bluuebunny/crossref_metadata_2025_split huggingface dataset:
Primary Processes in the Photoreduction of Acridine in Various Alcohols
Authors: Koizumi Masao , Ikeda Yoshinori , Yamashita Hiroshi 
Published: July 2006

Abstract
The effect of the addition of biacetyl on the quantum yield of photoreduction of acridine in methanol, ethanol, n- and iso-propanol has been studied under the aerated and deaerated conditions. From the analysis of the results, the quantum yields for four mechanisms ΦMS(S means that a reactive state is singlet excited states, S*, and M denotes a molecular mechanism), ΦMS (R denotes a radical mechanism), ΦMT (T indicates that a reactive state is a state other than S* and T(π–π*), most likely T(n–π*) and ΦRT have been decided, assuming that oxygen does not deactivate T(n–π*). The values are
5&for methanol, & &Φ_M^S(0.027) & &Φ_R^S(0.039) & &Φ_M^T(0.006) & &Φ_R^T(0.057)
&for ethanol, & &Φ_M^S(0.043) & &Φ_R^S(0.067) & &Φ_M^T(0) & &Φ_R^T(0.019)
&for n-propanol, & &Φ_M^S(0.030) & &Φ_R^S(0.036) & &Φ_M^T(0) & &Φ_M^T(0.022)
&for isopropanol, & &Φ_M^S(0.03) & &Φ_R^S(0.058) & &Φ_M^T(0) & &Φ_R^T(0)
The quenching constants of biacetyl on the fluorescence of acridine have been found to agree with the ones on the reaction at S* in all alcohols; the rate constants approximate diffusion controlled. In addition it has been confirmed by a flash method that biacetyl does not attack the T(π–π*) nor the semi-reduced acridine; this justifies the present method of analysis.
Phase Changes in Crystalline and Glassy-Crystalline Cyclohexanol
Authors: Adachi Keiichiro , Suga Hiroshi , Seki Syûzô 
Published: July 2006

Abstract
It has been known that cyclohexanol has low-temperature form (crystal-II) and high-temperature form (crystal-I) and that the supercooled crystal-I shows in its heat capacity curve an anomalous jump resembled to that associated with glass transition. In order to clarify whether this anomaly arises from relaxation phenomenon or not, we have reinvestigated the heat capacity of this substance from 14°K to 320°K and obtained the values of 8827 J/mol, 265.31°K, 1782 J/mol and 299.09°K for heat of transition, transition point, heat of fusion and melting point respectively. Comparing the ideal gas entropy of cyclohexanol calculated from thermal data and that from statisticalmechanical data, we have estimated that the residual entropy of the crystal-II is of zero and that the potential barrier of internal rotation of OH group is 7.0 kj/mol. From these results, the residual entropy of the supercooled crystal-I amounts to 4.72 J/(mol deg K). We have discussed the glass transition of this crystal and proposed a new term glassy crystal. We have also studied the heat capacity of metastable phase (crystal-III) and obtained the results 244.8°K and 8640 J/mol for transition point and heat of transition. The residual entropy of the crystal-III has determined to be zero.
Infrared Spectra of Crystalline CHCl3 and CDCl3
Authors: Kimoto Arata , Yamada Haruka 
Published: July 2006

Abstract
The infrared spectra for the fundamental absorption bands, ν1, ν2, ν4 and ν5, of CHCl3 and CDCl3 have been measured in polycrystalline films. For the C–H or C–D bending band a triplet has been observed in the pure crystal. The spectra of a mixed crystal (CHCl3: CDCl3) have also been studied over the entire concentration range. The space group of crystalline chloroform has been determined to be D2h16. The intensity of the band changes, going from the gas to the solid, depending on the symmetry species to which the vibrational mode belongs; the A1 bands increase in intensity, while the E bands decrease. The C–H stretching band shows an especially remarkable increase.
Manganese(II) and Mercury(II) Complexes Containing a Thio Derivative of Acetylacetone
Authors: Furuhashi Akiko , Watanuki Kunihiko , Ouchi Akira 
Published: July 2006

