bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Rotatory Dispersion and Stereochemistry of Organic Compounds. IX. The Nitrates of Glucose
Authors: Tsuzuki Yojiro , Tanabe Koko , Okamoto Kikuhiko 
Published: July 2006

Abstract
We have measured the rotatory dispersion (RD) and the ultraviolet absorption of twelve nitrates of glucopyranosides carrying a nitrate chromophore, –O–NO2, in the position of the carbon atoms 1, 2, 3, 4, and 6. On the basis of the experimental results and of those results already reported concerning four nitrates, studies have been made as to the correlation between the configuration and the Cotton effect. The sign of the Cotton effect has been determined by the RD curve as well as by the dispersion constant as computed from the dispersion data. A regular relation has been found, namely, irrespective of the position of the nitrate group on the carbon atom, α-glucosides with α nitrate chromophore in the α- or (d)-configuration show negative Cotton effects, while the sign of the Cotton effects of the corresponding β-glucosides is positive. On the contrary, α-glucosides with a nitrate chromophore in the β- or (l)-configuration show positive Cotton effects, while the sign of the Cotton effects of the corresponding β-glucosides is negative.
The Cation Effect on the Polarographic Reduction of cis-Dioxalatodiaquochromate(III) and Trioxalatochromate(III) Ions
Authors: Tanaka Nobuyuki , Itabashi Eiki , Tamamushi Reita 
Published: July 2006

Abstract
The cation effect on the polarographic reduction of cis-dioxalatodiaquochrormate(III) and trioxalatochromate(III) ions has been reported. cis-Dioxalatodiaquochromate(III) ions give an irreversible wave corresponding to a three-electron reduction in the solutions of univalent electrolytes, while they give a double wave in the solutions of bivalent electrolytes, the first wave being of a one-electron reduction and the second wave, of a two-electron reduction. Trioxalatochromate(III) ions are reduced to chromium(0) in the univalent and the bivalent electrolyte solutions at more negative potentials than cis-dioxalatodiaquochromate(III) ions. The reduction potentials of these complex anions depend on the nature and the concentration of cations of electrolytes present in the solution, and shift to less negative potentials with increasing ionic charges of the cation and, at the constant ionic charge, with decreasing radii of the hydrated ion and increasing concentrations of the cation present. The cation effect was explained by taking into consideration of both the structure of the electrical double layer and the formation of ion-pairs.
The Automatic Measurement of the Ohmic and Capacitive Components of the Impedance on a Platinum Electrode in Transient States
Authors: Shibata Shigeo 
Published: July 2006

Abstract
A new technique with an electronic circuit is described in which the ohmic and the capacitive components of the impedance of the electrode-solution interface may be registered simultaneously and continuously as a function of the time at a given frequency during polarization with a constant anodic or cathodic current. Impedance measurements were made on a smooth platinum in 2 n perchloric acid, 2 n sodium perchlorate and 2 n sodium hydroxide solutions in the region of oxygen deposition. According to the observed behavior of the impedance of the electrode, the oxide film on the electrode surface may be completed anodically through three stages; first, the adsorption of the hydroxyl radical; second, the formation of oxide (II), and finally, the conversion of this oxide to one of a higher grade. The dependence of the value of the electrode capacity at the first stage on the pH of the solution is discussed on the basis of the ion-exchange adsorption of cations and anions on the electrode surface covered by the hydroxyl radicals.
The Synthesis of Glycidylferrocenes and Related Compounds
Authors: Watanabe Hamao , Motoyama Izumi , Hata Kazuo 
Published: July 2006

