bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthetic Reactions by Complex Catalysts. XVI. The Dimerization of Acrylonitrile and Acrylate by Means of the Metal-Isocyanide Complex
Authors: Saegusa Takeo , Ito Yoshihiko , Kinoshita Hideo , Tomita Shimpei 
Published: July 2006

Abstract
Acrylonitrile and acrylate were dimerized to 2-methyleneglutaronitrile and 2-methyleneglutarate respectively by the binary catalyst system of a copper compound and an isocyanide in the presence of a protic solvent such as t-butanol. Transition metal acetylacetonates, such as Fe(II and III), Co(II and III), and Ni(II), in combination with isocyanide were also effective for this dimerization. A mechanistic discussion has been presented.
The Chemistry of Americium. I. A Study of the Preparation of Am (V) and Its Behavior by Means of TTA Extraction
Authors: Hara Mitsuo 
Published: July 2006

Abstract
The method for preparing Am(V) in various solutions was investigated by utilizing the difference in extractability between Am(V) and Am(III) in an TTA-isobutanol extraction system; Am(III) was quantitatively extracted with 0.1m TTA in isobutanol from a 1m acetate buffer solution at a pH greater than 3, while the percentage of Am(V) extracted into the organic phase was increased substantially with an increase in the pH from 3 to 5. When the organic phase containing Am(V) was shaken with an aqueous phase having a proper pH value and composition, Am(V) was selectively stripped into the aqueous phase. The stability of the valency state of Am(V) in the perchlorate, the acetate, and the sulfate solutions was then studied by examining the variation in the percentage of americium extracted as a function of the standing time. The rate of change in the valency state in the acetate and the perchlorate media is very slow, while it is rather rapid in the sulfate medium. This difference may be attributable to the faster rate of the disproportionation reaction of Am(V) in the last medium than in the former two. By applying the above results, the chemical behavior of Am(V) in the aqueous solution was investigated by TTA extraction; it was found that Am(V) would be in the form of AmO2+ in the absence of a complexing reagent. By the addition of acetate ions, the step-by-step formation of the acetate complex of Am(V) was observed. The stability constants of [AmO2Ac] and [AmO2Ac2]− were determined to be (25.0±3.1) (mol/l)−1 and (12.8±1.2) (mol/l)−2 respectively.
Stereospecific Polymerization of Allyl Vinyl Ether by BF3·OEt2
Authors: Yuki Heimei , Hatada Koichi , Ohta Koji , Sasaki Takashi 
Published: July 2006

Abstract
The polymerization of allyl vinyl ether was carried out by means of BF3·OEt2. The reaction proceeded through the vinyl double bond, and a polymer with allyl ether side chains was obtained. The effects of the polymerization conditions on the stereoregularity of the polymer were studied by means of NMR spectroscopy using a spin decoupling technique. A highly isotactic polymer was obtained at −78°C in toluene. The isotacticity of the polymer decreased slightly with a rise in the reaction temperature and with an increase in the initial monomer concentration. When the reaction was carried out in a mixture of toluene and nitroethane, a marked decrease in the isotacticity and the solution viscosity of the polymer was observed with an increase in the amount of nitroethane. The solution viscosity of the polymer decreased with an increase in the polymerization temperature and the catalyst concentration, and increased with an increase in the initial monomer concentration. The reaction between the polymer and HBr in acetic acid yielded a ternary copolymer consisting of vinyl alcohol, vinyl acetate, and vinyl bromide units.
Syntheses of Optically Active α-Amino Acids from Esters of α-Keto Acids by Hydrogenolytic Asymmetric Transamination, A Solvent Effect
Authors: Harada Kaoru , Yoshida Takao 
Published: July 2006

