bluuebunny/crossref_metadata_2025_split huggingface dataset:
Formation and Properties of Phenylthiomethyl Radical. Anodic Oxidation of Sodium Phenylthioacetate and Thermal Decomposition of t-Butyl Phenylthioperacetate
Authors: Uneyama Kenji , Torii Sigeru , Oae Shigeru 
Published: July 2006

Abstract
Phenylthiomethyl radical 1 was generated both from anodic oxidation of sodium phenylthioacetate 4 in sodium methoxide-methanol solution and from thermal decomposition of t-butyl phenylthioperacetate 5 in benzene. Both reactions afforded a similar trend of product ratios, phenyl disulfide 7 in 31–32% yield as a major product and 1,2-diphenylthioethane 6, the dimer of radical 1 in 1–2% yield. A chemical and electrochemical reaction process of 1 along with a plausible mechanism for α-elimination of 1 is discussed.
The Catalytic Reaction of Alcohols with Reduced Copper
Authors: Kawamoto Kazuaki , Nishimura Yoshiharu 
Published: July 2006

Abstract
The catalytic properties of a reduced copper catalyst in reaction to ethyl alcohol, n-propyl alcohol, n-butyl alcohol, 2-phenylethanol, 1-phenylethanol, 3-phenyl-1-propanol, cinnamyl alcohol, propionaldehyde, n-propyl propionate, and a mixture of ethyl alcohol and propionaldehyde were studied. The present investigation has been undertaken in order to find out whether or not the activity and the selectivity of reduced copper are affected by the method of the preparation of catalysts and the structure of alcohols used as the reactants, and to clarify the mechanism of the formation of the esters and ketones obtained from aliphatic alcohols. It has been found that, over reduced copper, saturated aliphatic alcohol gives considerable amounts of the corresponding aldehyde and ester. The formation of the ester may be explained by a hemiacetal mechanism. The hydroxyl group of aliphatic alcohol is very resistant to hydrogenolysis. However, with the phenyl-substituted alcohols the carbon-to-oxygen bond is easily broken.
The Reaction of α-Carbonyl Sulfides with Bases. I. The Reaction between α-Carbonyl Sulfides with Thiolates
Authors: Oki Michinori , Funakoshi Wataru , Nakamura Atsuko 
Published: July 2006

Abstract
It is found that carbonyl compounds, such as ketones and esters, bearing an alkyl(or aryl)thio group at the α-position, are smoothly reduced to the parent carbonyl compounds by the action of the thiolate anion. α-Halo or α,α-dihalo ketones are similarly reduced with the thiolate, probably via the corresponding sulfides. The mechanism of the reaction is discussed.
p-Toluenesulfonylation of 1,2-O-Cyclohexylidene-myo-inositol
Authors: Suami Tetsuo , Ogawa Seiichiro , Tanaka Takatoshi , Otake Toshiki 
Published: July 2006

Abstract
p-Toluenesulfonylation of 1,2-O-cyclohexylidene-myo-inositol (la) afforded one mono (1), three di (1,4, 1,5, and 1,6), three tri (1,4,5, 1,4,6, and 1,5,6), and one tetra (1,4,5,6)-O-p-toluenesulfonyl derivatives of myo-inositol, and all the structures have been established by way of their proton magnetic resonance (PMR) spectra and the reaction sequences.
Iminodithiocarbonates. IV. Pyrolyses of N-Acyl Immonium Salts of Iminodithiocarbonates
Authors: Ueno Yoshio , Nakai Takeshi , Okawara Makoto 
Published: July 2006