Abstract
New compounds of the type M(C5H7S2)2Cl4, where M is Mn(II) or Hg(II), were obtained by passing hydrogen chloride and hydrogen sulfide through ethanol solutions containing acetylacetone and metal chlorides. Such adducts seem to be isostructural to iron compounds, and are stable in the solid state. They seem to decompose when brought into contact with such solvents as water, methanol and dimethylformamide. Their magnetic susceptibilities show that these compounds are all bivalent. The infrared spectra and electronic spectra resemble those of the dithioacetylacetonato iron compound.
Electric Conductance and Density of Molten Salt Systems: I2+SbI3, SbBI3+SbI3, and SbCl3
Authors: Saito Kenji , Ichikawa Kazuhiko , Shimoji Mitsuo 
Published: July 2006

Abstract
Measurements of electric conductance as a function of temperature have been made for the pure liquids; I2, SbCl3, SbBr3 and SbI3, and the mixtures ; I2+SbI3 and SbBr3+SbI3, from 100 to 250°C. Furthermore, measurements of density by a pycnometric method as a function of temperature have also been made for these mixtures, from 100 to 300°C. The conductivities of these liquids lie in the range from 5×10−4 to 1×10−5 ohm−1 cm−1, and are about 10−4 times lower than those of alkali halide melts. In these poorly-conducting pure liquids, the molecules may be considered as constituting a solvent in which slightly dissociated ions are contained. The negative temperature coefficient of conductivity for iodine is in marked contrast to the antimony halide melts, and may be interpreted in terms of the ionic conduction and electron hopping mechanism rather than the metallic one.
Bromine to Chlorine Ratios in Igneous Rocks
Authors: Sugiura Tsutomu 
Published: July 2006

Abstract
Samples were decomposed by fusion with Na2O2 and benzoic acid in a Parr-bomb, then halogens were separated from other elements by distillation and determined colorimetrically; chlorine by the thiocyanate method and bromine by the rosaniline method. The chlorine and bromine contents of rocks cover a very wide range with no relation to the type of rock. The Br/Cl ratio, however, is in a relatively narrow range from 1×10−3 to 16×10−3 by weight, mostly from 1×10−3 to 6×10−3, and evidently lower than those reported by previous investigators. The average Br/Cl ratio is (3±2)×10−3, about one-seventh of the value generally accepted for igneous rocks. The halogen content of quartz and feldspar is usually so small that it was not usually determined. The Br/Cl ratio in biotite seems to be rather small and Qertainly is smaller than 3×10−3 on the average. The Br/Cl ratios in volcanic rocks are similar to those in volcanic gases for any one volcano studied.
Metal Ion-catalyzed Glycolysis of Terephthalonitrile
Authors: Ikeda Takashi , Kitabatake Michitoshi , Ito Masatomo , Noguchi Yoshitaka 
Published: July 2006

Abstract
The effects of various metal compounds on the glycolysis of terephthalonitrile were studied in the presence of water at 185°C. The catalytically-active species were found to be metal ions. Their catalytic activities were correlated with the acid ionization constants, pKa, of metal ions. The active catalysts were limited to the metal ions with pKa values larger than 7. The study of the reaction mechanism suggests that, while one group of metal ions accelerates the formation of glycol and hydroxyl anions, the other involves catalytic acceleration through the coordination of metal ions. The metal ions with pKa values of less than 7 showed no catalytic activities. These results were interpreted in terms of the tendency of the metal ions to form too stable coordination intermediates. Most of these metal compounds also served to inhibit the reactions. For a series of salts derived from a given metal, the catalytic activities were found to decrease with a decrease in their solubilities in water. On the other hand, metal oxides and hydroxides had high catalytic activities.
Stereochemical Studies of Monoterpene Compounds. VI. The Stereochemistry of 2-Hydroxypinocamphone and Its Reduction Products
Authors: Suga Takayuki , Shishibori Tsuyoshi , Hirata Toshifumi , Matsuura Tamon 
Published: July 2006