Abstract
Optically active α-amino acids were synthesized from esters of α-keto acid azomethines by catalytic hydrogenation. Solvent effect of the reaction was studied and the possible steric courses are discussed.
Conformers and Intramolecular Hydrogen Bond of trans-2-Halocyclohexanols
Authors: Fujimoto Etsuko , Takeoka Yoshiko , Kozima Kunio 
Published: July 2006

Abstract
By infrared studies it has been ascertained that trans-2-halocyclohexanols possess two conformers, namely, the ee-isomer and the aa-isomer, both in the liquid and in a solution, while only the eeisomer exists in the solid. In a dilute solution the ee-isomer is more stable and exists exclusively in the form with an intramolecular hydrogen bond. The values of the energy difference between the two isomers are 1.3, 1.9, and 2.2 kcal/mol for the chloro-, the bromo-, and the iodo-derivative respectively. The magnitude of the frequency shifts of the O–H stretching bands increases in the order: Cl&lt;Br&lt;I. These facts show that the intramolecular hydrogen bond stabilizes the ee-isomer and that the strength of the hydrogen bond increases in the order: Cl&lt;Br&lt;I. The electrostatic energy increases in the order: Cl&gt;Br&gt;I, while the delocalization energy due to the chargetransfer increases in the opposite order. Therefore, it can be concluded that the energy due to the charge-transfer contributes dominantly to the energy of the intramolecular hydrogen bond formed in the ee-isomer of trans-2-halocyclohexanols.
Corrosion Reaction of Iron in Phosphatizing Solution
Authors: Shirakawa Ryokai , Takeda Shiro , Umegaki Takao , Okabe Taijiro 
Published: July 2006

Abstract
An electrochemical investigation was made on the corrosion reaction of iron in phosphatizing solution to clarify the mechanism of the formation of phosphate coating. Polarization characteristic curves revealed the corrosion of iron to be under cathodic control implying that the formation of phosphate coating occurs thus under cathodic control. The corrosion rate increased considerably by the addition of KNO3 or KNO2 which is used as an accelerator in phosphatization. The formation of phosphate coating was much accelerated by cathodic polarization of iron, but repressed by anodic polarization and rotation of the iron electrode.
Thermal Annealing Behavior of the Recoil 57Co Formed by the Decay of 57Ni-Labeled Hexamminenickel(II) Complexes
Authors: Omori Takashi , Wu Shaw-Chii , Shiokawa Takanobu 
Published: July 2006

Abstract
Thermal annealing reactions of 57Co formed by the EC and β+-decay of the 57Ni-labeled hexamminenickel(II) halide complexes were investigated in detail by means of ion-exchange techniques. When the annealing is carried out at high temperatures, the chemical behavior of 57Co is remarkably affected by the thermal decomposition of the parent and daughter complexes. In the intrinsic annealing, however, the annealing curves have characteristic shapes and the plateau yields of 57Co(NH3)63+ ion are independent of the temperature, depending on the nature of the outer-sphere anion. The unusual oxidation reaction of the recoil 57Co(II) species is explained by the action of the crystal defects in the near-neighborhood of the recoil site.
Kinetic Studies of the Electron Transfer Reaction in Iron(II) and Iron(III) Systems. III. Complex Formation and Catalytic Action with Thiocyanate Ion in Dimethyl Sulfoxide
Authors: Wada Goro , Yoshizawa Noriko , Sakamoto Yoko 
Published: July 2006

