bluuebunny/crossref_metadata_2025_split huggingface dataset:
Vibrational Analysis of Substituted and Perturbed Molecules. III.Green’s Function Determination of Force Constants for XY3 Planar Molecules
Authors: Wolfram Thomas , Bass C D , DeWames Roger E , Lynds L 
Published: July 2006

Abstract
Using the Green’s function formulae for isotopic frequencies of the XY3 molecule together with the spectral theorem, explicit formulae for the molecular force constants directly in terms of the vibrational frequencies have been obtained. The relationship between the Wilson force constants and the cartesian force constants is discussed and leads to the above formulae. The procedure is applied to the BCl3 and BBr3 molecules and force constants are obtained. A simple procedure for calculating the variations in the force constants with variations in vibrational frequencies is suggested.
The Diffusion of Gases at High Pressures. I. The Self-diffusion Coefficient of Carbon Dioxide
Authors: Takahashi Shinji , Iwasaki Hiroji 
Published: July 2006

Abstract
The self-diffusion coefficients of carbon dioxide were measured over a pressure range from 2 to 250 atm. at 25, 50, and 75°C. The measurements of self-diffusion through a plug of porous bronze were made using the radioactive tracer technique. The products of the density and the diffusion coefficient increase slightly with the density in the region of lower density, below about 10 mol./l., for both isotherms at 50 and 75°C, but they decrease in the region of higher density. These results agree with the results obtained by O’Hern et al., but not with Enskog’s dense gas theory, and not with the values calculated by the generalized chart of Slattery et al.
The Fluorination of Ethylene and Ethane
Authors: Nagase Shunji , Tanaka Kiyoshi , Baba Hajime , Abe Takashi 
Published: July 2006

Abstract
Ethylene and ethane were electrochemically fluorinated in an electrolytic fluorination cell equipped with a bubbler. Several fluorinated ethanes were obtained from these samples in reasonable total-yields with reasonable current efficiencies. The influence of operating conditions on the reaction was investigated. A probable mechanism was described for the formation of the characteristic procucts obtained in the fluorination reaction.
The Crystal and Molecular Structure of 8, 8-Dicyanoheptafulvene
Authors: Shimanouchi Hirotaka , Ashida Tamaichi , Sasada Yoshio , Kakudo Masao , Murata Ichiro , Kitahara Yoshio 
Published: July 2006

Abstract
Crystals of 8, 8-dicyanoheptafulvene, C10H6N2, are monoclinic, with two molecules in a unit cell with the dimensions a=7.84, b=13.14, c=3.99 Å, and β=97.9°; the space group is P21⁄m. The intensities were recorded on multiple-film equi-inclination Weissenberg photographs and measured visually against a standard scale. A trial structure was constructed from the Patterson projections, P(u, v) and P(u, w), and a Harker section, P(u, 1/2, w). The atomic coordinates and anisotropic temperature factors were refined by the least-squares method. The final R factor for (hkl) reflections is 0.107. A considerable bond alternation in the conjugated seven-membered ring has been observed. The average long and short bond lengths in the ring are 1.44 and 1.34 Å respectively. The shortest C=C bond measures 1.31 Å, which is shorter than that in ethylene. The exocyclic C=C bond length is 1.42 Å, suggesting a considerable dipolar resonance structure, one which may be responsible for the stability of the compound. The C≡N bond length is 1.13 Å. The molecule deviates slightly from being planar; it lies nearly parallel to the (101) plane. All the intermolecular separations correspond to normal van der Waals interactions; the perpendicular distance between the molecular planes is 3.4Å. The thermal motion was interpreted in terms of rigid body vibrations, and the bond lengths and angles were corrected for the rotational oscillations.
Properties of Dilute Solutions of Polyurethanes. I. Linear Polymers
Authors: Sato Hiroshi 
Published: July 2006

Abstract
Polyurethanes were prepared from polycaprolactone, 4, 4′-diphenylmethane diisocyanate, and ethylene diamine. Two kinds of polymers were used for the present experiments. One contained polycaprolactone with the number-average molecular weight, \barMn, of 1.30×103, while the other contained polycaprolactone with an \barMn value of 2.80×103. Each polymer was fractionated from a dimethyl acetamide solution by progressive precipitation with a mixture of n-heptane and ethyl ether, and the fractions were characterized in terms of viscosity and sedimentation. The relations between the intrinsic viscosity and the molecular weight were found in DMF at 25°C to be:
[η]=5.52×10−4M0.66
for the polymer containing polycaprolactone (\barMn=1.30×103) and
[η]=7.71×10−4M0.62
for the polymer containing polycaprolactone (\barMn=2.80×103). The viscosities of the solutions of the polymers were measured in several solvents at different temperatures, and the polymer-solvent interaction parameters were obtained by using the Fixman theory for the expansion factor. The molecular-weight distribution of the polymer containing polycaprolactone (\barMn=1.30×103) was obtained from the distribution of the sedimentation coefficient, while the value of \barMw⁄\barMn was calculated from the distribution curve to be 1.95.
The Crystal Structures of l-Tryptophan Hydrochloride and Hydrobromide
Authors: Takigawa Takaji , Ashida Tamaichi , Sasada Yoshio , Kakudo Masao 
Published: July 2006