Abstract
The pyrolyses of N-acyl immonium salts of S,S′-dimethyl N-methyl- (II) and N-phenyl-iminodithiocarbonates (III) were studied. N-Methyl-immonium salt II gave S-methyl N-acyl-N-methyl-dithiocarbamate (V) at 100°C, but N-phenyl derivatives (III) gave phenyl isothiocyanate and S-methyl thiolbenzoate (VI) at 140°C. On the other hand, cyclic immonium salt, 2-(N-benzoyl-N-methyl)-1,3-dithiolanylium chloride (IV) gave 2-benzoylimino-1,3-dithiolane(VII) with elimination of N-methyl group at 200°C. It was found that N-acyldithiocarbamate V isolated was further decomposed to methyl isothiocyanate and thiolbenzoate at 200°C. Independent syntheses of N-acyldithiocarbamates V were performed on the reaction of N-monosubstituted dithiocarbamates and acyl chloride.
Dissociation Constants of the Oxalato-Titanium(III) Complex as Determined from Spectrophotometric Measurements
Authors: Pan Kuan , Lai Chin Chan , Huang Teh-Shoon 
Published: July 2006

Abstract
The dissociation constant of Ti(C2O4)2− ions in hydrochloric acid media was evaluated from the data obtained by spectrophotometric measurements at 25°C. The average value of pK for the reaction, Ti(C2O4)2−=Ti(III)+2C2O42−, at an infinite dilution was estimated as 9.0, while that for the Ti(C2O4)2−=Ti3++2C2O42− reaction was evaluated as 8.74.
Effect of Phase on Excitation Transfer in the Radiolysis of Isobutane
Authors: Miyazaki Tetsuo , Yamada Takahisa , Wakayama Terunobu , Fueki Kenji , Kuri Zen-ichiro 
Published: July 2006

Abstract
The effects of CCl4 on the formation of H2 and C4H9 radicals in the radiolysis of i-C4H10 have been studied in glass at 77°K and the liquid at 195°K. The yield of H2, which is not affected by the addition of N2O or SF6, decreases sharply upon the addition of CCl4 in the glass, as in the crystal (This Bulletin, 42, 1164 (1969); 43, 1017 (1970).), while it does not so sharply decrease in the liquid as in the solid. The effects of CCl4 on the yields of H2 correspond fairly well to those on the yields of the C4H9 radicals. The effects of CCl4 in the glass are explained by the excitation transfer from the excited butane molecule to CCl4, as in the radiolysis of i-C4H10 in the crystal. A kinetic treatment suggests that its mechanism may be the exciton transfer. Some remarks on the primary process of ionization in the radiolysis of solid hydrocarbons are given from the viewpoint of exciton transfer.
The Hydrogenation of Butadiene Catalyzed by Pentacyanocobaltate(II) in Aqueous and Non-aqueous Solvents
Authors: Funabiki Takuzo , Tarama Kimio 
Published: July 2006

Abstract
The hydrogenation of butadiene catalyzed by pentacyanocobaltate(II) was studied in water and in glycerol-methanol-water and ethylene glycol-methanol solutions. The amount of hydrogen absorbed, and the rate of hydrogen absorption, in the water solvent were much greater than in the other solvents. The composition of the butenes produced by the hydrogenation in the water solution was trans-2-&gt;&gt;1-&gt;cis-2-butene at CN/Co&lt;5.1, and 1-&gt;&gt;trans-2-&gt;cis-2-butene at CN/Co&gt;5.1; this composition was affected by the concentration of the complex. The composition of the butenes produced in the glycerol-methanol solution was trans-2-&gt;&gt;1–&gt;cis-2-butene at CN/Co&lt;5.4 and 1-&gt;cis-2-&gt;&gt;trans-2-butene at CN/Co&gt;5.4; a concentration effect similar to that in the water solution was observed. The composition of butenes in the glycerol-methanol-water solution at CN/Co=6.0 was remarkably affected by the composition of the solvent. In the ethylene glycol-methanol solution, cis-2-butene was much more producible than in the glycerol-methanol solution. The mechanism of the hydrogenation of butadiene by pentacyanocobaltate(II) was discussed on the basis of these solvent effects on the composition of products, and on the basis of the kinetical behavior of this hydrogenation reaction.
Average Values of Bond Angles
Authors: Kuchitsu Kozo 
Published: July 2006