Abstract
The formation constants K1 and K2 of the complexes Fe(NCS)2+ and Fe(NCS)2+ in dimethyl sulfoxide (DMSO) and the rate constants and the activation parameters of the electron transfer reaction between Fe(II) and Fe(III) in DMSO catalyzed by thiocyanate ion were measured. K1 and K2 are (8.4±0.9)×102 m−1 and (0.97±0.10)×102 m−1 at μ=0.1 m and 25°C, respectively. The apparent rate constant kapp is nearly independent of acid concentrations and increases markedly with total thiocyanate ion concentration. The rate constants k1and k2 of Fe2+-Fe(NCS)2+ and Fe2+-Fe(NCS)2+ systems are (2.24±0.35)×102 m−1sec−1 and (2.96±0.64)×103 m−1 sec−1 at μ=0.2 m and 25°C, respectively. ΔH1\eweq=8.9±1.0 kcal/mol and ΔS1\eweq=−17±3 cal/deg·mol are obtained from the temperature dependence of kapp. From a comparison with the data of cases catalyzed by Cl− and SCN− ions in water and DMSO, the present electron transfer reaction is deduced to proceed probably via the inner-sphere mechanism with the SCN− ion as a bridging ligand, similar to the Cl− ion-catalyzed reaction in DMSO.
Infrared Spectra of Pentacyanonitrosylmanganese (14NO and 15NO) Complexes
Authors: Miki Eiichi , Kubo Soto-o , Mizumachi Kunihiko , Ishimori Tatsujiro , Okuno Hisateru 
Published: July 2006

Abstract
The 15NO-complexes for K3[Mn(CN)5(NO)]·2H2O, K3[Mn(CN)5(NO)] and Ag2[Mn(CN)5(NO)] were prepared. By measuring and calculating the effect of the nitrogen isotope 15N on the infrared spectra, the Mn–N–O arrangement was found in all the complexes, and the absorption bands due to the skeletal vibrations between the manganese and the NO group were clearly assigned.
On the Growth Rate of Selenium Spherulite
Authors: Hamada Shuichi 
Published: July 2006

Abstract
The Radical growth rates of the selenium spherulites were measured by the microscopic method at temperatures ranging form 128.4°C to 192.3°C. The radial growth rate increased with an increase in the crystallization temperature up to about 180°C, reached a maximum value of 87.0 μ/min, and then decreased abruptly, judging form the observation of organic polymers at crystallization temperatures near their melting points. The process of the spherulite growth of selnium near the melting point could not be interpreted by only two elementary processes, that of the segmental jump and that of the formation of a two-dimensional nucleus of a critical size. The variation in the radial growth rate of selenium with the temperature was explained by considering the bond-breaking process as an elementary process. The estimated surface free energy at the liquid-crystal interface was 25.1 erg/cm2; this value was a reasonable one.
The Indirect Determination of Microamounts of Mercury(II) by Means of Dithizone Extraction and AC Polarography
Authors: Kambara Tomihito , Hara Minoru 
Published: July 2006

Abstract
It was found that dithizone in an aqueous alkaline solution shows sharp AC polarographic peaks; the indirect determination of mercury by means of these peaks was investigated. After the extraction of mercury(II) dithizonate into benzene, the excess dithizone was eliminated. Then the mercuric ion was stripped into the aqueous phase containing the iodide ion. The isolated dithizone in the benzene layer was back-extracted into the alkaline supporting electrolyte solution and the polarogram was recorded. By the present method, up to 30 μg of mercury can be determined.
The Effect of Solvents on the Adduct Formation of Uranyl Thenoyltrifluoroacetonate with Tributyl Phosphate
Authors: Akiba Kenichi , Suzuki Nobuo 
Published: July 2006

Abstract
Addition compound formation between uranyl bis-thenoyltrifluoroacetonate (UO2A2) and tributyl phosphate(S) was studied by a partition method, using uranium-237 as the tracer. The formula of the adduct complex was shown to be UO2A2·S. The solvent effect on the adduct formation constant was taken into account in connection with the activity; the activity coefficients of each species in various solutions were calculated from the molar volume and the solubility parameter. The formation constants based on the molar fraction, Kx, in a number of solvents were pre-estimated, employing logKx=7.08 in carbon tetrachloride as a reference. They are in agreement with the observed values. The formation constant in terms of activity was found to be constant logKS°=5.77±0.30. A correlation between the formation constants of the two adducts, UO2A2·S and ZnA2·S, was demonstrated.
Electronic Spectra of Phenanthrene Derivatives. Effect of Substitution
Authors: Akiyama Shuzo , Nakagawa Masazumi , Nishimoto Kichisuke 
Published: July 2006

