bluuebunny/crossref_metadata_2025_split huggingface dataset:
Measurement of Negative Ions Formed by Electron Impact. I. Negative Ion Mass Spectra of Nitroalkanes
Authors: Tsuda Satoru , Yokohata Akira , Kawai Michihiro 
Published: July 2006

Abstract
The negative ion mass spectra of nitroalkanes (nitromethane, nitroethane, 1-nitropropane and 2-nitropropane) have been mesaured with a mass spectrometer under electron energies of 80 eV, 40 eV, 9.5 eV and 4.5 eV in the range of pressure used for usual analysis. The spectral intensities of negative ions were compared with those of positive ions. In 80 or 40 eV electron impact experiments, m/e 16 (O−), 46 (NO2−), 26 (probably, CN−) and 42 (probably, CNO− or C2H4N−) ions were commonly found. Their yields showed good linearity against pressure under the present experimental conditions. The peaks of m/e 61 (parent ion; CH3NO2−) in nitromethane, of m/e 25 (C2H−) in nitroethane, 1-nitropropane and 2-nitropropane, and a relatively strong peak of m/e 60 (CH2NO2−) in 1-nitropropane were characteristic. For lower electron energies, the strong dependency of the yield of negative ions on the electron energy was confirmed. The yield of negative ions as compared with positive ions for 80 eV and 40 eV of electron energy was lower by a factor of ∼104. On the other hand, the comparison of the yield of positive ions for 15 eV electrons with that of negative ions for 9.5 eV electrons gave the value of ∼0.2. In addition, of the role these negative ions in radiolysis has been briefly discussed.
Mechanism of a Stereospecific, Photosensitized, Cyclization Reaction of 3-Methylene-1,5-heptadiene
Authors: Kita Sin-ichiro , Fukui Ken-ichi 
Published: July 2006

Abstract
In order to understand the mechanism of the photosensitized, stereospecific cyclization of 3-methylene-1,5-heptadiene, we calculated the electronic state of two intermediates (13 imaginary conformations) by the extended Hückel molecular orbital method and discussed its rotation angle dependency. We obtained the following conclusions. 1) In the two intermediates, the second model (we suppose this to be more like a real intermediate) has lower energy than the first model (we suppose this to be an initial intermediate) both in the ground state and the excited state. 2) If it is necessary for this cyclization that an overlap stabilization exists between two carbon atoms to be bonded and the intermediate has lower energy in that state, the intermediate seems to cyclize after the transition to the ground state singlet. 3) The overlap stabilization between two carbon atoms mentioned above is mainly defined by the interaction between 2p electrons in the highest occupied orbital. This fact coincides with the consequence of the frontier electron theory. 4) The existence of the overlap stabilization between 2p electrons mentioend above corresponds to the fact that the special valence atomic orbital of that two carbon atoms has the same symmetry. This fact is in line with the Woodward-Hoffmann rule on “electrocyclic reactions.”
Solubility of Ag2O in Na2O-B2O3 Melts
Authors: Maekawa Takashi , Yokokawa Toshio , Niwa Kichizo 
Published: July 2006

Abstract
The solubility of silver oxide in Na2O-B2O3 melts was determined as a function of the Na2O contents, the temperature (825°C–935°C), and the oxygen partial pressures. The results show that the silver oxide dissolves in a borate as a network modifier, just like alkali metal oxides, which destroy the B–O–B bonds to produce four coordinated boron as well as three. In the Ag2O-B2O3 binary system, the solubility of silver oxide increases with an increase in the oxygen partial pressures. In the Ag2O-Na2O-B2O3 ternary system, the solubility of Ag2O decreases with an increase in the Na2O contents. This shows that the silver oxide is a weaker base than sodium oxide. The activity of the oxygen ion, ao=, was determined from the iso-activity lines of silver oxide. In a constant basic oxide content, ao= increases with an increase in the Na2O content. By extrapolating the Ag2O contents to zero, the oxygen-ion activity in the Na2O-B2O3 melt was determined.
A Spectrophotometric Study of the Uranyl Chelate of 2-(1,8-Dihydroxy-3,6-disulfo-2-naphthylazo)-phenoxyacetic Acid
Authors: Shimoishi Yasuaki 
Published: July 2006

