bluuebunny/crossref_metadata_2025 huggingface dataset:
Vulcanized Aniline Black. Its Electrical Conductivity and Catalysis upon the Decomposition of Hydrogen Peroxide
Authors: Inoue Hiroo , Kida Yasuji , Imoto Eiji
Published: July 2006

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

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.
The Dipole Moments of the Oligether of Ethylene Glycol
Authors: Kimura Ko , Fujishiro Ryoichi
Published: July 2006

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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.
An Interstitial-Electron Model for the Structure of Metals and Alloys. IV. Magnetic Properties of Metals and Electronic Structures of Group VI–VIII Metals
Authors: Johnson Oliver
Published: July 2006

The interstitial-electron model leads to localization of d-electrons on the metal ion cores starting with group 6 metals which would have all the tetrahedral and octahedral interstices occupied by itinerant electrons. In the model the itinerant electrons play the role of ligands and determine the degeneracy of the d-orbitals localized on the ion core. There are mutual accomodations as far as location of itinerant electrons in specific interstices and d-electrons in preferred orbitals. Consideration of metal properties, especially Hall Coefficients, leads to reasonable values for both localized and itinerant magnetic moments. The relatively large spatial extension of 3d-orbitals at low intermetallic distances accounts for the magnetic moments in Cr, Mn, Fe, Co, and Ni. A striking consequence of the application of the interstitial-electron model to Fe is that it reproduces in detail the regions of positive and negative magnetization (including the interlocking rings on edges and faces) observed in neutron diffraction studies by Shull and Mook.
An Interstitial-Electron Model for the Structure of Metals and Alloys. V. Metal Alloys and Intermetallic Compounds
Authors: Johnson Oliver
Published: July 2006

On the basis of the interstitial-electron model for metals the essential feature of the metallic state is the relatively free movement of electrons, (\bare), between interstices in a close-packed array of metal ions (positive cores). For a solid solution of one metal in another in which the metal ions have nearly the same size and core charge, the interstitial-electron structures which incorporate spatial and spin correlation of electrons are the same as for metals. Metallic properties can also result when the ratios of two less similar metals in an alloy are such as to give interstices with a constant ratio of the two metals surrounding them. Occupancy of such “homogeneous interstices” is the basis for intermetallic compounds and accounts for the Hume-Rothery rules. Intermetallic compounds such as γ phases (e.g. Cu5Zn8) are unique in that \bare and electron pairs must be assigned to two or more types of interstices which have different ratios of the two metal ions around them. This localization of \bare density explains the very poor conductivity, the hardness, the brittleness and the large diamagnetic susceptibility of γ phases. The structural framework of the interstitial-electron description accounts for the large composition range of the interstitial phases and can naturally include effects of ion core size and charge. Interpenetration of d10 ion cores by itinerant electrons which gives a balancing of the positive fields of the 2 ion cores accounts for the preponderance of d10 metals among intermetallic phases.
Spectroscopic and Coordination Behavior of α-Cyanothioacetamide
Authors: Ray Arabinda , Sathyanarayana D N
Published: July 2006

α-Cyanothioacetamide (CTAM) complexes of cuprous chloride CuCl–2CTAM and cuprous bromide CuBr–2CTAM have been prepared. The infrared spectra of CTAM and its complexes, and the laser Raman spectrum of CTAM have been recorded. Assignment of the frequencies of the ligand has been made on the basis of a normal coordinate analysis using the Urey-Bradley force field. The copper (I) complexes are inferred to have thiocarbonyl sulfur and amide nitrogen bonded CTAM as evidenced from infrared and electronic spectra.
The Chlorination of Benzene with a Sodium ChlorideFerric Chloride Melt
Authors: Tamai Yasukatsu , Ohtsuka Yasuo
Published: July 2006

The chlorination of C6H6 with a NaCl–FeCl3 (52: 48 in mol) melt was studied in a batch reactor at 250 °C and at a constant pressure. The main chlorinated products were monochlorobenzene (MCB) and dichlorobenzene (DGB). The isomers in DCB were ortho and para, and did not include the meta form. The rate of chlorination was nearly proportional to the benzene pressure in the range from 0.5 to 2.0 atm. When O2 was introduced into the reaction system, both the rate of chlorination and the selectivity of MCB increased with the increase in the partial pressure of O2. These facts suggest that chlorination proceeds by the electrophilic substitution on the melt surface. It was indicated by an X-ray diffraction examination of the powder of the salts used, which lost the activity for chlorination after a prolonged experiment in the presence of O2, that the source of Cl was FeCl3 and not NaCl in this reaction.
Energy Transfer in the Radiolysis of Neopentane-Alkane Mixture in the Solid Phase at 77 K
Authors: Kato Masaki , Saitake Yoshiyuki , Miyazaki Tetsuo , Kuri Zen-ichiro
Published: July 2006

