bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Dipole Moments of the Oligether of Ethylene Glycol
Authors: Kimura Ko , Fujishiro Ryoichi 
Published: July 2006

Abstract
The dipole moments of ethylene glycol dimethyl ether (N=1), diethylene glycol dimethyl ether (N=2), triethylene glycol dimethyl ether (N=3), and tetraethylene glycol dimethyl ether (N=4), were measured in n-hexane or benzene at 25°C and 45°C. The observed dipole moments of N=1, N=2, N=3, and N=4 are 1.59 D, 1.92 D, 2.16 D, and 2.44 D, respectively, in n-hexane at 25°C, 1.71 D, 1.97 D, 2.22 D, and 2.45 D, respectively, in benzene at 25°C, and 1.72 D, 1.98 D, 2.27 D, and 2.50 D, respectively, in benzene at 45°C. The dipole moments were theoretically calculated on the assumptions that: (i) the dipole moments of these chain molecules are given by the vector sum of the polar groups of ether whose group moment is 1.20 D, and (ii) all the internal rotations of a chain molecule are free. The calculated values of N=1, N=2, N=3, and N=4 are 1.67 D, 2.03 D, 2.33 D, and 2.60 D, respectively. The agreement between the observed and the calculated values is satisfactory. The solvent effect and the temperature dependence of the observed dipole moments have also been discussed in terms of chain flexibility.
Effects of Pressure on the Chemical Properties of the Solid Surface. II. The Surface Acidity and the Catalytic Activity of Compressed Potassium Bisulfate
Authors: Ogino Yoshisada , Kawakami Takeshi , Tsurumi Kazuyuki 
Published: July 2006

Abstract
Experimental studies of the chemical properties of the surface of potassium bisulfate samples which had been subjected to compressions of 0–3750 kg./cm2 at room temperature were carried out. Namely, on the compressed sample, the surface acidity at room temperature was measured by the indicator method, while the catalytic activity for the conversion of acetaldehyde to metaldehyde was measured at the temperature of a dry ice-methanol mixture by the bulk polymerization technique. Experimental results showed that the compression of the bisulfate resulted in an increase in the surface acidity at H0=1.5 and in a reduction of the acidity at H0=4.0. Further, it was found that the increase in the compressing pressure resulted in an increase in the catalytic activity of the sample. Thus, the existence of a close relation between the catalytic activity and the surface acidity at H0=1.5, and the effectiveness of the pressure in the improvement of the catalytic activity through changing the acid strength distribution on the sample surface were experimentally demonstrated.
Molecular Structure Determination by Gas Electron Diffraction at High Temperatures. I. Arsenic
Authors: Morino Yonezo , Ukaji Takeshi , Ito Tetsuzo 
Published: July 2006

Abstract
A high-temperature nozzle assembly for gas-electron diffraction has been designed and constructed. The molecular structure of gaseous arsenic at 485°C has then been investigated by the use of this nozzle. The regular tetrahedral structure of the molecule has been confirmed from the observed index of resolution; the interatomic distance has been determined to be rg(As−As)=2.435±0.004Å, while the mean amplitude has been determined for the first time (l(As−As)=0.085±0.006Å). The observed amplitude has led to the evaluation of the bond-stretching force constant, fr(As−As)=1.5±0.3 mdyn./Å.
The Spectrophotometric Determination of Thiophene in Petroleum Naphtha with α-Nitroso-β-naphthol
Authors: Kashiki Masayuki , Ishida Kazuyoshi 
Published: July 2006

Abstract
A colorimetric method for the direct estimation of thiophene in petroleum naphtha without interference from the other sulfur compounds present has been worked out. The test is based on the blue-green color produced by the reaction between thiophene and α-nitroso-β-naphthol in the presence of sulfuric acid. The procedure accounted for from 10.0 mg./ml. of thiophene sulfur down to a mere trace of thiophene, of the order of 0.01 mg./ml. thiophene sulfur.
Single Stage Oxidation of p-Xylene with Ozonized Air
Authors: Takaya Tsuguo , Koga Tadashi , Hara Tadashi 
Published: July 2006