Abstract
Ferrocene derivatives with one or two glycidyl substituents, desired for the formation of polymeric ferrocene compounds, were synthesized by the epoxidation of chlorohydrin compounds obtained from the products of the addition of ferrocenyllithium to epichlorohydrin at −40–−78°C. In the course of this synthesis, mono- and di-chlorohydrin compound and a disubstituted ferrocene with a 3-chloro-2-hydroxypropyl and a glycidyl substituent were isolated. All of them are stable liquid compounds. The investigation of the relationship between the reaction conditions and the yield of glycidylferrocenes revealed that the larger molar ratio of each reactant to ferrocene at each reaction step causes a higher conversion into glycidylferrocenes. In the epoxidation reaction of chlorohydrins with caustic alkali, a small amount of ethers, formed by the reaction of epoxides and the solvent ethanol, was obtained under some reaction conditions. In all cases, a small amount of biferrocenyl was isolated; the formation of this compound was considered to be attributable to the Wurtz-type coupling reaction of ferrocenyl radicals. The structures of all these products were confirmed by their infrared absorption spectra and, in part, by the NMR spectra.
The Direct Formation of Biferrocenyl and Polyferrocenyls from Ferrocenyllithium
Authors: Watanabe Hamao , Motoyama Izumi , Hata Kazuo 
Published: July 2006

Abstract
In the presence or absence of n-butyl bromide, ferrocenyllithium and cobaltous chloride reacted to give various polyferrocenyls and butylated polyferrocenyls. They were isolated, mainly by alumina chromatography, and their structures were established, principally from the NMR spectra, to be heteroannularly-bonded ones. The formation of these compounds is considered to be due to the coupling reactions of the ferrocenyl radical, the ferrocenylene biradical and the butyl radical, which were formed by homolytic fissions of some reactive intermediate and butyl halide. The presence of the alkyl halide greatly affected the sorts and yields of the products. No cyclic polyferrocenylene was obtained. The “9—10 rule” concerning the infrared spectra of ferrocene derivatives was found not to apply to di-substituted biferrocenyls. It was found, by a study of the X-ray diffraction patterns and the infrared spectra, that terferrocenyl crystallizes in polymorphic forms according to the method and the solvent of crystallization. The polymorphism may be attributable to the rotational isomerism around the central ferrocene nucleus.
Studies of Organic Catalytic Reactions. III. The Hydration Mechanism of Nitriles to Amides with Nickel Catalysts
Authors: Watanabe Ken-ichi , Sakai Koji 
Published: July 2006

Abstract
Benzonitrile, benzyl cyanide, acetonitrile and 2-cyanopyridine give the corresponding amides by the hydration with nickel catalysts and water. The effect of pyridine and thiophene on the hydration has been investigated. In general, the yield of amides increases upon the addition of a suitable amount of pyridine. On the contrary, the reaction is distinctly suppressed by the addition of thiophene. This fact is in striking contrast to the effect on the hydrogenation of nitriles. The correlation of the catalytic functions in hydration and the hydrogenation of nitriles has been studied, and the hydration mechanism with nickel catalysts has been discussed.
The Crystal Structure of 1,2,3,4-Tetrachlorobenzo[g]sesquifulvalene
Authors: Nishi Yoriko , Sasada Yoshio , Ashida Tamaichi , Kakudo Masao 
Published: July 2006

Abstract
The molecular structure of 1,2,3,4-tetrachlorobenzo[g]sesquifulvalene has been ascertained by X-ray crystal analysis. The crystal of this substance is monoclinic, with four molecules in a unit cell of dimensions: a=21.31, b=16.88, c=3.83 Å, and β=93.3°, the space group being P21/a. The crystal structure was determined by the Harker-Kasper inequality and the Sayer’s method. The atomic coordinates and the anisotropic temperature factors of each atom were refined by the block-diagonal-matrix least-squares method. The average length of the C–Cl bonds is 1.705 Å, a value which is in good agreement with those of several chlorobenzenes. In the sesquifulvalene skeleton, longer and shorter bonds are disposed as may be expected from the conventional chemical formula. The average length of the longer bonds is 1.461 Å, while that of the shorter ones is 1.354 Å. The mean C–C bond length in the benzene ring is 1.413 Å. The whole molecule is not on a plane, although the component ring systems are nearly planar. The five-membered ring and the seven-membered ring twist to each other by an angle of about 31° around the bond connecting these two rings. This might be due to the repulsion forces between chlorine and hydrogen atoms which approach each other closely. The plane of the seven-membered ring makes an angle of about 5° with that of the six-membered ring.
The Oxidation of Chloromethyl Compounds with Lead Tetraacetate
Authors: Yukawa Yasuhide , Sakai Mitsuru 
Published: July 2006