Abstract
The hydrochloride and hydrobromide of l-tryptophan crystallize in the monoclinic space group P21. The cell dimensions of the hydrochloride are: a=7.45, b=5.30, c=14.67 Å, β=98.80°, and those of the hydrobromide are: a=7.64, b=5.41, c=14.58 Å, β=100.47°. There are two molecules in the unit cell. The two compounds are isomorphous. The crystal structure of the hydrobromide was first determined by the heavy atom method with two-dimensional data, and then that of the hydrochloride was refined by three-dimensional least-squares procedure. The molecular and crystal structure is mainly discussed for the hydrochloride here. The average of six C–C bond lengths in the benzene ring is 1.396 Å, that of C–N bond lengths in the indole ring is 1.384 Å. In the carboxyl group, one C–O bond length, 1.147 Å and two O–C–C angles, 106.8° and 125.7° are significantly different from those reported for amino and carboxyl acids so far investigated. The molecule consists of two planes of the carboxyl group and of the indole ring, the planes making an angle of 70.6° with each other. As to the conformation about the C(α)–C(β) bond, C(γ) lies at the gauche position with both of the carboxyl and the amino groups. The molecules are arranged in double layers parallel to the ab plane; the polar layer is held together by a network of the three N–H··· Cl− hydrogen bonds, 3.17, 3.19 and 3.24 Å and one O–H···C1−, 3.04 Å, and in the non-polar layer, the indole rings are packed mainly by van der Waals forces, the shortest C···C and C···N contacts being 3.74 and 3.42 Å respectively.
The Oligomerization of Isoprene by Cobalt or Iron Complex Catalysts
Authors: Misono Akira , Uchida Yasuzo , Hidai Masanobu , Ohsawa Yoshiro 
Published: July 2006

Abstract
The reaction of isoprene by the catalyst systems composed of cobalt(III) or iron(III) ace-tylacetonate, an electron donor, and triethylaluminum was studied. It was found that isoprene is selectively dimerized to form a mixture of 1,5- and 2,5-dimethyl-1,5-cyclooctadiene by the catalyst prepared by the reaction of iron(III) acetylacetonate, 2,2′-dipyridyl, and triethylaluminum. The intermediate complex of the reaction was then examined by studying the effects of the molar ratio of the catalyst components on the reaction or by the measurement of the electronic absorption spectra of the reaction solution. The reaction of butadiene with the catalyst systems described above was also carried out and compared with that of isoprene.
Copolymerization of Vinyl Chloride and Ethylene Initiated by Trialkylboron-Peroxide Catalyst Systems
Authors: Misono Akira , Uchida Yasuzo , Yamada Kunikazu 
Published: July 2006

Abstract
Low-pressure copolymerization was carried out in a water-methanol mixture (1 : 1 by weight) at 0°C. It was found that, when hydroperoxides were used as cocatalysts, triethylboron and tri-rc-butylboron were active as catalysts, while triphenylboron was inactive. As cocatalysts,, hydroperoxides were more active than disubstituted peroxides. The highest catalytic activity was observed when the cocatalyst/catalyst molar ratio was 0.4. The initiating radical has been suggested to be the hydroxy radical, and the initiating mechanism has been discussed briefly. The yield and the reduced specific viscosity of the copolymer decrease rapidly with an increase in the ethylene content of the monomer mixture. The monomer reactivity ratios were: r1(vinyl chloride) = 4.16 and r2(ethylene) = 0.05. This indicates that the copolymerization reaction proceeds via a normal radical mechanism. The resulting copolymer shows characteristic absorption peaks at 750 cm−1 in the infrared spectrum and at 8.37 τ in the NMR spectrum.
The Chlorine Quadrupole Resonances of Ethane Derivatives
Authors: Kondo Seiichi 
Published: July 2006

