio , Sakai Tsutomu
Published: July 2006

The steam-volatile constituents from leaves of Japanese pepper were separated by column chromatography and GLC, and their chemical structures were studied by IR, NMR, and mass spectrometry. The volatile oil was found to be composed of about 100 components; those identified were as follows: 15 hydrocarbons (α- and β-pinene, camphene, sabinene, myrcene, α- and β-phellandrene, limonene, p-cymene, terpinolene, α-copaene, caryophyllene, humulene, α-muurolene, and γ-cadinene), 16 alcohols (2-penten-1-ol, n-hexanol, 3-hexen-1-ol, trans- and cis-sahinene hydrate, cis-linalool oxide, linalool, isopulegol, neoisopulegol, terpinen-4-ol, α- and δ-terpineol, limonen-4-ol, benzyl alcohol, β-phenylethyl alcohol, and nerolidol), 2 aldehydes (2-hexenal and citronellal), 1 ketone (cryptone), 7 esters(isobutyl caproate, linalyl acetate, citronellyl acetate, terpinyl acetate, geranyl acetate, methyl salicylate, and methyl cinnamate) and 2 ethers (1,8-cineol and methyl chavicol).
Electronic Properties of Some Complexes of Tetracyanoquinodimethan with Aromatic Diamines
Authors: Ohmasa Masatake , Kinoshita Minoru , Sano Mizuka , Akamatu Hideo
Published: July 2006

Complexes of tetracyanoquinodimethan have been prepared with a number of aromatic diamines which are varied in their molecular shape and ionization potential. Infrared absorption spectra have revealed most of the complexes to be ionic in character. They showed a strong ESR absorption; in regard to its temperature dependence, however, three modes of variation were observed for these solid complexes. The complexes with N,N′-diphenyl-p-phenylenediamine and N,N′-di-β-naphthyl-p-phenylenediamine were considered to be of non-bonding type and showed no ESR absorption. However, no appreciable difference in semiconductive properties has been found between the ionic type and the non-bonding type complexes, except the complex of diaminodurene-TCNQ(1 : 2). The latter showed a high electrical conductivity and a paramagnetic behavior which was nearly independent of temperature.
A Theoretical Consideration on Chemical Reactions in the Kjeldahl Digestion
Authors: Morita Yazaemon
Published: July 2006

The decomposition of organic nitrogen compounds by Kjeldahl digestion was discussed and some experiments were carried out. The relationship between the amount of sulfuric acid consumed and the amount of ammonia produced at various stages including final ones of the decomposition was examined. As a result, chemical reaction of decomposition was evaluated, and the temperature at the initial stage reveals one of the important factors which determine the ratio of oxidative action of hot concentrated sulfuric acid to reductive action of sulfur dioxide produced in the reaction system. It is concluded that, if the temperature of initial stage is adjusted properly, it is possible to decompose mostly nitro and azo compounds into ammonia by sulfuric acid containing potassium sulfate without reductive pretreatment which has previously been believed to be indispensable.
Polarographic Behavior of Tris(2,2′-bipyridine)cobalt(II) and Tris(2,2′-bipyridine)cobalt(III) in Acetonitrile Solutions
Authors: Tanaka Nobuyuki , Sato Yuichi
Published: July 2006

The electrode processes of tris(2,2′-bipyridine)cobalt(II) and tris(2,2′-bipyridine)cobalt(III) complexes at the dropping mercury electrode in acetonitrile solutions have been investigated by the measurement of direct current, alternating current and Kalousek polarograms. The cobalt(II) complex gave a one-step oxidation and a four-step reduction wave and the cobalt (III) complex, a five-step reduction wave, when tetraethylammonium perchlorate was used as supporting electrolyte. The solution containing the cobalt(II) and the cobalt(III) complexes gave a reversible composite wave. The limiting currents of the first two steps named from positive to negative potentials of the reduction wave of the cobalt(II) complex were diffusion-controlled, the first step being of a one-electron reduction process and the second step, of a two-electron reduction process. From the effect of free 2,2′-bipyridine and water on the reduction wave of the cobalt(II) complex and from the Kalousek polarograms, the electrode processes of the first two steps taking place in the presence of a large concentration of free 2,2′-bipyridine were estimated as,