Abstract
A number of definitions with clear physical significance regarding the “average bond angles” (nonlinear case) are presented. Simple expressions of the average angles in terms of the linear and quadratic mean values of the displacements in the internuclear distances are given. The differences in the various average angles for H2O, D2O, CH4, CD4 and SO2 are estimated by means of a normal-coordinate analysis. The differences are shown to be small fractions of one degree. The root-mean-square angles for linear molecules (HCN, DCN, CO2 and CS2) are also calculated.
An MO-theoretical Interpretation of the Origin of the Orienting Effect in Aliphatic Systems
Authors: Fujimoto Hiroshi , Yamabe Shinichi , Fukui Kenichi 
Published: July 2006

Abstract
The importance of the charge-transfer interaction from the highest occupied (HO) molecular orbital (MO) of a donor to the lowest unoccupied (LU) MO of an acceptor molecule has been stressed on the basis of the numerical results of the calculation on a model of the SN2 reaction of methyl chloride. The effect of a counter ion on the frontier orbitals has been discussed. For the E2 reaction of ethyl chloride, it has been discussed how the orienting effect of the leaving nucleophile is transmitted to the trans-β-hydrogen by means of the frontier electron density. The influence of the rotation about the Cα–Cβ bond upon the reactivity of β-hydrogen has also been discussed.
Dielectric Relaxation and Molecular Structure. V. Application of the Single Frequency Method to Systems with two Debye Dispersions
Authors: Higasi Keniti , Koga Yoshinori , Nakamura Masahiko 
Published: July 2006

Abstract
There are four Debye equations for dilute solutions which can be used to determine the relaxation time of a polar solute molecule. This paper offers a critical examination of these equations, especially two representative formulas which are mutually independent. If the solute molecule has a non-rigid configuration and has two relaxation times, τ1 and τ2, for overall and internal rotations, respectively, average relaxation times will be obtained from these equations based on measurements at a single frequency. However, the analysis of this paper shows that under a certain condition (if a proper frequency for the measurement and a suitable equation for the calculation are employed) one may make a crude estimate regarding one of the two relaxation times. Further, the ratio of two relaxation times seems to afford a clue for investigating the mechanism of internal rotation. In addition, Cole-Cole dispersion and atomic polarization problems are also discussed.
A Remark on the Dipole Moment of Cyclohexane-1,4-dione in Relation to Its Flexible Molecular Conformation
Authors: Aihara Ariyuki , Kitazawa Chikazu 
Published: July 2006

Abstract
A critical remark on the interpretation of the polarity of cyclohexane-1,4-dione molecule has been made taking into consideration a possible contribution of atomic polarization estimated from the electric permittivity of the compound in the solid state. The value 9.6 cc has been assigned as the minimum for atomic polarization which gives dipole moments, 1.16D (28.6°C), 1.20D (42.9°C), and 1.22D (60.8°C) obtained in benzene solutions. A theoretical calculation of the dipole moment has been made also with an assumed potential barrier of the form, V(θ)=V0. [(π–θ)−2β]⁄2α, in relation to a flexing intramolecular movement of the molecule, where θ is the angle between two carbonyl groups substituted at the opposite sites of the molecule, V0 is the potential for a boat form A (with two carbonyl groups at the bow and the stern), and α, β are constants to be determined by applying boundary conditions: V(θ)=0 for θ=180°–137°, and V(91°)=V0. By taking 2.46D as the bond moment of carbonyl group, the best fit has been realized between the theoretical and experimental dipole moments when V0 is assumed to be close to 6000 cal/mol, i. e., twice as large as the hindering potential for the internal rotation of ethane molecule. Mention has also been made of the mechanism of dielectric absorption by this molecule in benzene solution with particular reference to the flexing motion suggested above.
ESR Studies of the Conformational Interconversion of the 9,10-Dihydrophenanthrene Radical Anion and Its Related Compounds
Authors: Iwaizumi Masamoto , Matsuzaki Takashi , Isobe Taro 
Published: July 2006