Abstract
2-(1,8-Dihydroxy-3,6-disulfo-2-naphthylazo)-phenoxyacetic acid reacts with the uranyl ion in an acidic medium to form a violet chelate. The composition of the chelate is 1 : 1 in the molar ratio. The apparent stability constants over the pH range from 3.4 to 5.2 and the formation constant of the chelate, are estimated spectrophotometrically at 25°C and an ionic strength of 0.1 by the use of KNO3. The value of the formation constant was calculated as 1.25×1010 from the apparent stability constants.
Electronic Structure of Tris(1,10-phenanthroline)iron(II) Complex
Authors: Ito Tasuku , Tanaka Nobuyuki , Hanazaki Ichiro , Nagakura Saburo 
Published: July 2006

Abstract
The SGF MO’s for the π-electron system of 1,10-phenanthroline have been determined by following the Pariser-Parr-Pople’s treatment. For the description of the lower excited states, the configuration interaction among nineteen singly-excited configurations with lower energy has been taken into account. The electronic spectrum of 1,10-phenanthroline has been interpreted on the basis of the results of the theoretical calculation. The SCF MO’s for the π-electron system of a coordinated 1,10-phenanthroline in the tris-iron(II) complex have been determined to be self-consistent under the electrostatic potential field of the central metal ion and the other ligand molecules. On the basis of the results for coordinated ligand, the π-electronic structure of tris-(1,10-phenanthroline)iron(II) ion has been investigated from the theoretical point of view. It has been shown that two kinds of the charge-transfer transitions are responsible for an intense absorption band in the visible region, namely electron transfers from the 3dπ orbital of iron to the lowest and the second lowest vacant π MO’s of the ligand 1,10-phenanthroline. The discussions have been given on the change of the π–π* states of 1,10-phenanthroline by the coordination.
Polarographic Study of Thallium(I) Chelates of 2,2′-Ethylenedioxybis[ethyliminodi(acetic acid)] and Cyclohexane-1,2-diamine-N,N,N′,N′-tetraacetic Acid
Authors: Kodama Mutsuo , Tominaga Yayoe 
Published: July 2006

Abstract
D.c. polarographic behavior of thallium(I) ion in 2,2′-ethylenedioxybis[ethyliminodi(acetate)] (GEDTA) and cyclohexane-1,2-diamine-N,N,N′,N′-tetraacetate (CyDTA) solutions was studied systematically. Compositions and stability constants of thallium(I)-GEDTA and CyDTA chelates were determined from the shift of the half-wave potential. In both GEDTA and CyDTA systems, thallium(I) ion gave a single well-defined wave corresponding to the following reversible one electron reduction.
(Remark: Graphics omitted.)
In contrast to the finding of Anderegg and Bottari, thallium(I) ion was found to form not only a normal chelate but also a protonated chelate with CyDTA.
Polarographic Studies of Copper(II) Chelates of Ethylenediamine-N,N,N′,N′-tetrapropionic Acid and Diethylenetriaminepentaacetic Acid
Authors: Kodama Mutsuo , Tominaga Yayoe 
Published: July 2006

Abstract
D. c. polarographic behavior of copper(II) in ethylenediamine-N,N,N′,N′-tetrapropionate (EDTP) and diethylenetriaminepentaacetate (DTPA) solutions was studied systematically. In EDTP solution, copper(II) ion invariably gave a single well-defined wave corresponding to the following reduction.
CuX2−+nH++Hg+2e−=Cu(Hg)+HnXn−4
In the DTPA solution, copper(II) ion gave a single wave reversible in nature at pH below 5.0, corresponding to the following electrode reaction.
(Remark: Graphics omitted.)
At higher pH, however, two waves could be observed. The second step was irreversible and its wave-height increased with increasing pH at the expense of the height of the first step.
Reaction of Methylsulfinyl Carbanion with Substituted Phthalic Esters
Authors: Otsuji Yoshio , Yabune Hideo , Imoto Eiji 
Published: July 2006