Abstract
In studying the reaction of styrene, olefins, vinyl ethers and vicinally-substituted compounds with lead tetraacetate, it was shown that the methyl group of 9-chloro-9-methylfluorene was easily acetoxylated with lead tetraacetate. This novel reaction was then applied to 1, 1-diphenylethyl chloride, 1-phenylethyl chloride and t-butyl chloride. In every case the methyl group of chlorides with an α-methyl group was acetoxylated preferentially.
The Solvent Effect on the Equilibrium of a Chemical Reaction in a Non-electrolyte Solution: Application to the Keto-enol Tautomerism and Dimerization of Nitrogen Dioxide
Authors: Tanaka Satohiro 
Published: July 2006

Abstract
A simple lattice theory of a non-electrolyte solution in which the equilibrium of chemical reaction is reached has been presented and compared with the data of the enolization of ethyl acetoacetate in various solvents and with those of the dimerization of nitrogen dioxide in chloroform. Predicted linear relationships has been obtained for the data of the enolization in non-polar solvents, but they could not be obtained for the reaction in ethyl alcohol or for the dimerization of nitrogen oxide in chloroform. The van’t Hoff-Dimroth relation has been derived by the present theory.
The Charge-transfer Complex and the Photochemical Reactions of Anthracene with Sulfur Dioxide in Various Solvents
Authors: Nagai Toshikazu , Terauchi Kenichi , Tokura Niichiro 
Published: July 2006

Abstract
The equilibrium constant, K, of the 1:1 charge-transfer complex formation of anthracene with sulfur dioxide has been estimated by spectrophotometric measurements to be 0.33 in carbon tetrachloride at 15°C. The values of ΔH (−4.8 kcal.mol−1) and ΔS° (−19 cal.deg−1mol−1) have been derived. The K value is nearly zero when estimated in the longer wavelength region, indicating that a contact charge-transfer complex is involved. A sort of contact charge-transfer complex of anthracene-SO2 is also observed in benzene. Irradiations by a high-pressure mercury lamp of anthracene with sulfur dioxide in various solvents have been carried out. In solvents such as n-hexane and carbon tetrachloride, which have no interaction with sulfur dioxide, anthracene gives sulfur-containing substances, such as anthracene-9-sulfonic acid (I) and dianthranyl-(9.9′)-sulfonic acid-(10) (II). On the contrary, in benzene or in carbon disulflde, no product such as the sulfonic acid, the dimer or the endoperoxide of anthracene is produced, indicating that the interaction of anthracene with sulfur dioxide is diminished by the solvent - sulfur dioxide interaction. A suggestion was made that the activated intermediate which induced the formation of I and II was of a singlet character.
Reactions of the Benzil-Triethyl Phosphite Adduct
Authors: Mukaiyama Teruaki , Kumamoto Takanobu 
Published: July 2006

Abstract
The decomposition of benzil-triethyl phosphite adduct in the presence of copper powder or cupric sulfate has been studied. When benzil, triethyl phosphite and cupric sulfate were treated in boiling toluene. cis-dibenzoylstilbene and triethyl phosphate were obtained. When the reaction was carried out in the presence of active hydrogen compounds, such as alcohol, carboxylic acid and amine, the corresponding benzoin derivatives were obtained. Further, when the adduct was decomposed in the presence of phenyl isocyanate or dicyclohexylcarbodiimide, 3, 4, 5-triphenyl-4-oxazoline-2-one or 2-cyclohexylimino-3-cyclohexyl-4, 5-diphenyl-4-oxazoline was obtained, along with triethyl phosphate.
The Syntheses of Peptides Related to the N-Terminal Structure of Corticotropin. VII. The Synthesis of Peptide Derivatives Corresponding to Positions 11 to 18 in the Corticotropin Molecule
Authors: Otsuka Hideo , Inouye Ken , Kanayama Makoto , Shinozaki Fusako 
Published: July 2006