Abstract
The stereochemical structure of (+)-2-hydroxypinocamphone (II), which was obtained from (−)-α-pinene (I) by the permanganate oxidation, was examined by a combination of physicochemical methods. It was thus found that the C-2 methyl group is trans with respect to the C-6 bridge and that the preferred conformation is V having an axial hydroxyl group. In addition, the preferred conformation of cis-α-pinene glycol (IX) and trans-α-pinene glycol (X), which were produced from II by the lithium aluminum hydride reduction, was found to be IXa and Xa respectively.
Preparation of Acetylene-Alcohol Dicobalt Hexacarbonyls and Their Reactivity towards Acid
Authors: Kim Pu-Jun , Hagihara Nobue 
Published: July 2006

Abstract
A series of acetylene-alcohol dicobalt hexacarbonyls was prepared from acetylene-alcohols and dicobalt octacarbonyl. The reactivity towards aqueous sulfuric acid in boiling methanol was investigated. From the ethynyl carbinol complexes, R1R2C(OH)C≡CH·Co2(CO)6, trinuclear cobalt complexes, R1R2CHCH2CCo3(CO)9, were obtained accompanying the reduction of C-OH to a C-H moiety. On the other hand, from the butynediol complexes, R1R2C(OH)C≡CC(OH)R1R2·Co2(CO)6, binuclear cobalt complexes, R1R2CHC≡CCHR1R2·Co2(CO)6, or 1,1,4,4-tetraphenyl-1,3-butadiene were obtained. The structures of all these compounds have been confirmed by analytical measurements and by a study of their absorption spectra.
Effect of the Counter-Electrode Material on the Emission Spectrochemical Determination of Silicon and Manganese in Steel
Authors: Suzuki Takanori , Kambara Tomihito 
Published: July 2006

Abstract
The line intensities of Si and Mn appear much more strongly in the spectrochemical analysis of high-carbon low-alloy steels when a low-voltage spark is employed. Considering the change in the line intensity with the time under various excitation conditions with graphite and zinc counter-electrodes, the present authors have established an improved method for the spectrochemical determination of Si and Mn. The effect of the heat-treatment on the metallurgical structure has been investigated by means of an electron-probe microanalyzer, and the results compared with the spectrochemical data.
Studies of Poly-2-vinylpyridine. VI. Thermodynamic Data on Solutions of Poly-2-vinylpyridine in Various Solvents
Authors: Arichi Shizuo , Tanimoto Yoshio , Murata Hiromu 
Published: July 2006

Abstract
The viscosities of dilute solutions of several fractions of poly-2-vinylpyridine have been measured in methanol, isopropanol, chloroform, benzene, dioxane, and methyl ethyl ketone at different temperatures, ranging from 15 to 65°C. The osmotic pressures of dilute solutions of fractions of the polymer have been measured in dioxane at 10, 25, 40, and 65°C. The data have then been analysed using the theories of Flory and Fox and of Kurata and Stockmayer. The results obtained are as follows: (1) the entropy parameters, ψ1, for the solutions of poly-2-vinylpyridine in methanol and isopropanol are negative, while the critical miscibility temperatures, θ, are positive and extraordinary high; (2) ψ1 is positive and θ is negative in chloroform; (3) These parameters behave regularly in benzene and dioxane. Qualitatively the same results have also been obtained with the poly-4-vinylpyridine fraction in several solvents, including methanol and chloroform. These results show that in alcohols and chloroform the temperature coefficient of the solubility of polyvinylpyridines is negative, and indicate the presence of strong interaction between segments and solvents, probably due to hydrogen-bond formation.
Microwave Spectrum of Cyclohexanone
Authors: Ohnishi Yoshitake , Kozima Kunio 
Published: July 2006