Abstract
The ESR spectra of the 9,10-dihydrophenanthrene radical anion change drastically with the temperature, and at temperatures around −30°C the spectra show a marked line-width alternation effect. These temperature-dependent ESR spectra and the line-width alternation effect have been interpreted in terms of the conformational interconversion of the 9,10-dihydrophenanthrene radical anion molecule. From an analysis of the spectra, the activation energy of the inversion has been estimated to be 6.3±0.6 kcal/mol. It has also been estimated, from the ratio of the axial and equatorial proton splittings, that the dihedral angle of the axial protons is about 11°. These data are compared with those of the 4,5,9,10-tetrahydropyrene radical anion. The ESR of the 4,5-dihydropyrene radical anion is also presented.
Molecular Vibrations and Force Fields of Alkyl Sulfides. II. Infrared Spectra of CH3S(CH2S)nCH3 (n=0–3)
Authors: Ohsaku Masaru , Shiro Yuji , Murata Hiromu 
Published: July 2006

Abstract
Infrared spectra recorded in the liquid and solid states of dimethyl sulfide, CH3SCH3, bis(methylthio)methane, CH3SCH2SCH3, bis(methylthiomethyl) sulfide, CH3SCH2SCH2SCH3, and bis[(methylthio)methylthio]methane, CH3SCH2SCH2SCH2SCH3, are reported. For the CH3SCH2SCH3 species, the gaseous spectra were also recorded. For these molecules, the observed bands were assigned to the fundamental modes of the vibrations with reference to those of reported analogous-structure molecules. The existence of the rotational isomers of the last three compounds was postulated. The regularity of the wave number of the fundamentals obtained and the intensity change in some of the bands for this series of compounds were discussed. The frequency shift in the liquid-solid phase transition was also described for a few bands.
Study on Oxidation of Chalcones with Lead Tetraacetate and Manganic Acetate
Authors: Kurosawa Kazu , Higuchi Junko 
Published: July 2006

Abstract
2′-Hydroxychalcones were oxidized with lead tetraacetate and manganic acetate to give trans- and cis-aurones, together with substituted benzoic acids and cinnamic acid. In the oxidation, 2′-benzyloxy-4,4′-dimethoxychal-cone gave 2-acetoxy-l-(2′-benzyloxy-4′-methoxy)phenyl-3-(4′-methoxy)phenylpropane-1,3-dione and erythro-2,3-diacetoxy-1-(2′-benzyloxy-4′-methoxy)phenyl-3-(4′-methoxy)phenylpropan-l-one. Structures of the products were elucidated spectrometrically and confirmed by syntheses.
Studies on Hydroxy Amino Acids. IV. Syntheses of Several Peptides Containing Aziridinecarboxylic Acid Derived from the Corresponding Hydroxy Amino Acid Derivatives
Authors: Nakagawa Yasuo , Tsuno Takashi , Nakajima Kiichiro , Iwai Michio , Kawai Haruki , Okawa Kenji 
Published: July 2006

Abstract
The β-elimination reaction of the O-tosyl β-hiydroxy amino acid peptide derivative was thoroughly investigated. The N-tosyl-l-serylglycine ester and the N-tosyl-l-threonylglycine ester gave the N-tosyl-l-aziridinecarbonyl-glycine ester and the N-tosyl-3-methyl-l-aziridinecarbonylglycine ester as the resulting products respectively by the elimination reaction. On the other hand, the N-carbobenzoxyglycyl-l-serylglycine ester was not converted into the aziridine peptide derivative; only the dehydroalanine peptide was obtained. However, the N-tosyl-l-phenylalanyl-l-threonylglycine ester and the N-carbobenzoxyglycyl-l-threonylglycine ester were converted into the corresponding aziridine peptide, and the N-tosyl-l-phenylalanyl-3-methyl-l-aziridinecarbonylglycine ester and the N-carbobenzoxyglycyl-3-methyl-l-aziridinecarbonylglycine ester were obtained respectively. It was concluded that the peptides containing threonine were easily converted into the aziridine peptides and not the serine peptides by the β-elimination reaction.
Heat Capacity of Ammonium Chloride between 8 and 300 K
Authors: Chihara Hideaki , Nakamura Minoru 
Published: July 2006