Abstract
The treatment of dimethyl 3-nitrophthalate (I) with a mixture of dimethyl sulfoxide and sodium methoxide, followed by the acidification of the resulting mixture with hydrochloric acid, gave azoxybenzene-2,2′,3,3′-tetracarboxylic acid (II) and 3-nitrophthalic acid (III). The similar treatment of dimethyl 4-nitrophthalate (IV) afforded 5-methoxy-2-nitroso-1,3-indanedione (V) and 4-methoxyphthalic acid (VI). The similar treatment of dimethyl 4-methoxyphthalate (XV) and dimethyl phthalate gave 2-chloro-2-methylthio-5-methoxy-1,3-indanedione (XVII) and 2-chloro-2-methylthio-1,3-indanedione (XIX) respectively. The general features of these reactions are described.
Eine Dienon-Phenol-Umlagerung von 5-Oxo-2-methyl-4,4-dibenzyl-3-äthoxycarbonyl-4,5-dihydro-indol
Authors: Suehiro Tadashi , Eimura Koji 
Published: July 2006

Abstract
Bei der Einwirkung von Acetanhydrid-Schwefelsäure auf 5-Oxo-2-methyl-4,4-dibenzyl-3-äthoxycarbonyl-4,5-dihydro-indol (I) bei 0°C, findet eine Dienon-Phenol-Umlagerung von I zu 4-Acetoxy-2-methyl-5,6-dibenzyl-3-äthoxycarbonyl-indol (III) statt, dessen Struktur aus der leichten Verseifbarkeit der 3-Äthoxycarbonyl-Gruppe von III und aus den spektroskopischen Befunden der von III abgeleiteten Verbindungen folgte.
Deoxygenation of Styrene Oxide by Zinc Metal and Lewis Acid
Authors: Miyano Sotaro , Hida Mitsuhiko , Hashimoto Harukichi 
Published: July 2006

Abstract
Styrene oxide was deoxygenated to styrene in 83% yield by zinc metal and zinc chloride in aqueous ether. Under the same reaction conditions phenyl glycidyl ether gave only 2.8% of phenyl allyl ether, and propylene oxide did not give propylene. Effects of the reaction variables on the deoxygenation of styrene oxide were investigated. The yield of styrene was varied with metal halide in anhydrous THF in the following order; ZnI2&gt;ZnCl2∼ZnBr2&gt;AlCl3&gt;SnCl4&gt;FeCl3&gt;NaI&gt;&gt;MgBr2. Styrene was formed from styrene oxide by zinc metal and zinc chloride in ca. 50% yield in THF, acetone, acetic acid, and aqueous ethanol, but not in anhydrous benzene. The yield of styrene increased almost proportionally with the increase of the molar ratio of zinc chloride to styrene oxide up to 1:1. 2-Phenyl-2-chloroethanol gave styrene when treated with zinc metal in the presence or absence of zinc chloride, but 1-phenyl-2-chloroethanol did not. Possible reaction paths of the deoxygenation of styrene oxide by zinc metal and metal halide were discussed.
Photo-Aryl Coupling and Related Reactions. II. The Formation of Triphenylenes from Halogeno-o-terphenyls
Authors: Sato Takeo , Shimada Shigeru , Hata Kazuo 
Published: July 2006