Abstract
The microwave spectrum of cyclohexanone has been investigated in the frequency region from 7.7 to 23.4 Gc/sec. The R- and Q-branches for both the a- and the c-type have been assigned for the vibrationally ground state. The rotational constants obtained are A=4195.30 Mc/ sec, B=2502.57 Mc/sec, and C=1754.49 Mc/sec. From these values it can be concluded that the molecules have the chair form. The value of the component of the dipole moment |μa| is 2.74±0.03 D, and that of |μc| is 0.86±0.03 D. The value of the total dipole moment is 2.87±0.04 D, a value which is in agreement with that obtained by Debye’s method. For the structural parameters Romers’ data obtained by the electron diffraction seems to be nearly correct.
Synthesis of Chelating Agents. VI. Chelating Behavior of 1,2,3-Triaminopropanehexaacetic Acid with Divalent Metal Ions
Authors: Moriguchi Yoshiki , Miyazaki Mitsumasa , Ueno Keihei 
Published: July 2006

Abstract
The chelate stability constants of 1,2,3-triaminopropanehexaacetic acid (TAPHA) with alkaline earth metals, cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) were determined at 25°C and an ionic strength of 0.1 (KNO3). The stability constants of monoprotonated mono nuclear-, dinuclear- and mixed metal dinuclear chelates as well as normal mononuclear chelate were determined. The structure and chelating behavior of TAPHA in an aqueous solution were discussed by refering to those of the other complexanes of related structure. The crystalline metal chelates of TAPHA were also prepared and their structures were proposed on basis of the results of elementary analyses and infrared spectra.
The Thermal Decompositions and Mass Spectral Studies of the Cyclic Anhydrides of Some β-Sulfocarboxylic Acids
Authors: Nishitomi Katsuhiko , Nagai Toshikazu , Tokura Niichiro 
Published: July 2006

Abstract
The thermal decompositions of the cyclic anhydrides of β-sulfopivalic acid (III) and β-sulfoisobutyric acid (IV) have been studied. The pyrolysis of III without a solvent gave pivalic acid, isobutene, isobutane, water, and a mixture of trimers of isobutene, while the pyrolysis of IV resulted in the formation of methacrylic acid and acetone. In the case of III, the evolution of sulfur dioxide and carbon dioxide occurred mainly. On the contrary, in the case of IV, the carboxylic acid derivative was the predominant product. These results might be interpreted in terms of a decomposition mechanism in which the compound (IV) having α-hydrogen to a carbonyl group undergoes thermal decomposition via a concerted mechanism. In the case of IV, it should be noted that acetone was formed. This paper will also be concerned with the mass spectra of III and IV and with the cyclic anhydride of β-sulfopropionic acid.
Nitration of Thenyl Derivatives. II. Preparation of Three Isomeric Mononitro Derivatives of 2-Thenyl Chloride and 2-Thenyl Acetate
Authors: Sone Tyo , Matsuki Yasuo 
Published: July 2006

Abstract
In connection with the investigation of the products of the nitration of 2-thenyl chloride (I) and 2-thenyl acetate (II), three isomeric mononitro derivatives of I and II were prepared, and it was shown by NMR spectral study that, as in the case of I, the product obtained in the nitration of II by nitric acid in acetic anhydride consisted of all three isomeric mononitro derivatives. The isomer distribution of the mononitro derivatives of II, as determined by infrared spectroscopy, indicated 77% of the 5-, 9% of the 4-, and 14% of the 3-nitro isomer.
Intramolecular Energy Transfer in Europium Chelates Due to Excitation of the Triplet State
Authors: Matsuda Yoshihisa , Makishima Shoji , Shionoya Shigeo 
Published: July 2006

Abstract
The purpose of this paper is to clarify whether intramolecular energy transfer in europium chelates occurs via the triplet state of the ligand. It is attempted to excite the triplet state of europium dibenzoylmethide (EuD) by utilizing intermolecular triplet-triplet energy transfer from lanthanum dibenzoylmethide (LaD). In mixed solutions of EuD and LaD, the intensity and decay time of the ligand phosphorescence of LaD decreases with increasing molar fraction of EuD at liquid nitrogen temperature. Nearly in proportion to this, the intensity of the europium emission of EuD is enhanced, veryfying the occurrence of energy transfer from LaD to EuD. This fact is taken as clear evidence that intramolecular energy transfer takes place via the triplet state.
Group Interactions in Polyelectrolytes. I. Amination Kinetics of Chloromethylated Polystyrene
Authors: Kawabe Hiroshi , Yanagita Masaya 
Published: July 2006