Abstract
Heat capacity of NH4Cl was measured between 8 and 300 K with an adiabatic calorimeter. The low-temperature limit of the Debye temperature is 352 K and its high-temperature limit in the harmonic approximation is 285 K. The λ transition point Tλ is 242.502±0.004 K with the heat of transition 1168 J mol−1 and the entropy of transition 5.00 JK−1 mol−1. It is very close to the first-order transition. From the analysis of the heat capacity between 242 and 300 K, an extra contribution to the heat capacity that amounts to 11.5 JK−1 mol−1 at 300 K is extracted and explained by a simple model which assumes an additional type of order-disorder in the arrangment of NH4 ions above Tλ. The energy difference between the parallel and the antiparallel pairs of NH4 ions is estimated to be 1.46 kj mol−1 from the low-temperature tail of the heat capacity anomaly near Tλ.
Fluorometric Determination of Aluminum and Gallium with Superchrome Garnet Y
Authors: Hiraki Keizo 
Published: July 2006

Abstract
A sensitive fluorometric determination of aluminum and gallium with Superchrome Garnet Y was described. The reagent reacts with aluminum and gallium to form complexes with reddish yellow fluorescence of emission maximum at 562 and 565 nm respectively. Several conditions for the determination, such as the pH of the solution, the reagent concentration, the time of standing etc. were investigated, and the composition of the complexes was determined. The maximum fluorescence intensity of the aluminum complex was found at pH 5 (heated for 10 min at 50°C), and that of the gallium complex, at pH 3. The fluorescence were stable at least for 2 hr. By using Superchrome Garnet Y, 0.02–4 μg of aluminum and 0.5–30 μg of gallium in 25 ml solution could be determined. Scandium and indium also formed fluorescent complexes. Iron(III), cobalt(II), copper(II), zirconium(IV), vanadate(V), and chromate(VI) ions interfered with the determination.
Trace Analysis of Metals by ESR. II. Indirect Microdetermination of Mercury(II) with Tetraethylthiuram disulfide Copper(II) Complex
Authors: Yamamoto Daijiro , Ikawa Noriaki 
Published: July 2006

Abstract
A method was devised for the indirect microdetermination of mercury by means of ESR. Tetraethylthiuram disulfide(TET)-Cu(II) complex dissolved in benzene showed a characteristic ESR spectrum. Quantitative determination of a small amount of mercury(II) was made by application of the replacement reaction of TET-Cu(II) by mercury(II)-ion in a benzene solution:
TET-Cu+Hg2+→TET-Hg+Cu2
The ratio of metal to ligand was considered to be 1 : 1 in the complex. 1.0–0.1 γ/ml and 0.1–0.01 γ/ml of mercury was determined rapidly in the presence of Mg2+, Fe2+, Ba2+, Mn2+, Zn2+, Co2+, Pb2+, Ni2+, I−, Br−, NO3−, and Cl− ions. CN− interfered with the determination. From a comparison of this and photometric methods a very small amount of mercury(II) ion can be determined with a very small amount of sample.
Dimerization and Isotopic Mixing of Ethylene by a Palladium Complex Catalyst
Authors: Kitamura Taketsugu , Maruya Ken-ichi , Moro-Oka Yoshihiko , Ozaki Atsumu 
Published: July 2006

Abstract
Dimerization and accompanied isotopic exchange of ethylene were studied with dichlorobis(benzonitrile)-palladium(II) complex in benzene solution. Dimerization as well as isotopic exchange take place simultaneously after an induction period, the extent of which is reduced by the presence of hydrogen releasing olefin such as 3-methyl-1-butene. Kinetics of dimerization is of first order in ethylene, but the dimerization rate does not immediately respond to the change in ethylene pressure. The results are interpreted in terms of a preformed palladium hydride complex.
Structures of Three Isomeric Dimers of 2,4,5-Triphenylimidazolyl
Authors: Tanino Hideo , Kondo Tadao , Okada Kunisuke , Goto Toshio 
Published: July 2006

