bluuebunny/crossref_metadata_2025 huggingface dataset:
Zero-point Average Structure of a Molecule Containing Two Symmetric Internal Rotors. Acetone
Authors: Iijima Takao
Published: July 2006

The theory of vibrational correction to the observed moments of inertia of a molecule which contains an internal rotor has been extended to the case of two symmetric internal rotors, and applied to the analysis of the structure of acetone. The zero-point average structure has been determined by using the moments of inertia obtained by microwave spectroscopy and the bond distances from gas electron diffraction. The zero-point average parameters have been determined as follows: C–C 1.517±0.003 Å; C=O 1.210±0.004 Å; C–H 1.091±0.003 Å; ∠HGH 108° 30′±30′; ∠CCC 116° O′±15′. The isotope effects in the structure parameters have also been observed in terms of the increase caused by deuteration to be δ(DCD)+10′±12′; δ(CCC)−17′±2′. The tilt angle of the methyl top was determined to be 2° 1′±30′.
Nuclear Quadrupole Resonance Study of Chloral Hydrate
Authors: Chihara Hideaki , Nakamura Nobuo
Published: July 2006

Three nuclear quadrupole resonance lines were observed in chloral hydrate at temperatures 20–300K, the frequencies being 38.2863±0.0004 MHz(ν1), 39.5415±0.0002(ν2), and 39.6252±0.0002(ν3) at 20.3K. Their temperature dependence was measured below 77K, showing monotonous decrease with increasing temperature. The difference in frequency between ν1 and ν2(or ν3) is probably due to a crystal field effect rather than OH···Cl hydrogen bonding as has been suggested. The spin-lattice relaxation time for all the lines, determined by pulse techniques, coincides with each other and tends to decrease rapidly above 250K. The decrease was interpreted as arising from hindered internal rotation of the CCl3 group with the activation energy of 8.8 kcal mol−1.
Photolyses of Ethoxalyl Azide in Alcohols and in Hydrocarbons Reactions of Ethoxalylnitrene
Authors: Shingaki Tadao , Inagaki Masao , Takebayashi Matsuji , Lwowski Walter
Published: July 2006

The photolysis of ethoxalyl azide gives ethoxalylnitrene and ethoxycarbonyl isocyanate. The nitrene adds to C=C double bonds and is inserted into O–H and C–H bonds. At high ethanol concentrations, where the singlet nitrene predominates, the O–H insertion product is formed dominantly. At low ethanol concentrations, where much of the nitrene changes to the triplet state, the hydrogen-abstraction product is preferred. The reactivity of the nitrene toward the C–H bonds of 2-methylbutane is more selective than that of ethoxycarbonylnitrene.
Sulfilimine. XVII. Syntheses and Reactions of N-Carbamoylsulfilimines
Authors: Oae Shigeru , Masuda Toshiaki , Tsujihara Kenji , Furukawa Naomichi
Published: July 2006

The physical and chemical properties of several new sulfilimines, N-carbamoylsulfilimines, and their syntheses were studied. The sulfilimines were prepared by the action of N-chlorourea on appropriate sulfides in acetonitrile, and their IR and NMR spectra were obtained. Thermolysis, hydrolysis and reactions with thiophenol and sodium nitrite were carried out and the results were discussed.
Preparations and Reactions of N-Benzoyl- and N-Ethoxycarbonylcarbodiimides
Authors: Mitsunobu Oyo , Tomari Masazumi , Morimoto Hiroo , Sato Toshio , Sudo Michio
Published: July 2006

The reaction of N-benzoyl-N-t-butylthiourea with either diethyl azodicarboxylate or azodibenzoyl resulted in the formation of benzoyl-t-butylcarbodiimide in 84% and 48% yields, respectively. Dehydrosulfurization of various thioureas was also effected with mercuribenzamide. Benzoyl- or ethoxycarbonylcarbodiimides were obtained in over 80% yields. The reaction of benzoyl-t-butylcarbodiimide with one equivalent each of N-benzoylglycine and glycine ethyl ester led to the formation of N1-benzoyl-N2-t-butyl-N3-(ethoxycarbonyl)methylguanidine in a good yield, no N-benzoylglycylglycine ethyl ester being isolated. When benzoyW-butylcarbodiimide was allowed to react with benzoic acid, dibenzimide and t-butyl isocyanate were formed. Similarly, N-ethoxycarbonylbenzamide and N-benzoylglycine(N′-ethoxycarbonyl)amide were prepared in good yields.
The Structural Elucidation of Sesquiterpene Lactones from Petasites japonicus Maxim
Authors: Naya Keizo , Hayashi Mitsuo , Takagi Ichiro , Nakamura Seisuke , Kobayashi Masakazu
Published: July 2006

The structures and absolute configurations of five new sesquiterpenic lactones—fukinolide (1), dihydrofukinolide (2), homofukinolide (3), S-fukinolide (4), and fukinanolide (5)—isolated from the flower stalks of Petasites japonicus Maxim. have been established by a combination of spectroscopic and chemical methods, and by correlation with the known fukinone (25).
The X-Ray Emission Spectra of the Compounds of Third-period Elements. II. The K Spectra of Phosphorus in Compounds
Authors: Takahashi Yoshihito
Published: July 2006

On sixteen compounds of phosphorus, the wavelength shifts of the Kα1,2 lines and the fine structures of the Kβ band of the phosphorus emission spectra were measured. For the oxygen compounds, the relationship between the intensity ratio of the Kβ′ line and the energy shift of the Kα1,2 lines was found to be expressed by a straight line similar to that found for sulfur and chlorine compounds. In the spectra of the oxyacids and their salts, the intensity ratio of the satellite line which is observed between the Kβ1 and Kβ′ lines is proportional to the number of the hydroxyl groups in a molecule. The appearance of this line seems to be attributable to the covalent bond between a third-period atom and a non-ionized atom. In the Kβ spectrum of triphenyl phosphite, the strong satellite line at the highest energy site seems to have a nature similar to those found in sulfite, chlorate, and phosphorus trichloride.
Spin Relaxation Effects on the ESR Spectrum of Gaseous Oxygen Atoms
Authors: Jinguji Mamoru , Mori Yuji , Tanaka Ikuzo
Published: July 2006