Abstract
The derivatives of lysyl-prolyl-valyl-glycyl-arginyl-arginine, lysyl-prolyl-valyl-glycyl-lysyl-arginyl-arginine and lysyl-prolyl-valyl-glycyl-lysyl-lysyl-arginyl-arginine, which correspond to the amino acid sequences in positions 11—14 plus 17—18, 11—14 plus 16—18, and 11—14 plus 11—18 of the corticotropin molecule respectively, have been obtained as intermediates for the synthesis of adrenocorticotropically active peptides.
The Radiation-Induced Addition of Hydrogen Chloride to Ethylene
Authors: Terakawa Akira , Nakanishi Jun , Hirayama Toru 
Published: July 2006

Abstract
In a stainless steel autoclave, ethylene and hydrochloric acid or dried hydrogen chloride were irradiated with cobalt-60 gamma-rays. n-Butyl chloride and ethyl chloride were thus produced efficiently, unlike as when an ultraviolet light or catalyst was used. The products were quantitatively analyzed by gas chromatography. This reaction was supposed to be a vapor-phase radical chain reaction; the proposed reaction mechanism agreed well with our results. The selectivity of ethylene to the products was considered to be practically 100%. The G values of ethyl chloride, n-butyl chloride and the ethylene consumed, using the ratio of the total absorbed dose to ethylene, were calculated to be 16000, 10000 and 35000 respectively at 50°C and at a dose rate of 1.10×104r./hr. The ratios of the rate constants for ethyl chloride and n-butyl chloride were 366, 499 and 580 at 50, 40 and 15°C respectively, and the apparent activation energies for ethyl chloride and n-butyl chloride were calculated from the reaction rates to be 6.94 and 8.95 kcal./mol. respectively.
The Barium Content of Barite-forming Hydrothermal Waters as Exemplified by Tamagawa Hot Spring Waters
Authors: Ichikuni Masami 
Published: July 2006

Abstract
An estimation of the barium concentration in Tamagawa Hot Spring water was made on the basis of the partition of lead between spring waters and barite deposits precipitated from the waters. As the lead content of the waters and the chemical composition of the deposits are already known, the barium concentration can be computed by the use of the following relation:
D=(\fracPbBa)S⁄(\fracPbBa)L
where D is the partition coefficient of lead, and where S and L denote the solid and liquid phases respectively. A value of 2±1 mg./1. was obtained for the barium concentration in the water issuing from the vents. It was pointed out that the water is supersaturated with barium sulfate. This supersaturation may be due to the addition of a considerable amount of sulfates, probably formed by supergene processes, to the original thermal water. The genesis of hydrothermal barite deposits was also discussed.
Asymmetric Synthesis with Sugar Derivatives. I. The Conjugate Additions of Grignard Reagents to α, β-Unsaturated Esters of Sugar Derivatives
Authors: Kawana Masajiro , Emoto Sakae 
Published: July 2006