[Co(bipy)_3]^2+\oversete\underset-e\ightleftharpoons[Co(bipy)_3]^+\overset2e\underset-2e\ightleftharpoons[Co(bipy)_3]^-

The effect of a small concentration of acrylonitrile on the reduction wave of the cobalt(II) complex was studied.
Preparation and Oxidation of Dihydrothiophenes
Authors: Takaya Takao , Kosaka Shigeo , Otsuji Yoshio , Imoto Eiji
Published: July 2006

The preparation and oxidation of 3,4-disubstituted 2,5- and 4,5-dihydrothiophenes are described. The oxidation of these dihydrothiophenes with 30% hydrogen peroxide in acetic acid gave the corresponding thiophene derivatives. However, the oxidation of the same compounds with perbenzoic acid in chloroform gave the corresponding sulfone derivatives. The mechanisms for these oxidation are discussed.
Stereochemical Studies of the 4-Hydroxyl Group of Polymethoxyflavan-3,4-diols
Authors: Hishida Shinzaburo , Umehara Misao , Kayanuma Fujiyuki , Miyazaki Ryoichi
Published: July 2006

In the previous papers, it was suggested that the 4-hydroxyl group of flavan-3.4-trans-diols altered in configuration upon the formation of the isopropylidene derivatives. In order to confirm this suggestion, the isopropylidene derivatives were prepared by the reaction of 4-16OH with acetone-18O, and of 4-18OH with acetone-16O, and the contents of oxygen-18 were analyzed. The oxygen atom from acetone was found in the isopropylidene derivatives of trans-3′,4′,5,7-tetramethoxy-cis- and trans-3′,4′,5′,5,7-pentamethoxy-flavan-3,4-diols.
Reactions of N,N′-Dichlorobarbital and Related Compounds with Organic Compounds
Authors: Otsuji Yoshio , Kuroda Tokuyuki , Imoto Eiji
Published: July 2006

N,N′-Dichlorobarbital (NDCB) reacted as a highly-reactive oxidizing or chlorinating reagent with ether, aldehyde, ketone, olefin and toluene. NDCB also showed a stereospecific chlorination of d-camphor, giving exclusively exo-3-chloro-d-camphor, and one of chloestanone, giving 2β-chlorocholestanone in part. The reactivities of a variety of N-halo compounds were compared and discussed in terms of the polarographic reduction potentials of the N–halogen bond in the compounds.
A Structural Study on the Catalytic Activity in Ionic Polymerization
Authors: Kagiya Tsutomu , Sumida Yūzō , Nakata Tetsuya
Published: July 2006

According to the theoretical conclusion reported previously on the activation energy of the catalytic polymerization, the experimental results relating to the monomer reactivity and the catalytic activity in anionic or cationic polymerization were interpreted. The catalytic activity in ionic polymerization can be quantitatively compared with the relative magnitude of the ionization potential or the electron affinity of monomer and components (A, D) of catalyst (AD). As a measure of the ionization potential or the electron affinity of monomer, the energy of the highest occupied (εho=α+λhoβ) or the lowest vacant (εlv=α−ηlvβ) π level of the monomer has been used, and as a measure of the electron affinity of component D, the pKa of the acid HD or the σ1 value. In anionic polymerization, it was found that the polymerization by the catalyst with the same component A took place only in the combination of the monomer and the catalyst in which the ηlv/pKa value was less than about 2.5×10−2, and that the catalytic activity, with the same component D, depends on the kind of solvent. The results in cationic polymerization were also discussed in connection with the electron affinity of component D or co-catalyst. And the monomer reactivity in ionic polymerization with the same catalyst was quantitatively discussed with the ηlv or λho value of monomer. From the accordance between the theoretical consideration and the experimental data, the present treatment was found to be useful for the purpose of the quantitative study of the catalytic activity and the monomer reactivity in ionic polymerization.
The Reactions of Acetylene Photosensitized by Cd(3P1)
Authors: Tsunashima Shigeru , Sato Shin
Published: July 2006