The linewidths of the single-quantum transitions of O(3P1) and O(3P2) in gaseous diluents, such as oxygen molecules and an inter gas, are measured with an ESR spectrometer of a usual type. The cross sections calculated from the pressure broadening are given. With regard to the multiple-quantum transitions in the Zeeman sub-levels of O(3P2) the dependence of the linewidths on the pressure is duscussed. The spin-lattice relaxation time, T1 for the single-quantum transitions of O(3P2) or O(3P2) is evaluated by employing the standard power saturation technique, and the effectiveness of an inert gas on T1 is studied. The spin-lattice relaxation between the Zeeman sublevels of the O atom is caused by the coupling between the orbital momentum and the electron-spin state upon collision. With regard to the multiple-quantum, the relaxation mechanism is also studied. Finally, we study the relationship between the spin-lattice relaxation time, T1, and the corresponding probabilities of ΔMJ=±1, ΔMJ=±2, ΔMJ=±3, and ΔMJ=±4 transition induced by collisions.
The Polymorphism and Physical Properties of the 1,6-Diaminopyrene-p-chloranil and Related Molecular Complexes
Authors: Koizumi Shigeo , Matsunaga Yoshio
Published: July 2006

The 1,6-diaminopyrene-p-chloranil complex is dark blue when crystallized from chloroform and brown when crystallized from benzene. These two substances are distinctly different in X-ray diffraction, electronic spectrum, vibrational spectrum, and also electrical resistivity. The brown form, the resistivity of which is about 105 ohm cm, can be transformed into a third form, exhibiting only a few ohm cm, by compression in the presence of benzene or some other aromatic solvents. Dimorphic forms are also found with the complexes of trichloromonobromo-and dichlorodibromo-p-benzoquinones. One of these forms is of a similar nature to the dark blue-colored p-chloranil complex. The other form is brown. Only the brown form is obtainable for the complexes of mono-chlorotribromo-p-benzoquinone and p-bromanil. All the brown complexes except that of p-chloranil are similar and exhibit resistivities of the order of 103 ohm cm. In addition, black products exhibiting resistivities of several ohm cm can be prepared by using acetone as the solvent with 1,6-diaminopyrene and tetrahalo-p-benzoquinones. Contrary to the afore-mentioned complexes, no definite composition can be assigned to these low-resistivity products.
Re-absorption Effect of Charge-Transfer Fluorescence by the Excited Electron Donor-Acceptor Complex
Authors: Masuhara Hiroshi , Mataga Noboru
Published: July 2006

It has been shown that excited electron donor-acceptor (EDA) complexes of s-tetracyanobenzene (TCNB) with benzene or toluene can be produced quite densely when excited with a giant pulse laser and that there arises a remarkable re-absorption of the charge-transfer (CT) fluorescence by the excited EDA complexes. We have investigated in detail the re-absorption effect by examining the dependence of the CT fluorescence spectra on the direction of observation, the decay function of the fluorescence, the effect of the concentration of solution as well as the effect of the exciting light intensity on it. The excited singlet-singlet (Sn←S1) absorption spectra have been obtained by analyzing the re-absorption effect. Since the CT fluorescence spectra are broad and have no structure, the fluorescence can work as a good light source for the absorption spectral measurement.
Polarographic Investigation of Alkali Metal Ions in Hexamethylphosphoramide
Authors: Izutsu Kosuke , Sakura Sachiko , Fujinaga Taitiro
Published: July 2006

The polarographic behavior of alkali metal ions in hexamethylphosphoramide (HMPA) has been found to be greatly influenced by the cations of the supporting electrolytes. With 0.05 m Et4NClO4 as the supporting electrolyte, cesium and rubidium ions give diffusion-controlled, reversible waves at−2.32 and −2.35 V, respectively, vs. the Ag/0.1 m AgClO4 electrode, but sodium and lithium ions are not reduced until the reduction of the supporting electrolyte (−3.1 V). The potassium ion gives a wave at −2.37 V with a limiting current controlled by the rate of the preceding process. In 0.05 m Bu4NClO4 solutions, the reduction wave of the potassium ion is diffusion-controlled, but that of the sodium ion is kinetic and is very small. The lithium ion is not reduced until −3.1 V. In 0.05 m LiClO4, even the sodium ion is reduced reversibly with E1⁄2 at −2.47 V, while the reduction of the lithium ion starts from −2.65 V. In mixed supporting electrolytes, the presence of the tetraethylammonium ion is the determining factor of the electrode processes. From the measurements of the electrocapillary curves and of the conductivities, the effect has been attributed to the change in the double-layer properties with the cations of the supporting electrolytes.
Electronic Spectra and Electronic Structure of Iron(II) Tetraphenylporphins
Authors: Kobayashi Hiroshi , Yanagawa Yasuo
Published: July 2006

Tetraphenylporphiniron(II) was synthesized and isolated in a pure state. The iron(II) porphin was in the state of S=2. The spin state of iron(II) porphin varies with the axial ligand field. Oxygeneous axial ligands such as tetrahydrofuran and dioxane gave an intermediate spin state (S=1), while nitrogeneous ligands such as pyridine gave a diamagnetic state (S=0). The electronic spectra of tetraphenylporphin complexes of iron(II) were measured for the three types of the spin state.
Magnetic Moments and Electronic Spectra of Low-spin Cobalt(II) Complexes
Authors: Nishida Yuzo , Kida Sigeo
Published: July 2006

Comprehensive elucidation of optical and magnetic properties of low-spin cobalt(II) complexes of various types has been attempted. The g-values and magnetic susceptibilities of the complexes have been calculated, the necessary numerical data being obtained from the spectral data and reasonable assumptions. Fairly good agreement has been obtained between the calculated and experimental values.
Reactions of Alkylidenetriphenylphosphoranes with Sulfur
Authors: Tokunaga Hirokazu , Akiba Kin-ya , Inamoto Naoki
Published: July 2006