Abstract
Partial asymmetric syntheses were carried out in the reaction of Grignard reagents with crotonic and cinnamic esters of 1,2:5,6-di-O-cyclohexylidene-d-glucose, 1,2:5,6-di-O-isopropylidene-d-glucose, 1,2-O-isopropylidene-5-deoxy-d-xylose and (−)-menthol. The reaction of 3-O-crotonyl-1,2:5,6-di-O-cyclohexylidene-d-glucose (Ic) with phenylmagnesium bromide, followed by the hydrolysis of the resulting ester, gave (−)-3-phenylbutyric acid (III) in 33% optical and 12% synthetic yields, while in the presence of cuprous chloride as a catalyst, III was obtained in 74% and 58% yields respectively. The reaction of 3-O-crotonyl-1,2-O-isopropylidene-5-deoxy-d-xylose (Ie) with phenylmagnesium bromide gave (+)-acid (III) without cuprous chloride in 16% optical and 32% synthetic yields and (−)-acid (III) with cuprous chloride, in 58% and 61% yields respectively. The reaction of 3-O-cinnamoyl-1,2:5,6-di-O-cyclohexylidene-d-glucose (IVc) with benzylmagnesium chloride, followed by the saponification of the resulting ester, gave (−)-3,4-diphenylbutyric acid (VI) in 18% optical and 62% synthetic yields without cuprous chloride, and in 17% and 58% yields with cuprous chloride. In the formation of acid (VI), cuprous chloride seemed to have no effect on optical and synthetic yields nor on the change in the sign of optical rotation. The steric courses of these reaction are discussed.
A Preliminary Study of the Carboxylation and Decarboxylation of Some Sulfides
Authors: Tagaki Waichiro , Ueyama Kenji , Minamida Isao , Kim Yong He , Ikeda Yoshinori , Oae Shigeru 
Published: July 2006

Abstract
Some sulfides with benzylic hydrogen have been carboxylated by carbonating the respective carbanions generated with dimsylsodium in dimethyl sulfoxide. The resulting mercaptocarboxylic acids have then been found to have considerably-enhanced rates of decarboxylation reaction.
The Crystal Structure of Tris(l-propylenediamine)cobalt(III) Bromide and the Absolute Configuration of the Complex Ion, [Co l-pn3]3+
Authors: Iwasaki Hitoshi , Saito Yoshihiko 
Published: July 2006

Abstract
Crystals of L-[Co l-pn3]Br3 (pn: propylenediamine) were prepared and their crystal structure was completely determined by means of X-rays. They are hexagonal, with the space group P63; a=11.08±0.03,c=8.59±0.02Å and Z=2. The structure is essentially ionic, consisting of complex ions and bromide anions. A complex ion has a three-fold axis of symmetry through the central cobalt atom. Five-membered Co-pn rings are puckered, and the C–C bonds in these rings are nearly parallel to the threefold axis. The methyl carbon bonds are equatorial with respect to the plane of the ring. The absolute configuration of the complex ion has been determined by using the absorption-edge technique. The Llll-type complex ion has been found to be laevorotatory with respect to the NaD lines. By the introduction of an asymmetric carbon atom into the ligands, the absolute configuration of a series of tris(bidentate)-complexes could be successfully correlated to the configurational series in organic compounds.
Chronopotentiometry of Tris(ethylenediamine)chromium(III) Ions in Various Supporting Electrolyte Solutions
Authors: Tanaka Nobuyuki , Yamada Akifumi 
Published: July 2006

Abstract
The reduction of tris(ethylenediamine)chromium(III) ions at the dropping mercury electrode has been studied chronopotentiometrically in various supporting electrolyte solutions. The electrolysis at constant cathodic current in an acid solution gives a well-defined chronopotentiogram which corresponds to the one-electron reduction of chromium(III) to chromium (II). The anodic chronopotentiogram which is obtained by the current-reversal techniques is clearly separated from the cathodic one. Two cathodic steps are obtained in alkaline ethylenediamine solutions, and two anodic steps, at the current reversed. No chemical reaction involving hydrogen ions or ethylenediamine takes place prior to the electron transfer. The presence of very small amount of surface-active substances was found to improve the shape of chronopotentiograms. In the presence of EDTA, the one-electron cathodic chronopotentiogram splits into two steps.
Chemical Studies of Minerals Containing Rarer Elements from the Far East District. LX. Thalenite from Suishoyama, Kawamata-machi, Fukushima Prefecture, Japan
Authors: Nagashima Kozo , Kato Akira 
Published: July 2006