Abstract
A new method has been found by which terephthalic acid can easily be obtained by a single-stage oxidation of p-xylene in glacial acetic acid. p-Xylene was oxidized with ozonized oxygen or air at 90°C in the presence of cobaltous acetate, ammonium bromide and an unsaturated aliphatic compound such as tetrachloroethylene. The effects of various factors on the oxidation rate were examined by measuring the absorption rates of oxygen. The reaction rates were measured for two steps, i. e., p-xylene to p-toluic acid and p-toluic acid to terephthalic acid, in the presence and absence of ozone respectively. The reaction mechanisms for each step have been discussed. It seems that the role of ozone and tetrachloroethylene in the present oxidation reaction can be attributed to the formation of ozonide which is transformed to hydroperoxide and which then participates in the chain reaction.
The Combustion-Gas Chromatographic Determination of Minute Quantities of Sulfur in Metals
Authors: Kashima Jiro , Yamazaki Takuo 
Published: July 2006

Abstract
The determination of minute quantities of sulfur in metals is an important problem in refinery processing. This paper will describe a combustion-gas chromatographic method which gives precise results. This method is applicable to various metals, including iron and steels. Standard samples containing 0.011% of sulfur show a standard deviation of 0.0001%. Titanium and copper containing from 0.004 to 0.008% of sulfur show a mean deviation of 0.0003%. The limit of detection is 10 μg. (0.001%) of sulfur in a 1.0 g. sample. It takes about 10 min. to determine the sulfur content by this method.
The Stereoselectivity of Catalysts in Hydrogenation. I. The Catalytic Hydrogenation of 2-Cyclopentylidenecyclopentanol and 2-Benzylidene-1-tetralol
Authors: Mitsui Sekio , Senda Yasuhisa , Saito Hideyo 
Published: July 2006

Abstract
2-Cyclopentylidenecyclopentanol (I) was hydrogenated over Raney Ni to produce a mixture of 95% of trans- and 5% of cis-2-cyclopentylcyclopentanol (III). However, over a Pd catalyst I gave a mixture of 2-cyclopentylcyclopentanone (IV), cyclopentylcyclopentane (V) and trans-and cis-III. In the hydrogenation of I over PtO2, trans-III was a predominant product (93%) in ethanol, whereas in acetic acid a mixture of 2 parts of trans- and 1 part of cis-III was obtained, and in acetic acid with one drop of hydrochloric acid, the ratio of trans and cis was one to two. A large amount of V was also obtained in cases of both acetic acid. The hydrogenation of 2-benzylidene-1-tetralol (II) resulted in 2-benzyl-1-tetralols (VI), the yields of trans- and cis-VI being as follows: over Raney Ni, 78% and 19%; over Pd, 33% and 63%; and over PtO2 in ethanol, 58% and 34%, respectively. From these results, it was found that, in the cases of Raney Ni and PtO2 in ethanol, the directive effect of the hydroxyl group is very efficient, but that it is small over Pd, while in acetic acid, especially with hydrochloric acid, such an effect decreases over PtO2.
The Reactions of Amido Phosphites. A New Synthesis of Oxazolidine, Imidazolidone and Thiazolidine Derivatives
Authors: Mitsunobu Oyo , Ohashi Takashi , Mukaiyama Teruaki 
Published: July 2006