Reaction of diarylmethylenetriphenylphosphoranes with sulfur gave thiobenzophenones and triphenylphosphine sulfide in good yields. Reaction of benzylidenetriphenylphosphoranes with sulfur gave triphenylphosphine sulfide and 5,7-diphenyl-l,2,3,4,6-pentathiepane. More active alkylidenetriphenylphosphoranes such as isopropylidene- or sec-butylidenetriphenylphosphorane gave the corresponding phosphonium betaine containing sulfur atoms or phosphonium salt produced through air oxidation and hydrolysis of the betaine. α-Benzoylbenzylidenetriphenylphosphorane did not react with sulfur. Reactivity of alkylidenephosphoranes toward sulfur was briefly discussed.
The Synthesis of the New 1,4,2-Dithiazine Ring
Authors: Hasegawa Kiyoshi , Hirooka Syuzi
Published: July 2006

Some derivatives of N-(2-phenylethene-l-sulfonyl)-N′-alkylthioureas of the R1C6H4CH=CHSO2NHCSNHR2  2 type were synthesized by a reaction between 2-phenylethene-l-sulfonamides 1 and isothiocyanates in acetone in the presence of K2CO3. A new heterocyclic system, 3-alkylamino-5-phenyl-1,1-dioxo-5,6-dihydro-l,4,2-dithiazine 3, was obtained by the intramolecular Michael cycloaddition of 2 in weakly basic media, and also by the thermal cyclization of 2. The carbon-sulfur bond in 3 could be cleaved to give 2 again in strongly basic media.
The Reduction of Chlorodeoxy Sugars by Tributyltin Hydride
Authors: Arita Hitoshi , Ueda Nobuhiko , Matsushima Yoshio
Published: July 2006

Acetylated chlorodeoxy sugars were prepared by the use of sulfuryl chloride. These chlorodeoxy sugars were then successfully reduced to deoxy sugars by the use of tri-n-butyltin hydride. α,α-Azobis-isobutyronitrile, which has been known to be an effective radical initiator, was found to be indispensable for the reaction.
The Synthesis of 2,3-Dimethyl-3-(5-bromo-2-methoxy-4-methylphenyl)-cyclohexene, a Potentially Useful Intermediate for the Syntheses of Aplysin and Related Sesquiterpenes
Authors: Yamada Kiyoyuki , Yazawa Hisatoyo , Hirata Yoshimasa
Published: July 2006

As a key intermediate for the syntheses of aplysin, 1, a bromine-containing sesquiterpene isolated from Aplysia kurodai, and related sesquiterpenes, 2,3-dimethyl-3-(5′-bromo-2′-methoxy-4′-methylphenyl)cyclohexene, 2, was synthesized, starting from an anisole derivative, 6. The reactivity of the double bond in 2 towards oxidizing reagents was examined: the cyclohexene, 2, reacted with ozone to give an epoxide, 12, and a cyclohexanone, 13; an isomerization product of 12; 2 could be converted to the diol, 15, with osmium tetroxide in the presence of pyridine.
Photoemission of Ion Radical Salts. Benzonitrile- and Triphenylene-Alkali Metal Complexes
Authors: Kawamura Haruki , Inokuchi Hiroo
Published: July 2006

The photoelectric emission of the benzonitrile-alkali metal salts were measured and compared with those of the hydrogen-chemisorbed samples. The adsorption of hydrogen onto the salt caused a decrease in the quantum yield of the photoemission at a higher energy region and also a decrease in the threshold energy. The threshold energies were 5.05± 0.02 eV for the benzonitrile-rubidium ion radical salt and 4.95± 0.02 eV for its hydrogenchemisorbed sample. Further, the spectral response of the quantum yield of the photoemission for the triphenylenecesium complex was measured. The threshold energies of the mono- and dinegative ions were 2.40 eV and 2.43 eV respectively, and the quantum yield of the mononegative salt was ten times than that of the dinegative one.
The Microwave Spectrum of trans-Ethylmethylsilane
Authors: Hayashi Michiro , Matsumura Chi
Published: July 2006

The microwave spectra of CH3CH2SiH2CH3 and CH3CH2SiD2CH3 in the trans form were studied. The rotational constants calculated from the spectra can be explained satisfactorily with a model which has structural parameters transferred with only a slight modification, from the values reported for dimethylsilane and ethylsilane. From the observed splittings of the spectra, the barrier to the internal rotation of the SiCH3 group was calculated to be 1520 ± 30 cal/mol, assuming that the coupling effect of the torsional motions of the other groups can be ignored. From the Stark shifts, the dipole moment was determined to be μa=0.036±0.030, μb=0.757±0.003, and μtotal=0.758±0.005 D, making an angle of 2°44′ with the b axis for the parent species, while it was determined to be μa=0.024±0.030, μb=0.758±0.003, and μtotal=0.758±0.005 D, making an angle of 1°49′ with the b axis for the deuterated species. From these results, the orientation of the dipole moment in the molecule was concluded to be along the direction slightly inclined from the bisector of the CSiC angle toward the ethyl group in the molecule.
The Diffuse Reflection Spectra of Bentonites Colored with Various Aromatic Compounds and Related Ion-radical Salts
Authors: Matsunaga Yoshio
Published: July 2006

Bentonites colored with each of the following aromatic compounds were examined by the method of diffuse reflection in the range from 4 to 30 kK: benzidine, 4,4′-dihydroxybiphenyl, 4,4′-dimethoxybiphenyl, perylene, tetrathiotetracene, and phenothiazine. By comparison with the spectra of the related ion-radical salts, the oxidation of the aromatic compounds to the mono- and/or di-valent cations could be proven in all of them. Except in the case of phenothiazine, the species in the colored clays was found to be drastically modified by moisture. In addition, the spectra of the copper-arene complexes recently reported by Mortland et al. were measured. The oxidation of perylene, tetrathiotetracene, and phenothiazine was found to proceed to a greater extent in the copperexchanged clays.
The Characterization of the Electronic Spectra of Heterocyclic Amine N-Oxides by Means of the Non-Aqueous Oxidation and Reduction Potentials and the Substituent Effects on Them
Authors: Miyazaki Hiroshi , Kubota Tanekazu , Yamakawa Masumi
Published: July 2006

The half-wave potentials of the voltammetric oxidation and the reduction of various heterocyclic amine N-oxides have been measured in CH3CN by the technique of a rotating platinum electrode. The reversibility of the electrode process was particularly examined for the oxidation reaction by analyzing the oxidation wave and by recording the ESR spectra. Then, the mutual relationship between the electronic spectra of these N-oxides and the values of the oxidation-reduction potentials was discussed in detail; we found that this kind of treatment is very useful in assigning the spectra. Finally, a good linear relation between the oxidation potentials of substituted pyridine N-oxides and the Hammett σ+ (Brown-Okamoto) constants was demonstrated and discussed.
Dipole Moment and Force Constants of NSCl from Microwave Spectrum
Authors: Mizumoto Setsuko , Izumi Jun , Beppu Tatsuro , Hirota Eizi
Published: July 2006

Dipole moment of 15N32S35Cl has been determined to be μa=0.5645±0.0085, μb=1.74±0.035, μtotal=1.836±0.036D by analyzing the Stark effect of the 11,1←00,0 transition.