Abstract
Chloromethylated polystyrene is quantitatively aminated by n-butylamine or n-dibutylamine in dioxane, but the plot of the logarithmic term in the simple second-order rate equation against the time is not represented by a single straight line, but is divided into two lines which intersect nearly at the half-amination point. These results are interpreted in terms of the step-by-step amination resulting from the steric effect of the already-aminated neighbors which have bulky alkyl groups. By assuming two distinct reactivities of chloromethyl groups according to their neighboring environment, rate equations for two separate steps are derived; these equations give k1, the rate constant in the first step, and k2, that in the second step. In the presence of a large excess of amine, the over-all kinetics can be expressed by:
dx/dt=[ab/(2k_1-k_2)][2k_1-(k_2)e^-2k_1at+k_1-k_2e^-k_2^at],
where x is the concentration of chloride ions at time t; a is the initial concentration of amine, and b, that of the chloromethyl group. The equation is found to be substantially valid for the values of k1 and k2 computed by the equations for the individual steps.
Studies on the Delayed Fluorescence by Means of a Flash Technique
Authors: Kikuchi Koichi , Kokubun Hiroshi , Koizumi Masao 
Published: July 2006

Abstract
It has been shown that the delayed and normal fluorescence can be measured accurately by a usual flash apparatus. Such measurements, combined with that of T–T absorption, have enlarged the potentiality of a flash technique to a large extent. As an example, a simple method of differentiation between E-type and P-type delayed fluorescence has been presented. Detailed studies have been made on the T–T annihilation process of anthracene (A) and the probability for Process AT+AT→A+A*, has been decided. The value obtained is 0.077±0.005. E-Type delayed fluorescence of eosine and proflavine have been studied and the value of kt·φST (kt, the rate constant of Process, T\ightharpoonupS*; φST, the probability of the intersystem crossing) have been evaluated, to be 3.36 and 2.78 sec−1 respectively. Some advantages of the present method over the sector method have been discussed.
The Preparation of Optically Active Trimethylcyclododecatriene by the Resolution of Racemic Oligomers and the Asymmetric Oligomerization
Authors: Furukawa Junji , Kakuzen Tsuneo , Morikawa Hiroyuki , Yamamoto Ryuzo , Okuno Osamu 
Published: July 2006

Abstract
Trimethylcyclododecatriene was prepared by the oligomerization of pentadiene, using the diethylaluminum chloride-titanium tetrabutoxide system as a catalyst. The resulting oligomer was fractionated by vapor-phase chromatography into geometrical (cis and trans) and structural (head-to-tail and head-to-head) isomers with respect to the pentadiene units involved. The structures of these isomers were proposed on the basis of infrared and NMR spectra of the oligomers and their hydrogenated products. The results of the oxidative degradation of the oligomers were compatible with the proposed structures. Further, the existence of stereoisomers was shown by resolution and asymmetric oligomerization. The resolution of d- and l-enantiomers was carried out through the asymmetric hydroboration of the oligomers, while the asymmetric oligomerization was achieved using the titanium menthoxide-diethylaluminum chloride system as a catalyst.
Anomalous Effect of the Concentration of Metal-salt Catalysts in the Liquid-phase Oxidation of p-Xylene and Toluene
Authors: Kagami Kanekichi 
Published: July 2006