Abstract
A new method for the preparation of various 2, 3-disubstituted oxazolidine, 2, 3-disubstituted thiazolidine and 1, 3-disubstituted imidazolidone derivatives from β-aminoethyl phosphites and either phenyl isocyanate or phenyl isothiocyanate has been developed. When 1 mol. of ethyl bis(β-anilinoethyl) phosphite, resulting from the reaction of ethyl bis(diethylamido) phosphite with N-phenyl ethanolamine, was treated with 2 mol. of phenyl isocyanate, 2-phenylimino-3-phenyl-1,3-oxazolidine was obtained in a 57% yield, along with an oily product. This oily product afforded a 36% yield of N, N′-diphenyl-2-imidazolidone when it was treated with sodium ethoxide. On the other hand, the pentavalent phosphorus compound, ethyl bis(β-N-phenyl-ureidoethyl) phosphate, did not afford an oxazolidine derivative but was converted to imidazolidone in the presence of sodium ethoxide. The reaction of β-anilinoethyl propylene phosphite with an equimolar amount of phenyl isocyanate gave only N, N′-diphenyl-2-imidazolidone in a 32% yield; 2-phenylimino-3-phenyl-1, 3-oxazolidine could not be obtained. These reactions were then extended to the preparation of exo-imino-thiazolidines. The reactions of β-aminoethyl phosphites with phenyl isothiocyanate resulted in the formation of 2-phenylimino-3-phenyl-1, 3-thiazolidine in fairly good yields.
Molecular Structure Determination by Gas Electron Diffraction at High Temperatures. II. Arsenic Triiodide and Gallium Triiodide
Authors: Morino Yonezo , Ukaji Takeshi , Ito Tetsuzo 
Published: July 2006

Abstract
The precise molecular structures of arsenic triiodide and gallium triiodide in the vapor phase have been determined by the sector-microphotometer method of electron diffraction at the nozzle temperatures of 230°C and 255°C respectively. The results of gallium triiodide have confirmed the regular triangle structure of the molecule. The force constants of these molecules have been estimated from the observed mean amplitudes.
Organic Syntheses by Means of Noble Metal Compounds. XVIII. Friedel-Crafts Reaction Catalyzed by Rhenium Pentachloride
Authors: Tsuji Jiro , Nogi Tatsuo , Morikawa Masanobu 
Published: July 2006

Abstract
Rhenium pentachloride has been found to be a Lewis acid with an efficient Friedel-Crafts catalytic property. Aromatic rings have been alkylated smoothly with olefins or alkyl halides. By the reaction of ethylene with benzene in the presence of rhenium pentachloride, s-butylbenzene has been obtained as the main product. In the Friedel-Crafts acylation, a quantitative amount of the catalyst has been consumed in the reaction at a low temperature. On the other hand, the acylation reaction at a high temperature can proceed catalytically. Rhenium pentachloride is also active in the oligomerization of olefins, and in the cyclization and oligomerization of acetylenes.
The Band Structure of Tetramethylammonium Pentaiodide
Authors: Kusabayashi Shigekazu , Mikawa Hiroshi 
Published: July 2006

Abstract
The iodine framework in the crystal is constructed by repeated translations of a group of two pentaiodide ions (repeating unit). The wave function of a repeating unit is calculated by Hückel’s approximation, the resonance integrals between iodine 5 p orbitals being estimated empirically from the data for the gaseous iodine molecule. The wave functions of the crystal are set up in the form of Bloch functions from the wave functions of the repeating unit. The energy is calculated by a tight-binding approximation, the values of the resonance integrals between nearest neighboring repeating units being estimated from the wave functions of the repeating unit. The band-gap energy thus calculated is 1.26 eV., satisfactorily near the experimental value of 1.36 eV. This finding supports our conclusion (This Bulletin, 37, 811 (1964)) that the iodine framework is primarily important in the electrical conductivity. It is also supposed that the band model may satisfactorily be applied to the conduction mechanism. The interactions, of the Bloch functions of different energies being very slight, the band-gap energy is influenced at most in the order of 10−2 eV. even when level interactions are taken.
The Vibrational Spectra and Vibrational Assignments of Isotactic Polybutene-1
Authors: Ukita Minoru 
Published: July 2006