The reactions of acetylene photosensitized by Cd(3P1) have been investigated at 270±1°C. The main products were benzene and vinylacetylene. The formations of polymer and hydrogen were not observed. From the studies of the effects of pressures and foreign gases on the quantum yields, the product formations were successfully explained by the reactions of excited molecules. The investigation of the reaction of a mixture of hydrogen and acetylene photosensitized by Cd(3P1) suggests that benzene is also formed from the reactions of hydrogen atoms and acetylene molecules.
The Inert Gas Extraction-Gas Chromatographic Determination of Hydrogen in Ferrous Metals
Authors: Kashima Jiro , Yamazaki Takuo
Published: July 2006

The inert gas extraction-gas chromatographic technique has been applied for the determination of hydrogen in ferrous metals. As this method was dependent on gas chromatography, the simplification was performed on the apparatus and the analytical operation. A procedure was evolved, according to which the extracged hydrogen was measured by means of gas chromatography using the precolumn technique, viz., (1) the hydrogen was rapidly transferred from the metal into an argon stream by means of H-F induction furnace, (2) this was concentrated into the cold precolumn for 4 min to collect the total amount of hydrogen from the extraction tube, (3) this was measured by gas chromatography. Analytical results obtained on 3 iron base metals suggest that the method can be widely used for the determination of hydrogen in ferrous metals.
Activation Analysis of Antimony in Tin Based on an Internal-Monitor Method using Thermal Neutrons
Authors: Oka Yoshinaga , Kato Toyoaki , Tsai Hui-Tuh
Published: July 2006

An internal-monitor method proposed previously has been applied to the determination of trace amounts of antimony in tin by activation with thermal neutrons. After the antimony activity is chemically separated from the irradiated sample, the γ-ray spectrum corresponding to a mixture of 124Sb and 125Sb formed by the β− decay of 125m,125Sn is measured. Synthetic mixtures of antimony and tin with known weight ratios have been prepared to check the accuracy of the method. Good proportionality has been obtained between the ratios of the 124Sb to 125Sb activities and the ratios of the concentrations. By using this relationship, antimony analysis can easily be carried out. The content of antimony in a sample of tin down to 0.2 ppm can be determined with a relative error of ±2%.
Stereospecific Synthesis of 1,4-Dienes. III. The Cobalt Chloride-Phosphorus Compound-Triethylaluminum Catalyst System
Authors: Hata Go , Miyake Akihisa
Published: July 2006

The admixture of cobalt chloride, (RO)nPCl3−n(n=0–3), and triethylaluminum catalyzes the codimerization of 1,3-dienes with ethylene to give exclusively cis isomers of 1,4-dienes, which result from the 1,4-addition of a C–H bond of ethylene to the 1,3-dienes. The addition of ethylene to methyl-substituted 1,3-dienes occurs predominantly on the substituted sides of the 1,3-dienes. The activity of the catalyst is strongly affected by the nature of the trivalent phosphorus components.
The Hydrogenation of Pyran Derivatives. IV. The Skeletal Rearrangement in the Gas-phase Dehydration of Tetrahydropyran-2-methanol
Authors: Misono Akira , Osa Tetsuo , Sanami Yoshitomo
Published: July 2006

The gas-phase dehydration of tetrahydropyran-2-methanol (TPM), prepared by the hydrogenation of the acrolein thermal dimer (3,4-dihyro-2H-pyran-2-carboxaldehyde (AD)), was investigated over various catalysts under atmospheric pressure. In this reaction, some of the pyran ring was found to be rearranged rapidly to a seven- or five-membered ring. For example, the highly-purified and crystalline η-alumina without any carrier produced cyclopentanecarboxaldehyde (GPA) as the main product in the yield of 71% at 330°C. Over the commercial alumina catalyst, considerable amounts of 2,3,4,5-tetrahydrooxepine (THO) and oxepane (OXP) were produced as by-products, though CPA was the main product; in some cases, as much THO and OXP were produced as CPA. On the other hand, the use of a dehydrogenation catalyst resulted in THO as the main product and CPA as a by-product; in the case of the use of copper-chromium oxide supported on Kieselguhr, with hydrogen as a carrier gas at 430°C, the yields of THO and CPA were 44.8% and 4.7% respectively. In these skeletal rearrangements, the seven-membered carbonium ion compound produced by the Wagner-Meerwein-type rearrangement must be a reaction intermediate. From this intermediate, mainly CPA was produced over alumina, influencing the lone-electron pair of the ethereal oxygen. THO, on the contrary, was produced mainly over a dehydrogenation catalyst. Moreover, twice as high a yield of 1,6-hexanediol was obtained from the hydrogenation of the hydrated THO than from the hydrogenolysis of TPM or AD, as has been noted in a previous paper.
The Stereochemistry of Perhydroacridines and Perhydrophenanthridines
Authors: Masamune Tadashi , Ohno Masaji , Takemura Ken , Ohuchi Shigehiro
Published: July 2006