When neopentane containing a small amount of cyclohexane is γ-irradiated at 77 K, the cyclohexyl radical is mainly formed by the energy transfer from neopentane to cyclohexane. The addition of CCl4, which is an electron scavenger and an excitation acceptor, to the mixture suppresses the formation of the cyclohexyl radical. This fact indicates that the energy transfer is not due to an ion-molecule reaction. When CO2, which can capture an electron in the neopentane matrix to form CO2−, is added to the neopentane–cyclohexane mixture, scarcely any CO2 is formed by the irradiation. When ethyl chloride or nitrous oxide is added to the neopentane–cyclohexane mixture, the formation of the cyclohexyl radical is not suppressed, although these additives capture electrons effectively in the solid neopentane. The addition of tetramethylethylene (TME) to the neopentane–cyclohexane–carbon dioxide mixture does not affect the formation of the cyclohexyl radical, although an appreciable amount of TME+ is formed. These results show that the energy transfer is not due to the ionic process, but to a non-ionic process. The energy transfer is explained by two possible mechanisms, a selective abstraction reaction by the hydrogen atom and an excitation transfer via a highly-excited state.
Radioactive Iodine Exchange and the Dushman Reaction
Authors: Furuichi Ryusaburo , Liebhafsky Herman A
Published: July 2006

Critical studies were made on the Dushman reaction, 6H++5I−+IO3−=3I2+3H2O. Rate measurements of radioactive iodine exchange away from chemical equilibrium gave results which made the rate law for the Dushman reaction doubtful. Measurements of d(H+)/dt confirmed the rate law. The contrary interpretation resulted because existing chemical information was not considered. This situation holds in many radioactive iodine exchange experiments done on the Dushman reaction.
The Crystal Structure of Orotic Acid Monohydrate (Vitamin B13)
Authors: Takusagawa Fusao , Shimada Akira
Published: July 2006

The crystal structure of orotic acid monohydrate (Vitamin B13) has been determined by the method of X-ray diffraction. The crystals are triclinic with the space group of P\bar1 and with cell dimensions of a=9.561, b=7.261, c=5.895 Å, α=117.6°, β=107.6°, and γ=90.4°. The structure was determined by an inspection of the sharpened Patterson map. The final R value was 5.75% for 1345 observed reflections. The uracil group of orotic acid resembles uracil itself in its molecular dimensions. The molecules are arranged in layers closely parallel to the (\bar2 1 1) plane. The orotic acid molecules are linked through two kinds of N–H···O hydrogen bonds in zig-zag chains extending in the [1 1 1] direction. Each chain is joined, by three kinds of O–H···O hydrogen bonds through the medium of a water molecule, with two neighboring chains, and each forms a sheet parallel to the (\bar2 1 1) plane. The hydrogen bond of the water molecule as an acceptor is of the F type, in which the bisector of lone pairs in the oxygen atom is directed toward a donor group.
The Crystal Structure of Dipicolinic Acid Monohydrate
Authors: Takusagawa Fusao , Hirotsu Ken , Shimada Akira
Published: July 2006

The crystal structure of the dipicolinic acid monohydrate has been determined by the method of X-ray diffraction. The crystal is orthorhombic, with a space group of P212121 and with cell dimensions of a=12.233, b=9.399, and c=6.817 Å. The crystal structure was solved by an inspection of the Patterson map. The final R value was 5.67% for 964 observed reflections. The pyridine ring has the C2v symmetry within the limits of experimental error. The protonation does not occur on the nitrogen atom of the pyridine ring, and two carboxyl groups consist of carbonyl and hydroxyl groups. There is a simple relation between the C–O bond length and the C–C–O bond angle. The molecules are arranged in layers closely parallel to the (0 0 1) plane. Each molecule on the same plane is hydrogen-bonded to form an endless chain along the b axis. These two chains on the planes at z=1⁄8 and 3/8 are linked together by the O–H···N hydrogen bond between the water and pyridine ring to form a double chain along the b axis. In this case, the angle between the N···H(7) vector of the hydrogen bond and the plane of the pyridine ring is 28°. This situation can be explained by the fact that two adjacent and bulky carboxyl groups wrap up the nitrogen atom as an acceptor of the hydrogen bond. The double chains are packed only by the van der Waals forces. The thermal diffuse scattering observed on Weissenberg photographs can be explained by this hydrogen-bond system.
Deuteron and Niobium-93 Magnetic Resonance Studies of the Nb-D System. Comments on the Effects of Interstitial Impurities
Authors: Nakamura Keikichi
Published: July 2006