Twenty-eight rotational transitions of 14N32S35Cl in the ground state have been analyzed to determine four centrifugal distortion constants: τaaaa=−6.99±0.30, τbbbb=−0.0110±0.0013, τaabb=0.176±0.014, and τabab=−0.0334±0.0068 MHz. These constants are combined with the vibrational frequencies and inertia defects to recalculate force constants: F11=10.032 md/Å, F22=1.444 md/Å, F33=0.749 mdÅ, and F23=−0.086 md.
Spectra of Anions in Pure Iodine Melt and Iodine Solution Containing Tellurium
Authors: Ichikawa Kazuhiko , Shimoji Mitsuo
Published: July 2006

The absorption spectra in the ultraviolet and visible region were measured as a function of the temperature for pure molten I2 and for I2+Te solutions. The two peaks found at about 305 and 370 mμ can be attributed to the I3− ion. These peaks increase with the addition of Te indicating an increase in the concentration of the I3− ion. This result is consistent with the previous interpretation of the conductivity of molten I2 containing Te. The ionization potential of I3− can be estimated to be about 3.1 eV on the basis of a cyclic analysis using the model of Stein and Treinin which was developed for anion spectra in aqueous solutions. The temperature shift of the absorption energy can also be interpreted in terms of the same model. The heat change for the I2(g)+I(g)=I3(g) reaction is estimated as −48.0 kcal·mol−1.
Reactions Leading to 1,2-Dibenzoylethanes: The Dehalogenation of Phenacyl Bromide and the Photolysis of Methyl Phenacyl Sulfoxide
Authors: Nozaki Hitosi , Shirafuji Tamio , Kuno Kiyosi , Yamamoto Yasusi
Published: July 2006

The dehalogenation of phenacyl bromide by means of lower-oxidation-state metallic ions complexed by DMSO gives 1,2-dibenzoylethane. The by-products are 2,4-diphenylfuran and phenacyl chloride in the presence of Cu(I) chloride, whereas acetophenone and ω-acetoxyacetophenone are produced in the reaction with Cr(II) acetate. Treatment with K3Co(CN)5/DMSO gives 1,2-dibenzoylethane and acetophenone. The second title reaction consists of the photolysis of methyl phenacyl sulfoxides, the isolated by-products being acetophenones and methyl methanethiolsulfonate. The product distribution is strongly affected by the pH of the reaction mixture and also by the benzene-ring substituents.
Molecular Orbital Treatment of Para Orientation in the Diels-Alder Reactions of 2-Substituted Butadienes with Methyl Acrylate
Authors: Inukai Takashi , Sato Hideo , Kojima Takeshi
Published: July 2006

The intermolecular orbital method was applied to the orientation phenomena in the Diels-Alder reactions of 2-R-butadienes (R=Me, Ph, Cl, and CN) with methyl acrylate assuming the parallel biplanar transition state geometries. Although qualitatively correct predictions of para orientation (major isomer) were obtained with the calculated overlap energies, it is suggested that the non-bonding interactions are overestimated. The simple perturbational molecular orbital method, which takes only the interactions at the terminal positions into account, was also unsatisfactory. However, frontier orbital interactions provided qualitatively correct prediction of the major isomeric product in every case.
Far Infrared Spectra and Internal-Rotation Potential of Ethyl Methyl Ether
Authors: Kitagawa Teizo , Ohno Keiichi , Sugeta Hiromu , Miyazawa Tatsuo
Published: July 2006

Far infrared spectra (700∼40 cm−1) of ethyl methyl ether and deuterated species (CH3CH2OCD3, CD3CH2OCH3, CH3CD2OCH3, and CD3CD2OCH3) were measured in the crystalline, liquid and gaseous states and carbon tetrachloride solution. A low temperature cell was constructed for measuring far infrared absorption of highly volatile samples in the liquid and crystalline states. Far infrared bands due to skeletal bending vibrations of the trans and gauche isomers and lattice vibrations were assigned. From analyses of isotope effects on infrared frequencies, internal-rotation vibrations of the CH3-CH2, CH2-O, and O-CH3 bonds of the trans isomer of ethyl methyl ether were found at 248, 115, and 202 cm−1, respectively, in the gaseous state. Normal vibrations were treated with the local-symmetry force field and force constants were adjusted by the method of least squares. By the use of Mathieu equation, the threefold potential barriers of the methyl groups of the trans isomer were estimated as V3(CH3-C)=3.3±0.1 and V3(O-CH3)=2.5±0.1 kcal/mol.
Exact Classical-Mechanical Calculation of the Translational-Vibrational Energy Transfer of Energized Anharmonic Diatomic Molecules
Authors: Kajimoto Okitsugu , Fueno Takayuki
Published: July 2006

The exact classical-mechanical calculation of the translational-vibrational energy transfer of diatomic molecules was extended to collisions between inert gas and anharmonic oscillator of varying initial vibrational energy. The systems investigated were H2–He, N2–Ar, and I2–Ar. It was found that, at lower vibrational levels, the transitions in both upward and downward directions become more efficient with an increase in the initial vibrational energy of molecules. In a high vibrational energy region, however, vibrational deactivation reaches a maximum and then diminishes as the initial vibrational energy approaches the dissociation threshold. The results illuminate the essence of a “bottleneck” to vibrational energy flow involved in the activation process of bimolecular dissociation of diatomic molecules.
The Crystal and Molecular Structure of 5-Chloro-7-iodo-8-quinolinol, Chinoform
Authors: Kashino Setsuo , Haisa Masao
Published: July 2006