Abstract
The polarized infrared spectra of isotactic polybutene-1 in a hexagonal form will be measured in the region from 4000 to 700 cm−1. The normal vibrations of this polymer, which takes a three-fold helical conformation, will be calculated by the use of the GF-matrix method, with the modified Urey-Bradley force field. It will be found that the parallel and perpendicular bands correspond reasonably well to the calculated frequaencies of the A and E(2π/3) symmetry species respectively. In accordance with these correspondences, the assignments of these bands will be made and their vibrational modes discussed.
The Electrical Resistivity of Carbon Black under Compression
Authors: Noda Tokiti , Kato Hajime , Takasu Toshihiko , Okura Akihide , Inagaki Michio 
Published: July 2006

Abstract
The electrical resistivity of carbon blacks was measured under compression (up to 9 kilobars) at room temperature using a pressure vessel of the piston-cylinder type. The slope of the logρ vs. logP relation was about −0.5 for all the carbon black specimens except the original channel black. For the thermal blacks heat-treated above 2100°C, i. e., the graphitized thermal blacks, the linear relation between logarithms of resistivity, ρ, and of pressure, P, broke at about 2.5—4.5 kilobars. After the break the slope of the logρ vs. logP relation for the graphitized thermal blacks had the same value as that for natural graphite. The original channel black had a value of the slope as high as −0.9, but the 1300°C-treated channel black had a value similar to that of the other samples. This was probably due to the removal of the high-resistance film on the particle surface by the heat treatment. The first stage of the decrease in electrical resistivity with an increase in the pressure seems to be due to the yielding deformation of carbon black particles caused by the increased packing of the particles, while the second stage may be due mainly to the increase in the contact of crystallites in the particles by the elastic deformation, accompanied by a change in the preferred orientation of crystallites with the pressure.
The Structure of a Yellow Pigment from the Mutant lemon of Bombyx mori
Authors: Goto Miki , Konishi Masaki , Sugiura Katsura , Tsusue Motoo 
Published: July 2006

Abstract
The structure of N8-methylsepiapterin was previously postulated for a new pteridine from Bombyx mori lemon (This Bulletin, 38, 503 (1965)). This structure must, however, be modified on the basis of some new experiments. We will now present the 7, 8-dihydro-6-lactyllumazine structure for this compound.
The Intramolecular Hydrogen Bond of the Diol Ethers as Model Compounds of the Diols
Authors: Saitô Hazime , Yonezawa Teijiro , Matsuoka Shinichi , Fukui Kenichi 
Published: July 2006

Abstract
The intramolecular and intermolecular hydrogen bonds of the diol ethers are examined as model compounds of the diols by means of a study of their infrared and NMR spectra. The hydrogen bond shift and the intramolecular hydrogen bond shift are obtained. The value of the intramolecular hydrogen bond shift is discussed in terms of the electric field effect due to lone-pair electrons of the proton acceptor.
Nickel(II) and Copper(II) Complexes of β-Ketoamines Derived from β-Diketones and Aromatic Amines
Authors: Yamada Shoichiro , Nishikawa Hiroaki , Yoshida Emiko 
Published: July 2006

Abstract
Nickel(II) and copper(II) complexes of β-ketoamines derived from acetylacetone or benzoylacetone and aromatic amines have been newly synthesized and characterized. The aromatic amines included aniline, o-, m- and p-toluidine, o,o′-dimethylaniline, o,o′-diethylaniline, o-, m- and p-chloroaniline, and α- and β-naphthylamine. The configurations of these complexes in pyridine have been examined and compared with those in non-donor solvents. All these complexes are considered to be square-planar in non-donor solvents and in the solid state. The nickel-(II) complexes of the o,o′-disubstituted derivatives do not combine with pyridine molecules, whereas the corresponding copper(II) complexes readily combine with the pyridine molecule. The difference between nickel(II) and copper(II) ions is discussed in terms of the bonding nature of the metal ions. The β-ketoamines and salicylideneimines are also compared.
3,4-Benzotropolone and Related Compounds. V. Bromo- and Hydroxy-2,3-benzotropones
Authors: Ebine Seiji , Hoshino Masamatsu , Takahashi Kazuko 
Published: July 2006