Abstract
Electronic effects on the photochemical conversion of o-terphenyl to triphenylene were examined by comparing the ultraviolet irraiation reaction, carried out in a benzene solution using iodine as an oxidant, of three classes of o-terphenyl derivatives, 4- (3) and 4′-substituted (4) and 4,4″-disubstituted derivatives (5). While a strong electron-withdrawing group such as nitro group, hindered the cyclization reaction to occur, methoxy, fluoro, chloro and bromo compounds afforded the corresponding triphenylene derivatives. With bromo and iodo compounds, however, a complex mixture of the products resulted due to photochemical cleavage of a carbon-halogen bonding, which led to the formation of phenylation products and hence phenyltriphenylenes together with reduction products. Further, with iodo compounds, it was found that no oxidant was necessary to effect the cyclodehydrogenation reaction since iodine was liberated during the photolysis. Possible pathways for the formation of the photolysis products from bromo and iodo compounds were discussed in relation to the relative rates of carbon-halogen cleavage and cyclization reactions. Comparison among three classes of halogeno compounds indicated that, with the exception of iodides, the cyclization reaction occurred more readily with type 4 compound than type 3 compounds, while type 5 compounds reacted only with difficulty.
Organic Syntheses by Means of Noble Metal Compounds. XXXVIII. Cyclohexanone Oxime Complexes of Palladium
Authors: Imamura Sinzo , Kajimoto Tsunesuke , Kitano Yukishige , Tsuji Jiro 
Published: July 2006

Abstract
Ligand exchange reactions of palladium complexes having π-allyl and acetylacetonate as ligands with cyclohexanone oxime were carried out and the formation of several new oxime complexes was reported.
The Structure and the Stereochemistry of Solidagonic Acid
Authors: Kusumoto Shoichi , Okazaki Tomomi , Ohsuka Akio , Kotake Munio 
Published: July 2006

Abstract
A new bitter principle, solidagonic acid C22H34O4, was isolated from the root of Solidago altissima L. It is a bicyclic diterpene carboxylic acid, having an acetoxyl group and two double bonds, and was formulated as II on the basis of chemical and spectroscopic studies. The other constituents of the root, kolavenic acid (XXIV) and kolavenol (XXVIII) were also isolated, and they were chemically correlated to II. The absolute configurations of II, XXIV and XXVIII were established by application of the octant rule on the ORD curves for some ketonic compounds derived from them.
Chemiluminescent Reaction between Polyphenols and Ozone in Acetic Acid
Authors: Iwaki Ryôjirô , Kamiya Isao 
Published: July 2006

Abstract
The chemiluminescence of polyphenols with ozone in acetic acid was investigated in the presence and in the absence of rhodamine B. The emission intensity in the presence of rhodamine B (IM) was about 100–500 times as large as that in the absence of the dye (IP). From the measurement of the emission intensity vs. the reaction time, it was found that the time required to attain the peak intensity of IM is almost equal to that required to attain the peak of IP at equal concentration of polyphenol. A similarity was found in the spectral distributions of IM and the fluorescence emission of rhodamine B determined under comparable conditions. Rhodamine B was scarcely decomposed for the production of the enhanced emission; this lent support to the conclusion that the enhancement effect of rhodamine B is due to an energy-transfer from an excited species produced by the oxidation of polyphenols to the dye. Determining the changes in the absorption spectra during the luminescent reaction, we also found that the emission results not from the decomposition of polyphenols but from the decomposition of an intermediate compound. On the basis of these results, a reaction scheme was proposed. If the increment of the total light emitted by the enhancement effect, (Δ), is defined as:
Δ = (Total light emitted in the polyphenol+rhodamine B system)−(Total light emitted in polyphenol alone)−(Total light emitted in rhodamine B alone),
the scheme gave the following equation:
Δ=A[R]0ln(1+[P]0⁄A[R]0) (1)
where [R]0 and [P]0 are the initial concentrations of rhodamine B and polyphenols respectively. A is the parameter, depending upon the experimental conditions. The values of Δ calculated from Eq. (1) were in fairly good agreement with the measured values.
Extraction of Hydrochloric Acid by Tri-n-octylamine in Benzene
Authors: Kojima Takashi , Fukutomi Hiroshi , Kakihana Hidetake 
Published: July 2006