Abstract
During the course of studies on the spectral regularities of linear conjugated systems bearing aromatic terminal groups (cf Tetrahedron Lett., 1964, 719; ibid., 1968, 1121; This Bulletin, 39, 2320 (1966); ibid., 40, 340 (1967)), we found that the free electron model (FEM) cannot explain the effect of substitution on the electronic spectrum of phenanthrene. In order to get further information the electronic spectra of forty-eight phenanthrene derivatives each bearing a substituent at 2-, 3-, or 9-positions have been examined, and it was found that the electronic spectra of these derivatives also cannot be explained on the basis of FEM. SCF-MO-CI calculation has been carried out on phenanthrylpoly-ynes and hydroxyphenanthrenes revealing that the discrepancy between the observation and the expectation from FEM in the behavior of La and Lb of phenanthrene derivative is attributable to a complex configuration interaction.
Sterically Controlled Syntheses of Optically Active Organic Compounds. XIV. Syntheses of Dipeptides from N-(α-Ketoacyl)-α-amino Acid Esters
Authors: Harada Kaoru , Matsumoto Kazuo 
Published: July 2006

Abstract
Optically active α-amino acids were synthesized from azomethines of N-α-ketoacyl-amino acid esters by catalytic hydrogenation. When optically active (S)-alanine was used, (R)-amino acyl-(S)-alanine ester was obtained. When alkyl groups of optically active (S)-amino acids in the N-α-ketoacyl-amino acid esters were larger than ethyl group, the configurations of newly formed amino acids were found to be (S). From these results possible steric courses of the asymmetric syntheses are discussed.
The Catalytic Dehydrogenation of Alcohols with Reduced Copper under Ultraviolet Light
Authors: Nakamura Shigeaki , Kawamoto Kazuaki 
Published: July 2006

Abstract
In order to investigate whether or not the dehydrogenation activity of the reduced copper is affected by ultraviolet light, the reaction of such alcohols as ethanol, 1-propanol, 2-propanol, and 1-butanol was carried out with reduced copper and ultraviolet light at 250°C. It was found that the conversion of alcohols and the yield of aldehydes were larger with the reduced copper under ultraviolet light than without the light, and that aldol condensation for the ethanol reaction was recognizable when the reduced copper catalyst was used without ultraviolet light.
Purity Determination of Organic Compounds by Time-temperature Freezing or Melting Curves with a Simplified Apparatus
Authors: Enokido Hisae , Shinoda Takako , Mashiko Yo-ichiro 
Published: July 2006

Abstract
A simplified apparatus has been constructed for determining the purity of organic compounds by time-temperature freezing or melting curves. The sample cell is small and the amount of the sample needed in only 0.2 ml or 2 ml. The thermometers used are a Shimadzu platinum resistance thermometer calibrated by the measurement of fixed points and a chromel p-constantan thermocouple calibrated against a standard platinum thermometer with a precision better than ±0.03°. Purities of several hydrocarbons were determined by measuring their freezing and melting curves.
The Catalytic Dehydrogenation, Dehydroxylation, and Dehydroxymethylation of Benzyl Alcohol. II. The Effects of Sodium Compounds as Additives
Authors: Ishige Masayoshi , Sakai Koji , Kawai Masatoshi , Hata Kazuo 
Published: July 2006