Abstract
Chemical studies of thanlenite from Suishoyama pegmatite, Fukushima Prefecture, showed its composition to be very close to the ideal formula, Y2Si2O7, and to a selective distribution pattern of rare earths belonging to the thortveitite-type as defined by Goldschmidt and Thomassen. The X-ray powder studies disclosed a metamict state hitherto unknown in this species, and the original state could be recovered by thermal treatment. Optical and other properties: color, colorless to light gray; luster, resinous; optical properties, α=1.709±0.002, β=1.716±0.002, γ=1.723±0.002, (−)2V∼70°, ρ&lt;v; specific gravity, 4.16, hardness; 6\frac12. Chemical analysis: SiO2, 30.68%; Al2O3, 0.10%; Fe2O3, 0.17%; ΣY2O3, 64.89%; UO2, 1.12%; ThO2, 0.20%; CaO,0.35%; MnO, 0.38%; MgO, 0.33%; Na2O, 0.02%; H2O(+), 1.56%; H2O(−), 0.11%; total, 99.91%.
The Dipole Moment and Polarizability in the n–π* Excited State of Acetone from Spectral Solvent Shifts
Authors: Abe Takehiro 
Published: July 2006

Abstract
This paper has presented the expression for the frequency shift, including the solvent refractive index and the dielectric constant; the expression has been determined on the basis of a previous paper (This Bulletin, 38, 1314 (1965)). According to the present theory and E. G. McRae’s theory (J. Phys. Chem., 61, 562 (1957)), the excited state dipole moment of acetone has been estimated to be 0.86 and 1.84 D respectively, both being smaller than the ground state value. The results calculated by the present theory show that the excited state polarizability is 163.1×10−25 cm3 and that the solvation energies in the solvents of n-heptane, cyclohexane, carbon tetra-chloride, ethyl ether, and methyl acetate are less in the ground states than in the excited states.
The Flotation of Cation by Cationic and Anionic Surfactants
Authors: Aoki Norichika , Sasaki Tsunetaka 
Published: July 2006

Abstract
The ion flotation of a cation by a cationic surfactant with the aid of an anionic chelating agent was studied for the system of Fe3+-ethylenediaminetetraacetic acid (EDTA)-octadecyldimethylammonium chloride (ODAC). The systems of Fe3+-EDTA and Fe3+-ODAC were also studied for purposes of comparison. The effects of the concentration of the above three components, the pH and the gas-flow time on the flotation efficiency were measured. The diagram of the flotation efficiency vs. the pH showed a W-shaped curve for the Fe3+-EDTA-ODAC system, which was explained by the formation of Fe3+-EDTA, Fe3+-ODAC and Fe3+-EDTA-ODAC complexes, each of which has a different optimum pH region of its formation. The flotation of a cation by an anionic surfactant was also studied using ferric, ferrous, silver and Malachite Green ions as cations and sodium dodecylsulfate (SDS) as an anionic surfactant. The flotation efficiency increased with the time of the gas flowing, except for the system of Fe3+-SDS. Such an increase was explained by the relatively insoluble nature of the corresponding SDS salts.
The Radiolysis of Aqueous Solutions of Potassium Iodide
Authors: Sawai Takeshi , Shinozaki Yoshiharu , Meshitsuka Gisuke 
Published: July 2006

Abstract
The radiolysis of potassium iodide aqueous solutions has been studied in order to elucidate the contribution of the hydrated electrons to the radiolysis mechanisms. The deaerated and aerated solutions were irradiated by 60Co γ-rays under various conditions, and the yields of iodine, hydrogen peroxide, hydrogen and oxygen were determined. The pH dependences of the initial yields of iodine and hydrogen peroxide in the deaerated solutions are different from the results obtained in the aerated solutions. These results can be reasonably explained by assuming the hydrogen atoms and hydrated electrons to be the reducing species. From an examination of the results, the radiolysis mechanisms of the potassium iodide aqueous solutions have been discussed. The rate constant of the reaction of hydrated electrons for iodine has been calculated to be 5.9×1010 M−1 sec−1.