Abstract
The equilibria involved in the extraction of HCl by tri-n-octylamine (TOA) in benzene have been investigated as a function of the HC1 and TOA concentrations. Two distinctly different extractions were observed for two different acidity ranges. From the extraction in the low acidity range (&lt;0.001 m HCl), it has been found that two complexes of TOA·HCl and (TOA·HCl)2are formed in the organic phase and that the equilibrium constants for the two reactions,
TOA(org)+H+(aq)+Cl−(aq)=TOA·HCl(org)
and
2TOA(org)+2H+(aq)+2Cl−(aq)=(TOA·HCl)2(org),
are K11=(1.51±0.02)×104 and K22=(2.92±0.07)×109 respectively. For higher concentrations of HCl&gt;3 m, it seems probable that two major complexes of (TOA·HCl)2HCl and (TOA·HCl)3-(HCl)2 besides the monomer and the dimer, and three minor complexes of (TOA·HCl)2(HCl)2, (TOA·HCl)3HCl, and (TOA·HCl)3(HCl)3 are formed in the organic phase.
Infrared Spectra of Partially Deuterated Acetamide
Authors: Uno Toyozo , Machida Katsunosuke , Saito Yutaka 
Published: July 2006

Abstract
The infrared spectra of orthorhombic crystals of CH3CONH2, CD3CONH2, and their N-deuterated and partially N-deuterated samples have been recorded in the region between 4000 and 400 cm−1. The bands due to the trans- and cis-NHD species have been assigned by comparing the spectra of various samples containing the NH2, ND2 and NHD species in different proportions. In the spectra of the 50% N-deuterated samples, the absorption bands near 1530 and 1360 cm−1have been assigned to the amide II and III modes, respectively, of the trans-NHD species characteristic of the trans conformation of the -CONH- group, and those near 1480 and 1400 cm−1to the NH in-plane deformation and the CN stretching modes, respectively, of the cis-NHD species. These assignments were confirmed by the normal coordinates analysis of eight isotopic species of acetamide based on the Urey-Bradley force field.
Some Experiments on the Triplet State Mechanism of the Spectral Sensitization of Poly(vinyl cinnamate) and Its Application for Searching New Sensitizers
Authors: Tsuda Minoru 
Published: July 2006

Abstract
The spectral sensitization of poly (vinyl cinnamate) is considered to occur by the triplet energy transfer from sensitizer to the cinnamoyl group of the polymer. The triplet state mechanism is useful for finding new sensitizers. Some new sensitizer were found on the basis of the theory, and the results may verify the mechanism.
Volumetric Determination of the Iodide Ion with Mercury(II) Ethylenediaminetetraacetate Using Mercury(II)-Methyl-thymolblue as an Indicator
Authors: Nomura Toshiaki 
Published: July 2006

Abstract
After 5 ml portions of 1×10−4 m methylthymolblue (MTB or H2Me4−) and mercury(II) nitrate solutions had been added to an iodide sample solution adjusted to pH 7.3–8.8, it was diluted to about 50 ml with water. This solution was titrated with a 1×10−2 m standard mercury(II) ethylenediaminetetraacetate (Hg-EDTA or HgY2−) solution until it turned blue from greenish yellow. The iodide-ion content was calculated by applying the volume of the standard Hg-EDTA solution on the calibration curve determined with solutions of known iodide-ion contents. The iodide ion reacts with HgY2− and with greenish-yellow HgMe4− to form colorless [HgY(I)]3− and blue [HgMe(I)]5− complexes respectively. The [HgMe(I)]5− complex reacts subsequently with the iodide ion to form mercury(II) iodide and greenish-yellow H2Me4−. It has been found that, except when an excess amount of the iodide ion existed, the [HgMe(I)]5− complex is the most stable among these mixed ligand complexes and mercury(II) iodide. Therefore, the iodide ion can be titrated directly with a Hg-EDTA solution by using HgMe4− as an indicator according to the following equation:
HgI2+H2Me4−+HgY2−→[HgMe(I)]5−+[HgY(I)]3−+2H+
Spectrophotometric Studies of Ethyl Xanthate Complexes in Aqueous Solutions
Authors: Nanjo Michio , Yamasaki Taro 
Published: July 2006