Abstract
The reaction of benzyl alcohol has been examined over stabilized nickel (S-Ni) catalysts which have been modified by treating the catalyst surface with solutions of sodium compounds; this has been done in order to obtain some information about the relation between the behavior of the molecule adsorbed on the metal catalyst and the chemical nature of the catalyst surface. On the basis of the fH, fCH3, and fCHO values, which were defined as representing the catalytic activity for the formation of benzene, toluene, and benzaldehyde respectively, the variation in the activity for each modified S-Ni was evaluated. The general aspects may be summarized as follows: (1) The reaction is generally retarded with an increase in the amount of a sodium compound which is adsorbed on the catalyst during the modification process. (2) When the modification is of a lower grade, the effect of additives on the catalytic activity represented by f values is in the following order: NaNO3&lt;NaOH&lt;Na2S2O3&lt;NaI&lt;NaBr&lt;NaCl. (3) A proper amount of NaCl on the catalyst promotes the reaction. The increase in SH and SCH3 values, which were defined as representing the selectivity factors for the formation of benzene and toluene toward that of benzaldehyde, is roughly associated with the increase in the corresponding f values.
Decomposition of cis- and trans-α-Phenylcinnamoyl Peroxide and t-Butyl cis- and frans-α-Phenylperoxycinnamate. Stereochemistry of 1,2-Diphenylvinyl Radical
Authors: Wada Naoto , Tokumaru Katsumi , Simamura Osamu 
Published: July 2006

Abstract
Decomposition of trans- and cis-α-phenylcinnamoyl peroxide and t-butyl trans- and cis-α-phenylperoxycinnamate were carried out in solution and the products were determined. t-Butyl trans- and cis-α-phenylperoxycinnamate, on decomposition in carbon tetrachloride, gave mixtures of cis- and trans-α-chlorostilbene in the same cis to trans ratio at 110°C, but in different ratios at 80°C, the higher ratio being obtained from t-butyl trans-α-phenylperoxycinnamate. In the decomposition of trans- and cis-α-phenylcinnamoyl peroxide in various solvents at 60°C, the α-halostilbenes formed in carbon tetrachloride and bromotrichloromethane and the stilbenes produced in cumene, chloroform and triethylsilane were shown to be richer in the isomer of the same configuration as the peroxide decomposed. The stereochemical course of the reaction of the 1,2-diphenylvinyl radical generated from these peroxy-esters and peroxides is discussed.
The Thermal Rearrangement and Degradation of 2,3-Bis(alkylimino)oxetane
Authors: Saegusa Takeo , Taka-ishi Naotake , Ito Yoshihiko 
Published: July 2006

Abstract
The thermal rearrangement of 2,3-bis(alkylimino)oxetane (1) was investigated. At 200°C, 2,3-bis(secondary alkylimino)oxetane was converted into 3-imidazolin-5-one (8). 2,3-Bis(tertiary alkylimino)oxetane was stable at 200°C, but it was rearranged at 300°C to a cyclobutanone derivative (18). A mechanism involving the β-lactam intermediate (12) (17) formed by the Chapman rearrangement of 1 was proposed.
Radical Cations of Halogenated Tetrahydroxybenzene Diethylene Ethers
Authors: Asahara Teruzo , Sen\={o} Manabu , Teshirogi Takuma 
Published: July 2006

Abstract
It was observed that two newly-prepared substances, 3,6-dichloro- and 3,6-dibromo-1,2,4,5-tetrahydroxybenzene diethylene ether, underwent one-electron oxidation to afford the corresponding radical cations in concentrated sulfuric acid. Their electronic spectra and ESR spectra were recorded in a sulfuric acid and nitromethane-AlCl3 medium. The chloro-compound gives an ESR spectrum with a hyperflne structure, while the bromo-compound shows a spectrum without hyperflne splitting. Some different behavior was observed in several model compounds with similar structures.
The Anchoring Effect of the Fine, Powdery Copolymer of Glycidyl Methacrylate-Divinyl Benzene for Antioxidants in Polypropylene
Authors: Mizutani Yukio , Kusumoto Koshi , Hisano Shigeo 
Published: July 2006