Abstract
The temperature broadening of the chlorine quadrupole resonance line-width was studied in three ethane derivatives (1, 1, 1-trichloroethane, hexachloroethane and 1, 1, 1, 2-tetrachloro-2, 2-dimethylethane) below the plastic crystalline phases. Most of the resonance frequencies observed at the temperature of liquid nitrogen were equal to those reported in the literature. The energies of activation (2.2, 2.6 and 4 kcal./mol. respectively for the three compounds mentioned above) were obtained from the line-width versus temperature curves in the low temperature phases. It was suggested, considering the smallness of the energies of activation, that the vibrational rotation of the molecule as a whole rather than the internal axial rotation may exist in those phases.
The Catalytic Hydrolysis of Oligophosphates by Ethylenediamine-Copper(II) and Poly-l-lysine - Copper(II) Complexes
Authors: Moriguchi Yoshiki 
Published: July 2006

Abstract
The hydrolysis of some oligophosphates (tetra-, penta- and hexaphosphates) has been studied at 45°C in the absence and in the presence of a metal complex, and the relation between the nature of the complex catalyst and the composition of the degradation products has been investigated on oligophosphates as substrates, especially on pentaphosphate. In the presence of the Cu(II)-en (1:1) complex, the intermediate chain of pentaphosphate is attacked to produce trimeta- and pyrophosphates as the main products; the hydrolytic reaction is apparently of a first-order kinetics which depends on the concentration of the catalyst. The Cu(II) - Poly-Lys complex shows a strong catalytic activity and attacks pentaphosphate exclusively, thus producing orthophosphate as the main product. The optimum conditions for the catalytic effect on the hydrolysis of pentaphosphate are as follows: 1) the ratio of the NH2 repeat unit of Poly-Lys to a mole of pentaphosphate ([-NH2]i/[P5]i) is about 1.6 at pH 8, the concentration of Cu(II) being constant; 2) the molar ratio of Cu(II) to the NH2 repeat unit of Poly-Lys ([Cu]i/[-NH2]i) is 1.0: 3) the activity reaches a maximum at about pH 10. Attempts have been made to explain these results on the basis of the structure of the Cu(II) - Poly-Lys complex.
Studies of Scandium in Various Solutions. III. The Solvent Extraction and Complex Formation of Scandium(III) with Acetylacetone and Thenoyltrifluoroacetone
Authors: Sekine Tatsuya , Koizumi Akira , Sakairi Mitsuo 
Published: July 2006

Abstract
The distribution of scandium(III) at a tracer concentration was determined between chloroform with acetylacetone or thenoyltrifluoroacetone and 0.1 m aqueous perchlorate solutions at 25°C. The change in the distribution ratio of the metal ion with the change in the chelating acid concentration or with the change in the hydrogen-ion concentration was explained in terms of the extraction of the tris chelate complexes into the organic phase and the formation of the primary complexes in the aqueous phases. The equilibrium constants in these systems were determined graphically, by a curve-fitting method to be as follows:
Kex=[ScA3]org[H+]3⁄[Sc3+][HA]3org
K 1=[ScA2+]⁄[Sc3+][A−]
(Remark: Graphics omitted.)
A Geochemical Study of Iodine in Volcanic Gases
Authors: Honda Fumihiro , Mizutani Yoshihiko , Sugiura Tsutomu , Oana Shinya 
Published: July 2006

Abstract
Volcanic gases from several active volcanoes in Japan have been analyzed for iodine and chlorine: Showashinzan (I=0.025–0.20 mg.I/kg.H2O, Cl=238–1830 mg.Cl/kg.H2O), Iwatesan (I=0.053–0.19, Cl=2720–3360), Issaikyoyama (I=0.030–0.087, Cl=104–213), Nasudake (I=0.16–3.9, Cl=188–9460), Yakedake (I=0.58–0.93, Cl=1250–1730), Kuju-Ioyama (I=0.13–1.3, Cl=266–8000), Kirishima-Ioyama (I=0.036–0.84, Cl=200–4200), and Miharayama (I=0.45–1.5, Cl=1640–2180). Each volcano has a characteristic I/Cl ratio. Analyses have also been made of hot-spring waters from the environs of Nasudake, Kuju-Ioyama, and Kirishima-Ioyama. It is indicated that the hot-spring waters are similar in I/Cl ratio to the volcanic gases from the same area.
Studies of the Chemiluminescence of Several Xanthene Dyes. IV. Theoretical Considerations
Authors: Kamiya Isao , Iwaki Ryojirô 
Published: July 2006