Abstract
Isomeric 5,7- and 4,7-dibromo-2,3-benzotropones were prepared, not via 2,3-benzotropone, but by the bromination and subsequent dehydrobromination of 2,3-benzocycloheptenone. The tropone structure of these compounds was based on spectral data and hydrogenation to 2,3-benzocycloheptenone. The dibromo-2,3-benzotropones, when treated with hydroxylamine, underwent cine-reaction to 5- and 4-bromo-6-hydroxylamino-2,3-benzotropone oximes, which were then hydrolyzed and debrominated to the same 6-hydroxy-2,3-benzotropone. 5,7,5′-Tribromo-2,3-benzotropone was obtained by the drastic bromination, followed by the dehydrobromination, of 2,3-benzocycloheptenone. The position of a hydroxyl group in 6-hydroxy-2,3-benzotropone was confirmed by oxidation to o-carboxycinnamic acid, while that of the 5′-bromo substituent in 5,7,5′-tribromo-2,3-benzotropone was confirmed by hydrogenation to 5′-bromo-2,3-benzocycloheptenone.
1,3-Dipolar Cycloaddition Reaction of Thiophenecarbonitrile N-Oxides with Various Dipolarophiles
Authors: Iwakura Yoshio , Uno Keikichi , Shiraishi Shinsaku , Hongu Tatsuhiko 
Published: July 2006

Abstract
Thiophenc-2-carbonitrile N-oxide (I) and 5-chlorothiophene-2-carbonitrile N-oxide (II) were synthesized by the chlorination of corresponding aldoxime with nitrosyl chloride. These compounds gave Δ2-isoxazolines and isoxazoles through 1,3-dipolar cycloaddition reaction with compounds having double or triple bond as dipolarophiles. In the cycloaddition reaction, II was less reactive than I. This would be explained by stability of II owing to electron-withdrawing ability of chlorine atom at 5-position in the thiophene ring. Furoxans, the dimers of the nitrile N-oxide, were formed from these 1,3-dipoles in the absence of dipolarophile.
The Formation and Chelate–forming Properties of 2-Chloriminocyclohexanone Oxime and Its Hydrochloride
Authors: Kobayashi Yoshinari , Wakamatsu Shigeru 
Published: July 2006

Abstract
Cyclohexane-1,2-dione dioxime (1) in absolute ethanol containing hydrogen chloride was subjected to an irreversible dehydration to afford 2-chloriminocyclohexanone oxime hydrochloride (2), which could be liberated by cautious neutralization with sodium carbonate. The novel free and salt-form compounds thus obtained reacted with metal ions, such as Cu(II), Co(II), Ni(II), and Pd(II), to afford stable complexes. The molar ratio and the consecutive stability constants of a Ni(II) complex of 2 were determined and compared with those of a complex of 1 with Ni(II). An approximate linear relationship between the logarithm of the rate constant of the N-chlorimination and the acidity function, H0, was observed.
The Structure of the Crystalline Adduct of Nitrosobenzene and 2,3-Dimethyl-1,3-butadiene
Authors: Oikawa Eizo , Tsubaki Suguru 
Published: July 2006

Abstract
The structure of the crystalline product obtained in up to an 18% yield in the reaction of nitrosobenzene with 2,3-dimethyl-1,3-butadiene in diethyl ether was determined to be the nitrone, II, by means of NMR, IR, and a series of reductions with lithium aluminum hydride and zinc–acetic acid, and by the ozonization of the reduction product.
Synthesis and Structural Investigation of trans-8-Oxabicyclo[4.3.0]nonan-3-ols
Authors: Leong Ta-Yan , Imagawa Takeshi , Kawanisi Mituyosi 
Published: July 2006