The deuteron and niobium magnetic resonance in the Nb–D system have been measured over a wide range of deuterium concentrations. It has been found that the order-disorder (β→α) phase transition temperature depends on the small amount of interstitial impurities as well as on the concentration of the deuterium. From the concentration dependency of deuterium (Nb) in the β phase, one can determine the amount of deuterium (Nb) in the β phase coexisting with that in the α phase. On the basis of this finding, a tentative Nb–D phase diagram has been proposed. It has been confirmed that the interstitial impurities decrease the deuterium concentration of the β phase which is in equilibrium with the α phase. The niobium signal intensity has been found to be greatly reduced by the interstitial oxygen and other impurities, while the line width is not affected. For the interpretation of these findings, a simple model has been proposed in which only the interstitial atoms, which are present within the spherical sphere of a critical radius, rc, from a niobium atom, eliminate the niobium resonance by means of the second-order quadrupole interaction.
Geometrical Structures of Excited States of Conjugated Molecules. II. The Calculated Vibronic Intensity Distributions in the Absorption Spectra of Naphthalene
Authors: Fujimura Yuichi , Onda Masamune , Nakajima Takeshi
Published: July 2006

The normal coordinates and the vibrational frequencies in the first excited singlet (1B2u), the second excited singlet (3B1u), and the first excited triplet (3B1u) states of naphthalene, whose geometries were calculated by a semiempirical method, are evaluated by assuming a simplified valence force field. The relation between the normal coordinates of two different electronic states is expressed on the basis of the Franck-Condon principle. The mixing among the excited-state normal coordinates, expressed in terms of the ground-state normal coordinates, is neglected in the present treatment. By using the simple relation between the normal coordinates of two different electronic states, the vibronic intensity distributions in the absorption spectra (1B2u←1Ag, 1Lb, 1B1u←1Ag, 3La, and 3B1u←1Ag,3La) have been calculated. The vibronic intensity distribution of the 1B2u←1Ag transition has been calculated, taking into consideration the intensity of the interpenetrating sets of the vibronic band groups on the basis of the Herzberg-Teller perturbation theory.
Vibrational Assignments of Ethylmethylsilane
Authors: Hayashi Michiro , Ohno Keiichi , Murata Hiromu
Published: July 2006

The infrared spectra of ethylmethylsilane, CH3CH2SiH2CH3, its deuterated species, CH3CH2SiD2CH3, and a mixture of CH3CH2SiHDCH3, CH3CH2SiH2CH3, and CH3CH2SiD2CH3 have been measured in the gaseous, liquid, and crystalline states. The Raman spectrum of ethylmethylsilane has also been measured in the liquid state. Vibrational assignments have been made in relation to the rotational isomerism, on the basis of a modified Urey-Bradley force field, in which the force constants have been transferred from those for dimethylsilane and ethylsilane. The conclusion regarding the molecular forms of the rotational isomers, which has been obtained from the experimental evidence of the SiHD deformation vibrations for an asymmetrically-deuterated species, CH3CH2SiHDCH3, can be considered to be also supported by the present results of the normal vibration calculations.
Determination of the Molecular Arrangement in Liquid Crystals. A New Method of Determining the Molecular Arrangement in Liquid Crystals by the Use of the Polarization of the Fluorescence
Authors: Sakagami Sakumitsu , Takase Akira , Nakamizo Minoru , Kakiyama Hitoo
Published: July 2006

The molecular order in the liquid crystal states of p-n-octyloxybenzoic acid (OOBA) has been measured by means of a new method utilizing the polarization of the fluorescence. The polarized components of the fluorescence observed for the isotropic liquid state are independent of the rotation angle; this indicates that no molecular order exists in the liquid state. The polarized components of the fluorescence observed for the nematic state show that the molecular order of the aligned nematic state can be represented by a partially uniaxial orientation. The results observed for the nematic phase are also quantitatively discussed by the use of the uniaxial prolate ellipsoidal orientation pattern. On the other hand, the smectic state of OOBA is not affected by the surface action, and the observed patterns of the polarization of the fluorescence have very little angular dependence, in contrast with those for the nematic state. Furthermore, the molecular orientation for the crystal state of OOBA is briefly described.
Electron-transfer Kinetics of Transition-metal Complexes in Lower Oxidation States. Part I. Electron Spin Resonance Measurements of the Electron-exchange Rate between Cr(bipy)31+ and Cr(bipy)3
Authors: Saji Tetsuo , Aoyagui Shigeru
Published: July 2006