Abstract
The stability constants of ethyl xanthate complexes of cadmium(II), zinc(II), nickel(II), and cobalt(II) were determined spectrophotometrically in aqueous solutions. Complexes with the 1 : 1 composition, M(EX)+, were found in all cases; the stability constants of these metal complexes were calculated to be 1.2×104, 5.2×10, 4.4×10, and 1.1×10 for Cd(EX)+, Zn(EX)+, Ni(EX)+, and Co(EX)+ respectively at an ionic strength of 1.0 and at 25°C. These values were then compared with the stability constants of other metal complexes.
The Synergistic Effect in Solvent Extraction. The Effect of the Chelating Ligands on the Stability Constant of Lutetium β-Diketonate Adducts with TOPO
Authors: Honjyo Takaharu 
Published: July 2006

Abstract
The steric effect and the inductive effect of the functional groups of β-diketones on the adduct formation between lutetium chelates and TOPO in benzene was studied by using various β-diketones with aliphatic groups (acetylacetone, dipropionylmethane, pivaroylacetone, diisobutyryl-methane and dipivaroylmethane), aromatic groups (benzoylacetone, naphthoylacetone and dibenzoylmethane) and fluoromethyl groups (trifluoroacetylacetone, furoyltrifluoroacetone, thenovltrifluoroacetone, benzoyltrifluoroacetone and hexafluoroacetylacetone). The effect of the temperature on the adduct formation was then estimated. These results may be summarized as follows: (1) The stability of the adduct increases, and the larger synergism appears, as aliphatic groups, aromatic groups, and fluoromethyl groups are successively substituted for the functional groups of β-diketones. This effect may be due to the electron-withdrawing effect of the fluoromethyl group and the conjugation effect (with a metal chelate ring) of the phenyl group. (2) The adducts contain one molecule of TOPO per metal chelate except for the HFA adduct, which contains two molecules of TOPO. The steric hindrance of the terminal groups is hardly recognizable. (3) The extraction constant of the chelates increases, while the stability of the adducts decreases, with a rise in the temperature. The apparent enthalpy change (−ΔH kcal/mol) upon the adduct formation increases in the order: DPM (5.5)&lt;BzA(5.9)&lt;BFA(8.6) chelates.
A Study of the Decomposition Reaction of Cumene Hydroperoxide in the Presence of Triphenylsulfonium Chloride
Authors: Ohkubo Katsutoshi , Yamabe Tokio , Fukui Kenichi 
Published: July 2006

Abstract
The homogeneous decomposition reaction of cumene hydroperoxide in cumene was studied by the use of triphenylsulfonium chloride over a low-temperature range (30–80°C). The hydroperoxide was decomposed remarkably in the presence of the sulfonium catalyst, whereas in the absence of the catalyst it was decomposed only a little. Among the homolytic decomposition products, acetophenone and dicumyl peroxide were found to be the main products, while α-cumyl alcohol was formed in only a small amount. Moreover, methyl alcohol was found in appreciable amounts. Traces of heterolytic reaction products, such as phenol and acetone, were also detected. After discussing the reaction mechanism and the nature of catalytic action, it is concluded that the partially-occupied d orbital of the sulfonium cation may play a role in breaking the oxygen-oxygen bond of the hydroperoxide homolytically. The counter chloride anion seems to take part in the heterolytic reaction to some extent.
Electronic Structures of Unsaturated Molecules Containing Hetero-atoms, — Configuration Interaction Treatment Including Doubly Excited Configurations
Authors: Hirota Fumihiko , Nagakura Saburo 
Published: July 2006

Abstract
The π-electron structures of several unsaturated molecules containing hetero-atoms were studied by SCFMO-CI scheme employing the Pariser-Parr-Pople method, special attention being paid to the effect of doubly excited configurations upon calculated transition energies, transition moments and π-electron distributions in the ground and lower excited states. The transition energies and oscillator strengths calculated for pyridine, phenol, aniline, pyrrole and furan were compared with their experimental values. Consequently, the inclusion of doubly excited configurations was found to improve the coincidence between the theoretical and observed values and to remove some difficulties in the application of the Pariser-Parr-Pople method to molecules containing hetero-atoms. One-center integrals WP and γPP for hetero-atoms were taken as parameters in the calculations of phenol and aniline. Their fittest values were determined reasonably to be WN=−24.71, Wo=−30.08, γNN=13.75, and γOO=16.78 eV.