Abstract
By studying the relation between the concentration and the oxidation activity of various metal catalysts, mostly naphthenates, oleates, linoleates, and caprates of manganese, cobalt, and nickel salts, as well as mixed catalysts of two kinds, it has been established that, in general, there is an anomalous effect of the catalyst concentration-namely, the catalytic activity disappears above a certain point in the concentration of the catalyst. The anomalous concentration effect of a catalyst is observed in the oxidation of toluene and p-xylene with all the catalysts, but chromium naphthenate is a lone exception in the oxidation of p-xylene. It has been shown that the anomalous effect is due to the association of the catalyst in the hydrocarbon solvent to be oxidised, and that the associated catalyst does not act to promote oxidation. The association is reversible, being dependent on the concentration of the catalyst, so the anomalous concentration effect of a catalyst disappears on dilution.
Studies of the Organic Reactions of Metal Carbonyls. XIII. The Reduction of Olefin Oxides with Potassium Iron Carbonylates
Authors: Takegami Yoshinobu , Watanabe Yoshihisa , Mitsudo Takeaki , Kanaya Isao , Masada Hiromitsu 
Published: July 2006

Abstract
The reaction between potassium iron carbonylates (KHFe(CO)4, K2Fe(CO)4, and K2Fe2(CO)8) and olefin oxides has been studied. Styrene oxide reacts readily with these carbonylates and with carbon monoxide under an atmospheric pressure and at 30°C. As the reaction products, styrene, ethylbenzene, and α- and β-phenylethyl alcohol are obtained. The major product is styrene or β-phenylethyl alcohol for the reaction of K2Fe(CO)4 or KHFe(CO)4 and K2Fe2(CO)8 respectively. The effects of solvents and additives are examined. Further, propylene oxide and epichlorohydrin are found to react with K2Fe(CO)4 and carbon monoxide to give not only carbonylated products, but also propylene. The results indicate that olefin oxides are generally reduced with K2Fe(CO)4 and carbon monoxide to give the corresponding olefins and carbon dioxide.
(Remark: Graphics omitted.)
Reactions of Dimethylaniline with Some Resonance-stabilized Radicals
Authors: Okazaki Renji , Inamoto Naoki 
Published: July 2006

Abstract
Reactions of dimethylaniline with some resonance-stabilized radicals were studied. 2-Cyano-2-propyl radicals and 2-methoxycarbonyl-2-propyl radicals reacted to give N-methyl-N-(3,4-dicyano-3,4-dimethylpentyl) aniline and the corresponding 3,4-dimethoxycarbonyl derivative, respectively, while benzyl radicals and α-methoxycarbonylbenzyl radicals did not give reaction products with dimethylaniline. Mechanism of these reactions was proposed and it was pointed out that electron transfer from dimethylaniline to radicals was an important stage in these reactions.
Analysis of Vapor Pressure of Some Molecular Crystals
Authors: Chihara Hideaki , Nakamura Nobuo 
Published: July 2006

Abstract
Vapor pressure equations of the form logPTn⁄2=a⁄T+b were derived, using high temperature Thirring expansion, which are applicable to crystals of polyatomic molecules. The exponent n is determined by the type of motion of molecules in the crystal, libration or rotation. If combined with the heat capacity data, the method of analysis may be used to derive such vibrational propoerties as static energy, zero point energy, geometric mean frequency, and molecular libration frequency. Examples of the analysis of existing vapor pressure data are given for solid iodine, iodine monochloride, and high temperature modifications of nitrogen, hydrogen chloride, and methane.
The Crystal Structure of the 1 : 1 Complex of 1,2,4,5-Tetracyanobenzene and Hexamethylbenzene
Authors: Niimura Nobuo , Ohashi Yuji , Saito Yoshihiko 
Published: July 2006

Abstract
The crystal structure of the 1 : 1 complex formed between hexamethylbenzene and 1,2,4,5-tetracyanobenzene has been determined by X-rays. The crystal is monoclinic, with two formula units of the complex in a cell of dimensions ; a=15.07, b=8.92, c=7.41 Å and β=104.9°. The space group is P21⁄n. The structure was deduced from a three-dimensional Patterson synthesis, and refined by block-diagonal least-squares method. The constituent molecules are stacked alternately in infinite columns along the c-axis. The relative configuration of the donor and acceptor molecules is consistent with the theoretical calculation.