Abstract
Various methods of the synthesis of trans-8-oxabicyclo[4.3.0]nonan-3-ols were examined; the best method for c-3-hydroxy-r-1-trans-8-oxabicyclo[4.3.0]nonane (2) was found to be the LAH reduction of the epoxide of trans-8-oxabicyclo[4.3.0]non-3-ene (1), while t-3-hydroxy-r-1-trans-8-oxabicyclo[4.3.0]nonane (3) could be obtained in a high stereoselectivity by the LAH reduction of trans-8-oxabicyclo[4.3.0]nonan-3-one (4). The structures of the two isomeric alcohols were investigated by means of nuclear magnetic resonance spectroscopy using the paramagentic shift reagent. The C-1 proton of 2 is shifted to a much greater extent than that of 3. Much as in the case of the cis analogues, there is almost no difference in the coordination abilities of europium ions with the alcoholic and ethereal oxygen atoms in these compounds.
The Reaction of Dicyclopentadiene with Ethyl Diazoacetate
Authors: Sato Tadashi , Mori Tamio , Shinoda Junichi 
Published: July 2006

Abstract
The reaction of endo-dicyclopentadiene (1) with ethyl diazoacetate (3) was carried out in the presence of several copper compounds. Two patterns of reaction were observed, depending on the type of copper compound used; the following schemes were proposed for the two reactions. I: The reaction proceeds through a coordination of the olefinic group to copper to form an olefin-copper complex, followed by an attack of the diazo compound on the complex. II: The reaction proceeds through a coordination of the diazo compound to copper to form an inversed ylide (11), followed by an electrophilic attack of the carbonium-ion center in 11 on the olefin to form a three-membered cyclic transition state, 12.
The Mechanism of Photo-substitution of Ferrocene in Haloalkane–Ethanol Solutions
Authors: Akiyama Takeo , Sugimori Akira , Hermann Horst 
Published: July 2006

Abstract
The mechanism of photo-substitution of ferrocene in haloalkane–ethanol solutions was investigated by the flash photolysis technique and other chemical methods mainly on the ferrocene–carbon tetrachloride–ethanol system. The photoreaction is initiated by the excitation of charge transfer state (electron transfer from ferrocene to carbon tetrachloride). In the absence of ethanol, CT-excitation leads to the decomposition of ferrocene to FeCl3 with first order reaction kinetics of k=(1.6±0.5)×105 s−1. The formation of FeCl3 was inhibited by ethanol effectively to give ethyl ferrocenecarboxylate. Diethylamine quenched the formation of FeCl3, whereas dimethyl sulfoxide, a stronger base than ethanol, is a less effective quencher than ethanol. These facts suggest that the most important role of ethanol is to ethanolyse trichloromethylferrocene, which otherwise decomposes to FeCl3.
Reaction of Alkylbenzene. IX. A Study of the Reaction of Methylbenzenes under the Influence of Aluminum Chloride-Hydrogen Chloride by Means of NMR
Authors: Okami Yoshihide , Otani Noboru , Katoh Daigo , Hamanaka Sawako , Ogawa Masaya 
Published: July 2006

Abstract
The 1H and 13C NMR spectra of the complex layers obtained by the reaction of several methylbenzenes with aluminum chloride were measured at room temperature, and the proton exchanges were investigated. The ring 1H signal shifted to a higher field as a result of fusion with the signal of the aliphatic CH2 group of the methylbenzenonium ion, which resulted from the protonation to ring carbons. Thus, the proton exchange is considered to proceed among the ring carbons of aromatic hydrocarbon and its benzenonium ion in the complex layer intermolecularly as well as intramolecularly. This finding agrees with the results obtained from the 13C NMR spectra of the complexes. The 13C spectral data showed that the ease of the protonation to ring carbons depends upon the differences in the chemical shifts between the complex layer and the starting aromatic hydrocarbon, and some facts concerning the isomerization of methylbenzenes were discussed.