Isomorphous crystals of 5-chloro-7-iodo- and 5,7-dibromo-8-quinolinols have been examined by X-ray analysis. Both compounds crystallize in the monoclinic space group P2⁄a with four formula units in the unit cell. The cell dimensions are: a=16.98; b=4.16; c=14.84 Å, and β=112.0° for 5-chloro-7-iodo-8-quinolinol, and a=16.34, b=4.02, c=15.52 Å, and β=115.6° for 5,7-dibromo-8-quinolinol. The structure of the former, chinoform, has been determined by the Patterson methods from data collected with MoKα radiation on Weissenberg photographs, and refined by the block-diagonal least-squares method, with anisotropic temperature factors. The final R value is 0.081 for 836 observed reflections. The quinolinol molecule is nearly planar. In the crystals, the molecules related by two-fold axis are held together by hydrogen bonds to form bent dimers, which are stacked closely by van der Waals forces along the b axis.
Structure of Ethylene Oxide Oligomer Complexes. I. A 1:1 Complex of Tetraethylene Glycol Dimethyl Ether with Mercuric Chloride
Authors: Iwamoto Reikichi
Published: July 2006

Molecular and crystal structure of a 1 : 1 molecular complex of tetraethylene glycol dimethyl ether CH3O-(CH2CH2O)4CH3 (TGM) with mercuric chloride has been determined by means of X-ray diffraction. The complex has a monoclinic unit cell with a=14.29, b=15.10, c=7.84 Å, and β=97.0°. The space group is P21/n. Four molecules of both TGM and mercuric chloride are contained in the unit cell. The structure was determined by the ordinary heavy atom method. The molecular conformation of TGM in the complex is approximately

CH3–O\undersetT–CH2\undersetG–CH2\undersetT–O\undersetT–CH2\underset\barG–CH2\undersetT–O\undersetT–CH2\undersetG–CH2\undersetT–O\undersetT–CH2\underset\barG–CH2\undersetT–O\undersetT–CH2\undersetG–CH2\undersetT–O–CH3,

where T, G, and \barG indicate trans, gauche, and minus gauche forms, respectively. All the CH2–O bonds are trans, while the CH2–CH2 bonds are gauche and minus gauche in the adjacent chemical units. The conforma-tional unit of

O\undersetT–CH2\undersetG–CH2\undersetT–O\undersetT–CH2\underset\barG–CH2\undersetT–

was found to be very important and favorable for coordination between the O and Hg atoms. The molecule is circular but not closed, and the five oxygen atoms, which are nearly coplanar and located at the inner side of the circular molecule, enclose one HgCl2 molecule with close interatomic distances (2.78–2.96 Å) between the O and Hg atoms.
ESR Study of γ-Irradiated Ammonia-Silica Gel System
Authors: Nagai Siro
Published: July 2006

Ammonia-silica gel system was γ-irradiated at −196 °C. ESR spectrum observed from samples with low ammonia content showed a marked linewidth anomaly in the hf lines at −196 °C and changed with temperature reversibly. The free radical responsible for the spectrum was assigned to NH2 radical which undergoes a preferential rotation about an axis perpendicular to the radical plane at low temperatures and a substantially free rotation above −90 °C.
Properties of Water in Macromolecular Gels. V. Anomalous Temperature Dependence of the Nuclear Magnetic Resonance Line-width of Water in Macromolecular Gels
Authors: Aizawa Masuo , Suzuki Shuichi , Suzuki Teruo , Toyama Hiroshi
Published: July 2006

The line-width of the nuclear magnetic resonance (NMR) signal gets narrow, in general, with an increase in the temperature. In contrast, the NMR line-width of the water proton in agarose gels was found to increase with an increase in the temperature up to about 30°C. As for the other polysaccharide gels, such as curdlan-type polysaccharide, and κ-and λ-carrageenan gels, the NMR line-width of water increases with an increase in the temperature. The anomalous temperature dependence of the line-width was most marked in agarose gels than in other polysaccharide gels. The close relationship between the gel network, which consists of small cavities (microspace) of the micelle, and the magnitude of the anomality was revealed, this anomalous effect was named the “Micro-Space Effect.”
The Oxidation of Iron(II) by Molecular Oxygen Catalyzed by Chloride Ion, Thiocyanate Ion, and Ethylenediamine in Dimethyl Sulfoxide
Authors: Unno Yuriko , Wada Goro
Published: July 2006

The rates of the oxidation reactions of iron(II) to iron(III) by molecular oxygen in DMSO were measured under the catalyses of Cl−, SCN−, and en. The rate was proportional to the partial pressure of oxygen and was of the second order to [Fe(II)] in catalyses of Cl− and SCN− while it was of the first order to [Fe(II)] in catalysis of en. The reaction rate was also linear to [X]2 and [H+], where X represents Cl− or SCN−, indicating that the reaction proceeds via both the electron-transfer and hydrogen-atom-transfer mechanisms, side by side. The reaction order of [Fe(II)] depends upon which step is rate-determining among those of the oxygenation of Fe(II), its spontaneous decomposition, and its bimolecular reaction with another Fe(II) and, therefore, may be variable according to the concentrations of the reacting species. The autoxidation rate can be affected by the kinds of the catalyzing ligands. The autoxidation may be slow when an Fe(II) complex with low spin is oxidized to an Fe(III) complex with high spin and may be fast when from high spin type to low spin one. In the present cases of Cl−, SCN−, and en in DMSO, it seems to go from high spin type to high spin one with moderately large rates.
The Calculation of Dipole Polarizability and Anisotropy by the CNDO Method
Authors: Miyazaki Tomoo , Shinoda Hiroyuki
Published: July 2006