Abstract
On the basis of the results shown in the previous papers, the following reaction scheme was proposed for the chemiluminescent reaction. Hydrogen peroxide decomposes spontaneously to the radical (R·). A portion of the radical then reacts with the dye molecule (E) to produce an energy-rich intermediate (ME*): E+R·→ME* The energy-transfer takes place from ME* to an unoxidized dye, so the dye is excited electronically: ME*+E→E*+··· However, most of the ME* is decomposed by non-radiative processes. E* is deactivated by fluorescence emission processes (E*→E+hν) or quenching processes (E*+E→E+E). According to this reaction scheme, most of the experimental results can be explained reasonably. It is expected that further experimental evidence, such as the detection of an intermediate, will verify the theory.
Mineral Acids as Photoinitiators of Vinyl. Polymerization in Aqueous Media
Authors: Saha Mihir K 
Published: July 2006

Abstract
A few mineral acids, namely hydrochloric, hydrobromic and sulfuric acid, have been used as photoinitiators for the polymerization of methyl methacrylate in aqueous media in the presence of ultraviolet light. The endgroups incorporated in the resulting polymers have been determined by the application of the sensitive “Dye Techniques” lately developed in our laboratory. On the basis of the endgroup results, attempts have then been made to explain the mechanism of such polymerization, and also the nature of the initiating species involved.
The Polarographic Behavior of Tris(1,10-phenanthroline)cobalt Complexes and the Univalent Phenanthroline-Cobalt Complex.
Authors: Morinaga Kenichi , Nakano Kunio , Saito Shigeru , Nakamura Keizo 
Published: July 2006

Abstract
The oxidation-reduction behavior of tris(1,10-phenanthroline)cobalt complexes at a dropping mercury electrode has been studied by the d. c. and a. c. polarographic methods. The trivalent cobalt-phenanthroline complex ion is reduced in two steps in 1 m sodium sulfate in a quite similar way as the trivalent cobalt-dipyridyl complex ion. Both electrode processes, cobalt(III)→cobalt(II) and cobalt(II)→cobalt(I), are considered to be reversible. The univalent cobalt-phenphenanthroline complex has been obtained as a black powder by the reduction of the divalent cobalt complex with sodium borohydride; the atomic ratio of nitrogen to cobalt has been found to be close to six. The ethanolic solution is brown-black, in remarkable contrast with that of the corresponding dipyridyl complex, deep blue.
The Synthesis of Sulfoxides by the Oxidation of Sulfide with the Bromine Complex of 1, 4-Diazabicyclo(2, 2, 2) octane
Authors: Oae Shigeru , Ohnishi Yutaka , Kozuka Seizi , Tagaki Waichiro 
Published: July 2006

Abstract
1, 4-Diazabicyclo(2, 2, 2)octane readily forms an addition complex with two moles of bromine. This complex has been found to be an excellent oxidizing agent for the selective oxidation of various sulfides to the corresponding sulfoxides when the reaction is performed in an aqueous medium. The bromine-addition complexes of pyridine and quinoline have also been found to be useful for the same purpose. The reaction has been shown to be a superb way of incorporating 18O into sulfoxides.
Some Reactions of the Glycidyl Esters of Sulfonic Acids
Authors: Nakabayashi Nobuo , Masuhara Eiichi , Iwakura Yoshio 
Published: July 2006

Abstract
1-Chloro-2-hydroxypropyl sulfonates are obtained by the reaction of glycidyl sulfonates with hydrochloric acid at room temperature. They are converted into 1,3-dichloro-2-propanol by the action of hydrochloric acid at 100°C, or into epichlorohydrin by that of bases. The reaction of glycidyl sulfonates and sodium carboxylates affords glycidyl carboxylates. In the preparation of glycidyl carboxylates, glycidyl sulfonates act as a direct alkylation agent for sodium carboxylates. The addition of amines to the epoxide is carried out at first in the reaction of glycidyl sulfonates and amines. The adducts are converted into glycidyl amines by the action of sodium hydroxide, or into N-[β-hydroxypropylene(α,γ)]-ammonium sulfonates by the isomerization, by heating them or letting them stand for a long time. The latter is an intermediate used in preparing 1,4-dioxane derivatives in the presence of sodium hydroxide.
Intramolecular Interaction between Hydroxyl Group and π-Electrons. XIX. Steric Effects on the Interaction in o-(1-Alkenyl)phenols
Authors: Oki Michinori , Iwamura Hiizu 
Published: July 2006

