bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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.
Improvement of Zone Melting Apparatus. I. Zone Melting Apparatus with a Device to Prevent Breakage of a Sample Tube
Authors: Wakayama Nobuko I , Nakano Yasuko , Mashiko Yo-ichiro 
Published: July 2006

Abstract
A glass sample tube is widely used in zone melting of organic substances since it is transparent, inert to most substances and easily prepared in the laboratory. The glass tube, however, is frequently broken owing to the volume increase of the sample. A new device was worked out to prevent breakage of the sample tube, to purify the sample efficiently and to make replacement of the atmosphere inside the sample tube possible. The apparatus requires much less space than for one ever reported and consists of a sample tube with a set of stainless steel spring and Teflon plug and a new mechanism for carrying it. It was successfully used for biphenyl and p-dichlorobenzene.