The rate of the electron-exchange reaction between Cr(bipy)31+ and Cr(bipy)3 was measured in N,N-dimethylformamide by the ESR method, with the line-broadening procedure. The width of the partly-overlapped hyperfine lines was determined by comparing the observed spectrum with the computer-simulated one. The observed second-order rate constant was (1.5±0.4)×109 M−1 sec−1 at 25°C. When corrected for diffusion, this yielded the activation-controlled rate constant of 2.0×109 M−1 sec−1. It was pointed out that the rate constant obtained here was the largest of all those ever reported for the electron-exchange reactions in which the transition-metal complexes participated. The observed rate constant was in good agreement with the one calculated non-empirically according to the theory of R. A. Marcus. Although the value for the molecular radius must be chosen somewhat arbitrarily in applying this theory, the “good” radius was a reasonable one in view of the molecular geometry and dimensions of the reactants. The rate constant of the Heisenberg spin-exchange process was also determined to be 1.8×109 M−1 sec−1 at 25°C in the same solvent.
Cathodic Waves of o-Hydroxyphenylmercury Chloride in Aqueous Nitric Acid Medium. Inhibition by Reaction Product and Reduction of Precipitate
Authors: Murayama Teisuke , Morioka Motonobu
Published: July 2006

Polarographic behavior of o-hydroxyphenylmercury chloride was examined in aqueous nitric acid medium. An abnormal first wave and a peculiar angular-shaped second wave were observed. Equations of the current-potential curves of the first and second waves are derived on the following assumptions: the first wave is inhibited by a reduction product adsorbed on the surface of the dropping mercury electrode as solid particles, the adsorbed precipitate being reduced at the second wave. The equations agree well with the observed results.
Polarography of Ammonium 1-Pyrrolidinecarbodithioate and Ammonium 2-Carboxy-1-pyrrolidinecarbodithioate at the Dropping Mercury Electrode
Authors: Kitagawa Toyokichi , Taku Koji
Published: July 2006

Direct current and alternating current polarographic behaviors of ammonium 1-pyrrolidinecarbodithioate (APCD) and ammonium 2-carboxy-1-pyrrolidinecarbodithioate (ACPCD) were investigated at the dropping mercury electrode. APCD showed an adsorption pre-wave (−0.70 V vs. SCE) and one-electron oxidation wave (−0.42 V). ACPCD showed only an adsorption wave (−0.65 V). These results were also confirmed by the investigation of the electrocapillary curves and the current-time curves. The surface excess of APCD or ACPCD on the surface of mercury drop electrode at the potential which the adsorption process was observed were 5.76×10−10 mol/cm2 and 2.62×10−10 mol/cm2, respectively.
Reactions of N-Sulfinylamines with Carbodiimides
Authors: Minami Toru , Fukuda Michihiko , Abe Masahiro , Agawa Toshio
Published: July 2006

N-Sulfinylsulfonamides 1a, b reacted with carbodiimides 2 to give the 1,2-cycloadducts, 3-imino-1,2,4-thiadiazetidin-1-oxides 3, which were readily thermolyzed to sulfonylcarbodiimides 4 and N-sulfinylamines 5. The alkaline or acidic hydrolysis of the cycloadducts 3a, b, d in ethanol gave the corresponding 1,3-disubstituted-2-p-toluenesulfonylguanidines 6a, b, d in good yields. Reduction of 3a by the Raney Ni produced similarly 6a in 87% yield. Reactions of N-sulfinylacylamides 1c, d with 2 led to the formation of an oily mixture of the 1,2-cycloadducts, 3-imino-4-acyl-1,2,4-thiadiazetidin-1-oxides 7 and the 1,4-cycloadducts, 5-imino-1,2,4,6-thiaoxadiazines 8. Thermal decomposition of the mixture gave 5, isocyanates 9, nitriles 10, and amides 13 as major products.
Ferricyanide Oxidation of 4-Arylazo-2,6-di-t-butylphenols
Authors: Manda Eiichiro
Published: July 2006

Alkaline ferricyanide oxidation of 4-arylazo-2,6-di-t-butylphenols (I) gave molecular nitrogen, diphenyl derivatives (VI), 2,6-di-t-butyl-p-benzoquinone-N-(3′,5′-di-t-butyl-4′-hydroxyphenyl)arylhydrazone (V) and red tarry compounds. Picryl derivative of phenol (I) gave 2,6-di-t-butyl-p-benzoquinone-picrylanil (X) instead of hydrazone (V). The reaction path was studied on the basis of isolated compounds.
The Synthesis of γ-3,4,5,6-Tetrachlorocyclohexene (γ-BTC) by Means of a Diels-Alder Reaction
Authors: Shinoda Kiichi
Published: July 2006