The dipole polarizabilities and the anisotropies of small linear molecules have been calculated according to a formula in which the frequency of the incident light is taken into account, as derived by the time-dependent perturbation theory. The wave functions and the energies were calculated by the CNDO method, involving the configuration interaction treatment. The effect of the parametrization in the CNDO method on the calculated polarizability and anisotropy has also been discussed. The method has been used to calculate the variations in the anisotropy, the polarizability, α, and its derivatives, (∂α⁄∂Si)0 and (∂2α⁄∂Si2)0, with the frequency of the incident light, where Si is the appropriate symmetry coordinate of the molecular vibration.
Studies on Reactions of the JV-Phosphonium Salts of Pyridines. II. A New Method for the Activation of Carboxylic Acids via the N-Phosphonium Salts by Means of the Oxidation of Phosphorous Acid and Its Monoesters in the Presence of Tertiary Amines
Authors: Yamazaki Noboru , Higashi Fukuji
Published: July 2006

The oxidation of phosphorous acid and its monoesters with mercuric chloride was carried out in pyridine; they were then treated with carboxylic acids and with aniline. The oxidation reaction was conducted also in the presence of carboxylic acids, after which the mixture was treated with aniline. By both procedures, the corresponding anilides were obtained in good yields. The influence of the steric factors of carboxylic acids, their acidity, and the tertiary amines were observed in the reaction. Phosphorous acid provided a better result than the monoesters. In addition, the chain length of carboxylic acids in the case of the esters influenced the yields of the anilides, which decreased with an increase in the chain length. The structural effect of tertiary amines was studied on pyridine derivatives. The ester residues also affected the yield, and of the esters examined the monophenyl ester was more favorable than the alkyl esters. Other mercuric halides and mercuric acetate were also found effective as oxidizing agents. The reaction was proposed to proceed via the N-phosphonium salts of pyridines.
Stereospecific Addition Reaction between Butadiene and Amines
Authors: Narita Tadashi , Imai Nobuyoshi , Tsuruta Teiji
Published: July 2006

The reaction of butadiene with secondary amines initiated by n-butyllithium was found to proceed selectively to produce 1-dialkylamino-cis-butene-2 under appropriate reaction conditions. For instance, diethylamine produced 1-diethylamino-cis-butene-2 in a 98–99% purity. By kinetic and spectroscopic studies, it was concluded that the lithium dialkylamide-dialkylamine (1:2) complex plays an important role in this addition reaction. The second-order rate constants of the reaction are 0.85×10−3 l/mol sec for diethylamine and 2.4×10−3 l/mol sec for diisobutylamine.
Studies on Aminosugars. XXXIV. Synthesis of 4-O- and 6-O-(4-amino-4-deoxy-α-d-glucopyranosyl)-2-deoxystreptamine
Authors: Nishimura Yoshio , Tsuchiya Tsutomu , Umezawa Sumio
Published: July 2006

Racemic O-isopropylidene derivative of N,N′-diethoxycarbonyl-2-deoxystreptamine was glycosidated with 4-azido-2,3,6-tri-O-benzyl-4-deoxy-α-d-glucopyranosyl chloride to afford two kinds of position isomers of α-glucoside, which was led to 4-O-(4-amino-4-deoxy-α-d-glucopyranosyl)- and 6-O-(4-amino-4-deoxy-α-d-glucopyranosyl)-2-deoxystreptamine.
The SCF Screened Potential in π-Electron Systems
Authors: Terasaka Toshitaka , Ijima Taizo , Fujimura Yuichi , Nakajima Takeshi
Published: July 2006

The screened potentials π-electron systems have been calculated using the SGF orbitals and energies, and compared with Little’s screened potentials calculated using the Hückel orbitals and energies. The characteristics of the screened potentials in benzenoid and nonbenzenoid aromatic hydrocarbons and in linear polyenes have been studied. It has been found that the use of the screened potential brings about considerable improvements in the triplet excitation energies in particular.
Studies on Fragment Ion Distribution and Reaction by the Use of a Charge Spectrometer. I. Mass Spectra of Methylamine after Charge Exchange with Fast Positive Ions and Their Recombination Energies
Authors: Nagatani Toshio , Yosihara Kenji , Shiokawa Takanobu
Published: July 2006

Charge exchange reactions with fast positive ions were used to obtain the break down curve and internal energy distribution function of methylamine which differ in several points from those obtained by Sjögren with very slow ions. In the higher region, our results on the population in internal energy distribution function is greater than the previous ones. A valley of the internal energy distribution curve was found in the region 12.0–13.8 eV which is higher than that obtained by Sjögren. The values of RE were reestimated according to recent results.
Determination of the Intersystem Crossing Probabilities of Acridine in Various Alcohols
Authors: Tokumura Kunihiro , Kikuchi Koichi , Koizumi Masao
Published: July 2006

Intersystem crossing probabilities φST of acridine in methanol, ethanol, and 2-propanol were determined by two newly developed methods, relative (r) and absolute (a). The results are as follows. Methanol; 0.27 (r), 0.31 (a). Ethanol; 0.29 (r), 0.33 (a). 2-Propanol; 0.43 (r), 0.45 (a). The above φST values added to the quantum yield values already obtained of photoreduction occurring at T(n-π*), viz., 2φRT (radical mechanism via T(n-π*), disproportionation of semiquinone being taken into account by a factor of 2) + φMT (molecular mechanism via T(n-π*)), become about the same for the three alcohols. Thus the present data are consistent with our previous data on photoreduction if the intersystem crossing is assumed to occur mainly via S*(π-π*)→T(n-π*)→T(π-π*) with the same total φST for the three alcohols but with T(n-π*) participating in the reaction in different extent according to the alcohol.
The Determination of the CMC of Surfactants in Some Organic Solvents
Authors: Muto Shinya , Meguro Kenjiro
Published: July 2006

Extra absorption spectra appeared when 7,7,8,8-tetracyanoquinodimethane (TCNQ) was solubilized into surfactant organic solvent solutions above the critical micelle concentration (CMC). It was found also that extra absorption spectra appeared when iodine was solubilized into surfactant organic solvent solutions above the CMC. In the former case, the extra absorption spectra are attributed to TCNQ anion radical salts formed between TCNQ and the surfactants. In the latter, the extra absorption spectra are due to charge-transfer interactions of iodine with the surfactants. The intensity of the absorption bands increased with the concentrations of the surfactant. The values of the CMC of the surfactants were determined from this spectral change. The CMC values obtained by the TCNQ solubilization method were larger than those obtained by the iodine solubilization technique. The difference in the CMC between the two methods was interpreted in terms of the difference in solubility and chargetransfer power to the organic solvent between iodine and TCNQ, and the difference in type of electron transition, that is, n(D)→σ(A) or n(D)→π(A).
Effective Ionic Charges of Several Uniaxial Crystals
Authors: Hiraishi Jiro
Published: July 2006