Abstract
Nine o-(1-alkenyl)phenols, o-HOC6H4CR1=CR2R3, have been prepared and their ultraviolet absorptions and the O–H stretching bands (vO-H) in the infrared absorption measured in an effort to explore the effect of the substituents, R1–R3, on the strength of the intramolecular interaction between the OH group and the π-electron system. The K-band of the styrene chromophore at 240–250 mμ is lost in the samples involving R1, which is bulkier than methyl. As the size of R1 increases from H, by way of Me, Et, and i-Pr, to t-Bu, the angle of the twist between the planes made by the benzene ring and the ethylenic group must increase; this trend is nearly parallel with the amount of the interacting vO-H in the infrared spectrum. The phenomenon is interpreted mainly by means of the favorable overlap between the O–H group and π-orbitals. o-Isobutenylphenol shows a νO-H triplet at 3610, 3576 and 3539 cm−1. The latter two bands are assigned to the hydroxyl group interacting with π-electrons on the vinyl group intramolecularly. A tentative explanation has been developed which attributes the two interacting bands to the presence of two interacting conformations. The solvent effect on the ultraviolet absorptions is in accord with this explanation.
A New Synthesis of Polyhydroxydihydroflavonols
Authors: Oyamada Taichiro , Baba Hajime 
Published: July 2006

Abstract
An alkaline hydrogen peroxide oxidation of chalcones with methoxymethoxyl groups in the 2′-position and in other positions gave the corresponding poly(methoxymethoxy)chalcone oxides; these were then, in turn, easily converted into polyhydroxydihydroflavonols, with a simultaneous splitting of all the O-methoxymethyl groups, by warming with acid. The general applicability of the new method was illustrated by the synthesis of the following hydroxydihydroflavonols: 3,7-dihydroxy- (m.p. 170–171°C),3,4′-dihydroxy- (m.p. 214–216°C),3,4′-dihydroxy-3′-methoxy- (m.p. 217–218°C),3,4′,7-trihydroxy- (m.p. 214–215°C), and 3,3′,4′,7-tetra-hydroxyflavanone (dl-fustin, m. p. 217–218°C). The first four new compounds were identified by converting them into known methyl ethers, while the last one was identified by comparing it with natural dl-fustin. Their structures were also confirmed by infrared and ultraviolet spectra.
The Mass Spectra of Chalcones, Flavones and Isoflavones
Authors: Itagaki Yasuhiro , Kurokawa Tadashi , Sasaki Shin-ichi , Chang Chin-Te , Chen Fa-Ching 
Published: July 2006

Abstract
The fragmentation of flavonoid compounds by electron impact has been studied and the following results described: 1) Chalcones gave the usual fragmentation pattern; however, 2′-hydroxy chalcones showed complex spectra according to the isomerization of chalcone to flavanone. 2) The fragmentation pathways of flavones were decided by comparison with many kinds of halogen-substituted flavones. 3) Isoflavone gave the M-1 ion as the base peak, and no loss of CO was observed.
Vulcanized Aniline Black. Its Electrical Conductivity and Catalysis upon the Decomposition of Hydrogen Peroxide
Authors: Inoue Hiroo , Kida Yasuji , Imoto Eiji 
Published: July 2006

Abstract
New semiconductive polymers have been prepared by the vulcanization of the oxidative condensation products of aniline. The polymers vulcanized are infusible black or black-violet powders insoluble in any organic solvent. The spin concentrations of the polymer vulcanized are about 1.5–2.5×1019 spins/g., about ten as much as those of the oxidative condensation products of aniline. The electrical conductivity increases with the increase in the sulfur content; the electrical resistivity at 20°C is 106–109 ohm-cm., and the activation energy is 0.68–1.18eV. The polymers vulcanized have catalytic effects on the decomposition of hydrogen peroxide at 30°C. The catalytic effects of phenothiazine and the oxidative condensation products of aniline are, however, extremely slight. The catalytic ability depends not only on the structure of the polymer vulcanized, but also to some extent on its electrical conductivity.
Semi-empirical Treatments of the Nonlinearity of Free Energy Correlations in Aromatic Side-chain Reactions. The Multiplicity of Substituent Constants
Authors: Fueno Takayuki , Okuyama Tadashi , Furukawa Junji 
Published: July 2006

Abstract
The nonlinearity of free energy correlations of the substituent effects in aromatic side-chain reactions has been treated by the simple LCAO MO method. The ionization equilibria of substituted phenylacetic acids, leading to the definition of “normal” substituent constants, σ0, were taken as the basis for theoretical tests of the correlations. Thus, the integral parameters for various substituents were determined in such a way that the calculated π-electron charge densities for meta and para carbons in benzenes were proportional to the corresponding σ0-constants. Several other typical side-chain reactions of substituted benzenes were simulated by the corresponding standard processes, and the effects of substituents on these reactions were examined by the perturbation calculations of the π-electron energy changes accompanying the reactions. It has been found that the substituent constants, σ, σ+ and σ−, are linearly related to the calculated energy changes. It is suggested that the treatment may be extended to other reactions to account for the sliding-scale variation in substituent constants from reaction to reaction.