The configurations of three stereoisomers, α, β and γ, of perhydroacridine and those, α, β and γ, of perhydrophenanthridine have been assigned as trans,syn,trans, trans,anti,cis, trans,syn,cis, trans,anti,trans, trans,syn,cis and cis,syn,cis, respectively, on the basis of both the process of their syntheses and the rate of formation of methiodides of the N-methyl derivatives. These configurations are consistent with the infrared-spectral behavior of their N-methyl derivatives in carbon tetrachloride solutions containing n-butanol as well as with the result of their exhaustive methylations. The relative steric requirement of the lone pair and the hydrogen on the N atom is also discussed.
A Cationic Polymerization of N-Phenylethylenimine by Various Carboxylic Acid Catalysts
Authors: Kagiya Tsutomu , Kondo Tomizo , Fukui Kenichi
Published: July 2006

The polymerization of N-phenylethylenimine was carried out using various carboxylic acid catalysts (pKa=0.23–4.87) in acetonitrile at 0°C. The number-average molecular weight was determined by measuring the allyl-group content in the infrared spectrum of the polymer initiated with allylformate. The relationship between the number-average molecular weight and the reduced viscosity was determined. Both the conversion and the number-average molecular weight increased with the reaction time when weak acid (pKa=2.85–4.87) was used. On the other hand, when strong acid (pKa=0.23–2.85) was used, conversion reached a limited value which increased in proportion to the amount of the catalyst. With the strong acid, the efficiency factor of the catalyst was almost unity, and was independent of the reaction time. On the other hand, with the weak acid, it was smaller than unity and increased proportionally with the amounts of the polymer formed. The rate constants of the elementary reactions were evaluated on the basis of the kinetic study. The rates of the initiation, propagation, and termination reaction increased with a decrease in the pKa of the acid. With a weak acid, the termination reaction is slow at a low temperature (below 50°C), and increases with the reaction temperature, whereas with a strong acid the termination reaction occurs markedly even at a low temperature (above 0°C), and increases slightly with the temperature. The mechanism of the termination reaction was discussed on the basis of a structural study of the end group of the polymer.
The Grignard Reaction of 3-Halotropolone Methyl Ethers
Authors: Tsuruta Haruki , Mukai Toshio
Published: July 2006

The Grignard reaction of the methyl ethers (I and III) of 3-bromotropolone and those (II and IV) of 3-chlorotropolone with methylmagnesium iodide or phenylmagnesium bromide were investigated. When I or II was allowed to react with methylmagnesium iodide, 2-methoxyphenyldimethylcarbinol (V) and 2-methoxy-6-isopropylphenol (VI) were obtained. The reaction of I or II with phenylmagnesium bromide afforded 2-phenyl-7-halotropones (XIII or XVII), accompanied by 2-halobenzophenones (XV or XVIII) and the triphenylcarbinol derivative (XIV). The Grignard reaction of III or IV using phenylmagnesium bromide gave 2-phenyl-3-halotropones (XVI or XIX). The mechanistic pathway for the formation of these products was discussed.
Reaction of Alkylbenzene. III. The Reaction of sec-Butylbenzene Induced by Aluminum Chloride
Authors: Itoh Kazuyoshi , Yamada Genji , Hamanaka Sawako , Ogawa Masaya
Published: July 2006

The products successively obtained from the reaction between sec-butylbenzene and aluminum chloride were investigated. Transalkylation was the first observed reaction, followed by the isomerization of the side chain and then by dealkylation. The isomerization of the side chain was observed in the transalkylation products of a high basicity, such as m-di- and 1,3,5-tri-substituted compounds, and not in the others. The n-butane, resulting from dealkylation, was obtained simultaneously with 2,2di-phenylbutane. On the basis of these results, the reaction mechanism was discussed.
Decomposition of Formic Acid over Metal Phthalocyanines
Authors: Tanaka Sadao , Onishi Takaharu , Tamaru Kenzi
Published: July 2006