γ-3,4,5,6-Tetrachlorocyclohexene (γ-BTC) was synthesized in a yield of 14–30% by a Diels-Alder reaction between trans,trans-1,4-dichloro-1,3-butadiene and trans-dichloroethylene. The s-cis requirement and stereochemical relationships consistent with Alder’s rule are shown. Antioxidants are effective in this reaction.
Syntheses of Organic Phosphates. III. Syntheses and Properties of 2-Amino-3-pyridylmethyl and 2-Chloro-3-pyridylmethyl Phosphates
Authors: Murakami Yukito , Sunamoto Junzo , Kinuwaki Seiichiro , Honda Haruomi
Published: July 2006

Two substituted pyridylmethyl phosphates, 2-amino-3-pyridylmethyl (I) and 2-chloro-3-pyridylmethyl phosphates (II), were prepared and their properties were discussed. Acid dissociation constants and NMR data suggested that the neutral species of I exists in the zwitterion form consisting of the protonated amino group and the monoanionic phosphate moiety, while that of II in the dihydrogen phosphate form analogous to the simple alkyl phosphates. In addition, physical properties of 2-amino-3-pyridylmethanol and 2-chloro-3-pyridylmethanol, which are respectively precursors of phosphates I and II, as well as l,2-dihydro-2-oxo-3-hydroxymethylpyridine, were examined by IR and NMR measurements.
Crystal and Molecular Structure of ω-Amino Acids, ω-Aminosulfonic Acids and Their Derivatives. III. The Crystal and Molecular Structure of γ-Guanidino-β-hydroxypropane Sulfonic Acid
Authors: Kim Yang Bae , Wakahara Akio , Fujiwara Takaji , Tomita Ken-ichi
Published: July 2006

γ-Guanidino-β-hydroxypropane sulfonic acid C4H11O4N3S crystallizes in the monoclinic space group P21/c, with four formula units in a unit cell of dimensions, a=7.44, b=9.89, c=11.11 Å and β=97.75°. The crystal structure was determined by the heavy atom method and refined by block-diagonal least-squares to an R-value of 0.12 using intensity data collected photographically. The molecule takes the zwitterionic form, (NH2)2+CNH-CH2CH(OH)CH2SO3−. The skeletal conformation of the molecule is planar trans zigzag. The molecules are held together in the crystal by a three-dimensional network of NH···O and OH···O hydrogen bonds.
The Oxidative Coupling of Alkyl Aryl Ketones by Iron(III) Chloride
Authors: Inoue Hiroo , Sakata Mitsuya , Imoto Eiji
Published: July 2006

The oxidative carbon-carbon coupling of two enolizable ketones, propiophenone and butyrophenone, with iron(III) chloride is investigated. The ketones are converted to γ-diketones(II) and 2,5-diphenylfurans(III) in high yields, while iron(III) chloride is reduced to iron(II) chloride. III is produced by the dehydration of II with iron(III) chloride and/or hydrogen chloride. During the reaction, iron(III) chloride is regenerated partially by the oxidation of iron(II) chloride with oxygen in the presence of hydrogen chloride. However, oxygen enhances the formation of III and the polymeric material. The addition of pyridine, calcium oxide, or zinc oxide to the iron(III) chloride-ketone system brings about the selective formation of α-chloroketones. A combination of iron(III) chloride with copper(II) chloride or oxide is effective for the oxidative coupling. Under irradiation, the reactions result both in oxidative coupling and in chlorination at the α-position of the carbonyl group, accompanied by chlorination at the β-position.
Reactions of Phenylhydrazinium Thiocyanate with Ketones and Aldehydes
Authors: Arai Isamu
Published: July 2006

Reactions of phenylhydrazinium thiocyanate with various ketones and aldehydes gave 1-phenyl-3-alkyl-5-mercapto-Δ4-1,2,4-triazoline compounds in 80–90% yield by the cycloaddition of thiocyanic acid to the phenyl-hydrazones intermediately formed from phenylhydrazine and the ketones or aldehydes. Their structure were determined by elemental analyses, spectral data (IR, NMR, and MS) and chemical reactions. Many 2-phenyl-thiosemicarbazone and 1-phenyl-1,2,4-triazole derivatives were synthesized in good yields.