Abstract
In addition of the piezochromic and the photochromic (dimer A) dimers of 2,4,5-triphenylimidazolyl, two new isomeric dimers were prepared; one (dimer B) being photochromic and the other (dimer C) non-photochromic. Several p-substituted derivatives of the dimers were also prepared. By comparison of their NMR and IR spectra, structures (a), (b), and (c) were assigned to the dimers A, B, and C, respectively. On treatment with hydrochloric acid in ethanol, dimer A underwent heterolytic cleavage and gave a mixture of 2-ethoxy-2H- and 4-ethoxy-4H-2,4,5-triphenylisoimidazole, and 2,4,5-triphenylimidazole.
The Biosynthesis of Linalool in Cinnamomum Camphora Sieb. var. linalooliferum Fujita
Authors: Suga Takayuki , Shishibori Tsuyoshi , Bukeo Michie 
Published: July 2006

Abstract
The labelling pattern in linalool biosynthesized from [2-14C] mevalonic acid in Cinnamomum Camphora Sieb. var. linalooliferum Fujita was found to be consistent with the predicted biosynthetic pathway involving the condensation of isopentenyl pyrophosphate with 3,3-dimethylallyl pyrophosphate. The radioactivities at C-4 and C-8 (and/or C-10) were about equal, in contrast to the asymmetric pattern of labelling observed for bicyclic monoterpenes, which contained a tracer predominantly in one position of the skeleton derived from isopentenyl pyrophosphate. The efficiency of the incorporation of the tracer into linalool was almost independent of the season of the examination, although a slight increase was observed in the season of the active growth of the plant.
Hydrogen Transfer Polymerization of Malononitrile
Authors: Kawabata Nariyoshi , Chen Chung Kuang , Yamashita Shinzo 
Published: July 2006

Abstract
Treatment of malononitrile with a catalytic amount of cuprous chloride and triethylamine under a nitrogen atmosphere resulted in the formation of solid polymer in high yield. The polymer was soluble in dimethyl sulfoxide, pyridine and hexamethylphosphoramide but insoluble in other organic solvents. The polymer was characterized by elemental analyses and IR and NMR spectra to have a mixed structure of an enamine form, (Remark: Graphics omitted.), and a ketimine form, (Remark: Graphics omitted.).
Intramolecular Hydrogen Bonding of ortho-Substituted Benzenethiols
Authors: Kobayashi Takahiro , Yamashita Akihiko , Furuya Yoshihiro , Horie Rumiko , Hirota Minoru 
Published: July 2006

Abstract
From the infrared, NMR, and dipole moment measurements on several substituted benzenethiols, the intramolecular hydrogen bonding in o-halo, o-methoxy, o-nitro, and o-carbomethoxybenzenethiols is verified. Fivemembered S–H···X hydrogen bonds cause remarkable enhancements of their S–H stretching absorptions without considerable frequency shifts. The favorable s-cis conformations in these thiols are also proved by comparing their experimental dipole moments with theoretical values. By far stronger hydrogen bond is observed in o-carbomethoxybenzenethiols which can form six-membered chelate ring by the intramolecular hydrogen bonding.
Measurements of the Vapor and Dissociation Pressures of Potassium Sulfate and Carbonate at High Temperatures
Authors: Kosugi Tetsuo 
Published: July 2006

Abstract
The dissociation reactions of potassium sulfate and potassium carbonate were determined using a quadrupoletype mass spectrometer with a Knudsen-cell-type ion source. The vapor and dissociation pressures of potassium sulfate and the dissociation pressure of potassium carbonate were obtained, by the use of the Knudsen effusion method at temperatures from 900 to 1700°K, as follows:
logP=−1.253×104\left(\frac1T\ight)+7.724(K2SO4)
logPd=−3.275×104\left(\frac1T\ight)+20.83(K2SO4)
logPd=−1.135×104\left(\frac1T\ight)+9.257(K2CO3)
The equilibrium constants of the dissociation reaction were estimated from the above data and from those of Kröger and Stratmann:
logKp=−6.94×104\left(\frac1T\ight)+38.8(K2SO4)
logKp=−1.38×104\left(\frac1T\ight)+9.80(K2CO3)