The decomposition of formic acid was studied over two sorts of metal phthalocyanines: Mg-and Fe-phthalocyanines. The rates of the decomposition reactions over Mg-Phc and Fe-Phc were proportional to the pressure of formic acid, and the decomposition proceeded to dehydrogenation as well as to dehydration over these phthalocyanines. The isotope distribution in the hydrogen (H2, HD, and D2) produced by the decomposition of HCOOD leads to the conclusion that the hydrogen molecule is mainly formed between the hydrogen atom bonded to the carbon atom and that bonded to the oxygen atom in the formic acid molecule. Formic acid was adsorbed to a considerable extent over Mg-Phc in the temperature range between 70°C and 220°C. The amount of formic acid adsorbed obeyed the Langmuir adsorption isotherm, and the infrared spectra demonstrated the presence of the formate ion HGOO− on the Mg-Phc. It was also confirmed that Mg-Phc was hydrogenated during the course of the decomposition. The adsorption during the catalytic reaction was also measured. These measurements revealed that the overall rate of the reaction is proportional to the amount of formic acid adsorbed. The mechanism of formic acid decomposition was discussed on the basis of these results.
Quenching of the Scintillation from a γ-Irradiated Cyclohexane Solution Containing p-Terphenyl by Electron Scavengers, Positive Ion Interceptors and Some Hydrocarbons
Authors: Saito Tsunenari , Takahashi Koji , Sato Shin
Published: July 2006

The luminescence from a cyclohexane solution containing p-terphenyl irradiated with 60Co γ-rays has been quenched by various compounds. The quenching efficiencies were found to be in the following order; sulfur hexafluoride∼carbon tetrachloride>nitrous oxide>ethanol>ammonia>carbon dioxide. These compounds are known in radiation chemistry as electron scavengers or as positive-ion interceptors. Cyclopropane and ethylene have also shown an appreciable quenching ability, but n-butane has shown scarecely any. These results have been explained by assuming that ionic reactions are responsible for the luminescence from a cyclohexane-p-terphenyl scintillator.
The Analysis of the Solubility of Hydrocarbons in Water
Authors: Shinoda K\={o}z\={o} , Fujihira Masamichi
Published: July 2006

Enthalpy and entropy of solution of non-polar solutes in water diverge strikingly from the normal behavior established for regular solutions. This abnormality has been considered mostly due to the iceberg formation around solute molecules in water. The abnormal solubility and enthalpy and entropy of solution of non-polar solutes in water have been explained coherently by the extension of the regular solution theory, taking into account the iceberg formation of water molecules. Unlike currently accepted views on the hydrophobic bonding, it is concluded that the enthalpy of mixing (interchange) of non-polar solute with water is large, but the enthalpy decrease due to the iceberg formation of water largely cancels the enthalpy increase of mixing (interchange). Thus, the apparent enthalpy of solution is small or negative at low temperature. It is concluded that 1) the small solubility of non-polar solutes in, water is not an entropy effect, and 2) the solubility of non-polar solutes is promoted by the iceberg formation of water molecules.
β-Diketonates of a Few Lanthanide Elements
Authors: Hasan M , Kumar K , Dubey S , Misra S N
Published: July 2006

The reactions of isopropoxide of praseodymium and neodymium with benzoylacetone, dibenzoylmethane have been studied and the derivatives of the type M(O–iPr)2(lig.), M(O–iPr)-(lig.)2 and M(lig.)3 (where lig.=benzoylacetone or dibenzoylmethane) have been isolated. The isopropoxide-diketonates on treatment with tertiary butanol interchange their isopropoxide group with tertiary butoxide group. Anhydrous acetylacetonates of lanthanum, praseodymium, neodymium and samarium have been prepared from the reactions of the alcoholic solution of the chlorides with alcoholic solution of ammonium acetylacetonates. The molecular weights of these β-diketonates and alkoxides β-diketonates have been measured ebullioscopically in boiling benzene.