Abstract
The anchoring effect of the fine, powdery copolymer of glycidyl methacrylate-divinylbenzene, blended in polypropylene, for phenolic antioxidants was studied by the oxygen absorption method and by studying the infrared spectrum. As a result, the anchoring effect was recognized, and it was confirmed that the effect came from the reaction between the phenolic hydroxyl groups of antioxidants and the epoxy groups of the fine, powdery copolymer and that, furthermore, the anchoring effect was related to the molecular structure of the antioxidants. It is interesting to note that these results suggests that polymeric antioxidants practically overcome the defect of the migration or the volatility observed on low-molecular-weight antioxidants.
The Effect of Pressure on the Rate of the Acid-catalyzed Hydration of Propylene
Authors: Takaya Haruo , Todo Naoyuki , Hosoya Tadasuke , Minegishi Toshio 
Published: July 2006

Abstract
In order to confirm whether a water molecule (or molecules) is held in a protonated activated complex by electrostatic interaction or by a partial valence bond, the pressure dependency of the activation volume, ΔV\ewq, for the hydration of propylene was measured at 180°C. The pressure effect on the rate of the hydration of propylene was studied in such dilute sulfuric acid solutions of a 0.0000108 mole fraction (0.00060n under S.T.P.) that the dielectric constant, D, and the density of pure water could be replaced for those of the reacting solution. The absolute value of the ΔV\ewq decreases steeply from 19 ml/mol at 300 kg/cm2 to 4 ml/mol at 5000 kg/cm2. The activation energies and entropies, obtained from the temperature dependency of the reaction rate, are 22.7 kcal/mol and −16.6 e.u./mol respectively at 1000 kg/cm2 and 21.9 kcal/mol and −17.0 e.u./mol respectively at 3000 kg/cm2. The ΔV\ewq is approximately proportional to the −∂D⁄D2∂p value, (D: dielectric constant of medium; p: pressure), which follows from the Krichevski equation; hence, it was concluded that the contraction of water around an activated complex by electrostatic interaction contributes to the ΔV\ewq and that a water molecule (or molecules) is held in the activated complex by electrostatic interaction. The case of a water molecule being held by a partial valence bond was discussed in terms of the molar volumes of the reactants.
A Theoretical Study of the Catalytic Activity of Group I Metal Salts in the Homogeneous Liquid-Phase Oxidation
Authors: Ohkubo Katsutoshi , Shimada Hidetoshi , Shiotani Yasuhiro , Okada Masahide 
Published: July 2006

Abstract
A theoretical consideration of the catalytic activity of group I metal salts, especially of lithium ones, for the homogeneous liquid-phase oxidation of hydrocarbons was developed by extended Hückel molecular orbital calculations, with particular reference to the interaction between the salts and molecular oxygen. We made several findings. First, a marked activity of lithium salt-catalysts was reflected by a remarkable “electron-partial occupation” of the lithium cation in their salts. Second, a strong interaction of the lithium catalyst with O2 occurred at the angle of 15° to the direction of the 1πg-orbital expansions of O2. Third, the lithium catalyst participated strongly in the activation of O2 at the distance of 2 Å–3 Å, increasing the electron-population of one oxygen atom located farther from the lithium cation. Finally, the contribution of the “activated” oxygen molecule to the initiation of the oxidation of hydrocarbons was discussed.
ESR Study of Adsorbed Monomer and Dimer Cation Radicals of Benzene and Its Methyl Derivatives
Authors: Nagai Siro , Ohnishi Shun-ichi , Nitta Isamu 
Published: July 2006

Abstract
Benzene, toluene, o-, m-, p-xylene, and mesitylene adsorbed on silica gel were γ-irradiated at −196°C. ESR spectra observed at −196°C for these systems at low contents of the methylbenzenes were assigned to the respective monomer cations. Dimer cations of benzene, toluene, and p-xylene were produced on γ-irradiation at −196°C of the adsorbed systems at higher contents and also by the reaction of monomer cations and neutral molecules at higher temperature than −160°C.