A simple equation was derived for obtaining the effective ionic charges of uniaxial crystals on the basis of a rigid ion model by using the optically active lattice vibration frequencies of the TO and LO modes. It was applied to several uniaxial crystals such as wurtzite type (ZnO, ZnS, CdS, and BeO) and rutile type (ZnF2, TiO2, SnO2, and GeO2) crystals. Lattice vibration frequencies of orthorhombic hydrogen chloride crystal were calculated by means of a point charge model to estimate the effect of the long range Coulomb interaction on the vibrational frequencies of molecular crystals.
ESR of Hot Ions: Ni(I) Complex Ions Produced in Rigid Solutions by γ-Irradiation
Authors: Amano Chikara , Fujiwara Shizuo
Published: July 2006

Electron spin resonance has been used to study Ni(I) complex ions produced at 77 K through reduction by γ-irradiation of Ni(II) complexes in glassy solvents. The Ni(I) complex ions give axially symmetrical spectra, suggesting that the Ni(I) ions favor tetragonally elongated octahedral form. From the g-values it can be shown that the Ni(I)-to-ligand bonding for different ligands increases in covalency in the order: H2O<edta<<py∼en∼xanthate<phen<dipy<<CN−. It can also be shown that the metal-to-ligand bonding of the Ni(I) complex ions is less covalent than that of the corresponding Cu(II) complexes. Measurement of the integrated intensity of the ESR spectrum of [Ni(I)(H2O)6]+ with reference to a standard sample of [Cu(II)(H2O)6]2+ shows that at a total dose of 1×106 R the yield of the Ni(I) species is 0.21±0.04% of the host complex [Ni(II)(H2O)6]2+. In addition to the anisotropic spectra of the Ni(I) complex ions, isotropic spectra have been observed in several cases, which are probably due to Ni(III) complex ions. Isotropic feature of these spectra may be explained in terms of dynamic Jahn-Teller effect involving the Ni(III) complex ions.
Kinetics and Mechanism of the Transformation of Vaterite to Calcite
Authors: Rao M Subba
Published: July 2006

The transformation of vaterite to calcite was investigated systematically. The transition temperature and the energetics of the transformation were determined from differential thermal curves. The variations of lattice constants and crystallite size, accompanying the transformation were studied by X-ray diffractometry. The kinetics of transformation were investigated in the temperature range 460–490°C. The kinetic data were analysed with the help of three separate solid-state models.
A Method of Correction of the Angular Resolution for Determination of Absolute Total Cross Sections Using Molecular Beams
Authors: Kusunoki Isao
Published: July 2006

A general method is given for the correction of angular resolution for the case in which primary beams have a monochromatic velocity and the target gases in the scattering chamber have Maxwellian distribution. In the center-of-mass system the differential cross section for small angles are expressed by three analytical formulas. An apparent differential cross section in the laboratory system is given by averaging contributing differential cross sections in the center-of-mass system. For correction of the angular resolution, the detection probability R is defined for rectangular beams and detector. Using the apparent differential cross section with R-function and beam profile, we can determine the correction factor ΔQeff(vi)⁄Qeff(vi). The expression of angular resolution has been applied to previous experimental data.
Derivatographic Studies on Transition Metal Complexes. X. Thermal Octahedral-to-Square Planar Transformation of Ni(NN-deen)2X2·nH2O in Solid Phase
Authors: Tsuchiya Ryokichi , Joba Seiji , Uehara Akira , Kyuno Eishin
Published: July 2006

Thermal reactions of the complexes [Ni(H2O)2(NN-deen)2]X2·nH2O (NN-deen is N,N-diethylethylene-diamine and X is Cl or Br) were investigated. It was found by derivatography and spectral and magnetic measurements that the bromide undergoes transformation from octahedral to square planar structure by “deaquation” upon heating, whereas the chloride turned to the dichloro complex by thermal “deaquation-anation” losing the coordinated water and drawing chloride ion into the coordination sphere with retention of octahedral structure around the central metal. No such transformation could be found in the corresponding iodide and nitrate, since only diamagnetic complexes, [Ni(NN-deen)2]X2 (X is I or NO3), and no paramagentic complexes were obtained.
Electronic Spectra of High-Spin Iron(III) Tetraphenylporphins
Authors: Kobayashi Hiroshi , Yanagawa Yasuo , Osada Hisajiro , Minami Shuji , Shimizu Masayuki
Published: July 2006

Characterization of the electronic absorption spectra of high-spin iron(III) porphyrins was carried out on the basis of observation and theoretical calculation for tetraphenylporphinatoiron(III) and -manganese(III) complexes.
Formation of Sulfur Ylids by Catalytic Action of Dialkoxy Disulfides
Authors: Matsuyama Haruo , Minato Hiroshi , Kobayashi Michio
Published: July 2006

In the presence of a catalytic amount of a dialkoxy disulfide, dimethyl diazomalonate spontaneously reacted with a dialkyl sulfide in the absence of light at room temperature, and the corresponding sulfonium ylid was formed. The kinetics and products of this reaction were investigated, and its mechanism was discussed.
The Synthesis of Crystalline Rare Earth Carbonates
Authors: Nagashima Kozo , Wakita Hisanobu , Mochizuki Akihiko
Published: July 2006

The factors which influence the crystallization of rare earth carbonates were studied. Crystalline rare earth carbonates were precipitated at various temperatures from aqueous solutions by using sodium carbonate, sodium bicarbonate, trichloroacetic acid, and urea as precipitants. The crystal parameters, compositions, and factors concerning the formations of various carbonates, such as lanthanite-type Ln2(CO3)3·8H2O(Ln=La, Ce), tengeritetype Ln2(CO3)3·nH2O(Ln=Nd, Sm, Gd, Dy, Ho, Er, and Y, n=2–3), monoxocarbonate-type Ln2O(CO3)2·nH2O(Ln=La, Ce, Nd, and Sm, n=1–2) and a hydrated double carbonate of rare earth and sodium (rare earth= La, Ce, Nd, Sm, Gd, Dy, and Y) were determined by chemical analysis and X-ray powder diffractometry.
The Adiabatic Compressibility of Nonelectrolyte Aqueous Solutions in Relation to the Structures of Water and Solutions. II.
Authors: Endo Harumi
Published: July 2006

From the temperature dependency of the adiabatic compressibility in aqueous systems of nonelectrolytes, established by ultrasonic measurements, it is concluded that structural units to be termed “liquid clathrate hydrates” do exist for various systems, the concentration of the zero temperature coefficient of adiabatic compressibility representing the composition-mole-ratio, rcβ(water/solute), for these hydrates. Hydrates with rcβ=7.2⁄3 (for methanol, formamide, and urea) and 17 (for acetone and ethanol) correspond to the solid clathrate hydrates of Structures I and II respectively, while those with rcβ=24, 28, 32, etc, can be explained on the basis of appropriate assumptions.
The Absolute Configuration of the (−)589-Oxalatobis(ethylenediamine)-cobalt(III) Ion as Determined by X-Ray Structure Analysis
Authors: Aoki Tadashi , Matsumoto Keiji , Ooi Shun’ichiro , Kuroya Hisao
Published: July 2006

The absolute configuration of (−)589-[Co ox en2]+ has been determined by the X-ray diffraction method. The crystals of (−)589-[Co ox en2]Br·H2O are orthorhombic, with the space group P212121, and the unit cell dimensions are: a=16.67(1)Å, b=12.40(1)Å, c=6.183(7)Å, and Z=4. The crystal structure was solved by the conventional Patterson and Fourier methods, and refined by the least-squares procedure to an R factor of 9.97%. The cobalt atom has an octahedral coordination, being chelated by an oxalate anion and two ethylenediamine molecules which are of the ob-lel conformation. The absolute configuration of the complex cation can be denoted as Δ(δλ).
Methylene Analogs of Cyclobutenedione. VI. Interconversion between 3,4-Dimethylcyclobut-3-ene-1,2-dione and 3,4-Dimethylenecyclobutane-1,2-dione
Authors: Toda Fumio , Ooi Nobuhiro
Published: July 2006

Treatment of 3,4-bis(diphenylmethyl)cyclobut-3-ene-1,2-dione (I) with bromine in ROH (R=H, Me, Et, and i-Pr) afforded 3,4-bis(diphenylmethylene)cyclobutane-1,2-dione (IV) and 3-diphenylmethyl-4-alkoxydi-phenylmethylcyclobut-3-ene-1,2-dione (III) in various ratios depending on the steric bulkiness of R of ROH. Acidification of a solution of III in KOH–MeOH, in which III exists in the form of enolate anion (VIII), afforded III and IV in various ratios depending on the steric nature of the substituent R. Bromination of IV in 99% acetic acid afforded 3,4-bis(hydroxydiphenylmethyl)cyclobut-3-ene-1,2-dione (XI). Although the bromination of XI with phosphorus tribromide afforded IV, that with bromine afforded the 2,5-dihydrofuran derivative (XVII). The reaction of I with o-phenylenediamine to afford azamethylenecyclobutane derivatives XXV and XXVI is described.
N-Halogen Compounds of Cyanamide Derivatives. I. Rearrangement of N-Alkylhaloamidines
Authors: Fuchigami Toshio , Ichikawa Eiichi , Odo Keijiro
Published: July 2006

The reactions of N-chloroamidines with various dehydrochlorinating reagents were studied. N-Alkyl-N-chloroamidines were treated with sodium alkoxide, sodium hydroxide, and silver oxide to form O-alkylisoureas, ureas, and carbodiimides, respectively. However, N′-chloro-N′,N′-dialkylamidines did not afford corresponding products. The mechanisms for the rearrangements are discussed.
A New Route for the Preparation of Pyrazolo[4,3-c]pyridines
Authors: El-sayed Abdou Ahmed , Ohta Masaki
Published: July 2006

The anhydride (II) of 4-carboxy-1,5-diphenylpyrazole-3-acetic acid (I) has been prepared. The reactions of II with primary amines resulted in the formation of the monoamides IIIa–c. 2,3-Diphenylpyrazolo[4,3-c]pyridine-(5H,7H)-4,6-dione (VIIa), has been obtained by heating the ammonium salt of I in a vacuum at 220 °C. The ring closure of IIIc with acetyl chloride in benzene afforded VIIb. Compound VIIb was coupled with benzenediazonium chloride to give the 7-phenylazo derivative (XII) and also condensed with aromatic aldehydes giving 7-arylidene derivatives (XV).
The Stability of Fused Rings in Metal Chelates. IX. Copper(II) and Nickel(II) Complexes of Schiff Bases Derived from Salicylaldehyde and Dipeptides Containing Glycine and/or β-Alanine
Authors: Nakao Yasuo , Nakahara Akitsugu
Published: July 2006

Copper(II) and nickel(II) complexes of Schiff bases derived from salicylaldehyde(Sal) and dipeptides containing glycine and/or β-alanine have been prepared. It has been found that Schiff base ligands containing glycylglycine (Gly·Gly), glycyl-β-alanine (Gly·β-Ala) or β-alanylglycine (β-Ala·Gly) as the peptide moieties give rise to square-planar, quadridentate copper(II)- and nickel(II)-chelates, while the N-salicylidene-β-alanyl-β-alanine (Sal=β-Ala·β-Ala) does not form the same type of copper(II)- or nickel(II)-chelate. It is concluded on the basis of spectrophotometric, polarographic and other measurements that the stability decreases in the order 6-5-5-([Cu(Sal=Gly·Gly)])≥6-5-6-([Cu(Sal=Gly·β-Ala)])≥6-6-5-([Cu(Sal=β-Ala·Gly)])>>6-6-6-([Cu(Sal=β-Ala·β-Ala)])fused-ring system.