bluuebunny/crossref_metadata_2025_split huggingface dataset:
Pseudohalogen Chemistry. III. Orientation of Heterolytic Addition of Thioeyanogen Chloride to Some Unsymmetrical Alkenes
Authors: Guy Robert G , Pearson Ian 
Published: July 2006

Abstract
Thiocyanogen chloride reacts with various unsymmetrical alkenes, cycloalkenes, and α-arylalkenes in the presence of a radical inhibitor in acetic acid in the dark at 25 °C to yield α-chloro-β-thiocyanates, α-acetoxy-β-thiocyanates, α-hydroxy-β-thiocyanates, vinylic thiocyanates or allylic isothiocyanates in various combinations. The additions to the α-arylalkenes are regiospecific, yielding the Markownikov-orientated products, but the regiospecificity of the additions to the aliphatic alkenes depends on the structure of the alkene. The orientation of addition is discussed in terms of open carbonium ions, e.g. 17, for the α-arylalkenes and cyano-sulfonium ions, e.g. 18, for the aliphatic alkenes.
Dielectric Transition in a Solution of Linear Poly(vinyl acetate)
Authors: Mashimo Satoru , Iwasa Yasuo , Chiba Akio , Higasi Keniti 
Published: July 2006

Abstract
The dielectric constants and losses of linear poly(vinyl acetate) (PVAc) in carbon tetrachloride were measured at various temperatures and frequencies. The results provide proof that dielectric transition in solution occurs for PVAc, irrespective of its sources.
Benzene Induced Shift for Some Organometallic 8-Quinolinolato Complexes: A New Criterion for the Interaction of Nitrogen with Metal
Authors: Kawasaki Yoshikane 
Published: July 2006

Abstract
The benzene induced shift was measured for some organometallic 8-quinolinolato complexes. A large upfield shift (0.5–0.7 ppm) of the 2-proton of the 8-quinolinolato ligand was found in benzene when the nitrogen in the 8-quinolinolato ligand coordinated to the metal. But the shift was small (0–0.3 ppm) in the absence of nitrogen coordination.
Stability Constants of the Rare Earth Complexes with 2-Ethyl-2-hydroxy-3-methylbutyric Acid
Authors: Suzuki Yasuo , Powell Jack E 
Published: July 2006

Abstract
The stability constants of the rare-earth complexes with 2-ethyl-2-hydroxy-3-methylbutyric acid have been determined potentiometrically at 25.0 °C and at an ionic strength of 0.10, with sodium perchlorate as the supporting electrolyte.
The Reduction of Divalent Copper and Tetravalent Tellurium by Ascorbic Acid–Application to Copper Telluride Analysis
Authors: Joshi M K , Raoot Sarala 
Published: July 2006

Abstract
Quantitative reduction of Cu2+ to metal copper and Te4+ to metal tellurium by ascorbic acid in alkaline and acid medium respectively has been studied. Based on this a new method for easy and simultaneous determination of copper and tellurium as in copper-telluride has been developed with reproducible results.
Preparation of Hindered Esters from Acid Chlorides and Alcohols in the Presence of Silver Cyanide
Authors: Takimoto Seiji , Inanaga Junji , Katsuki Tsutomu , Yamaguchi Masaru 
Published: July 2006

Abstract
Sterically hindered esters were prepared from the corresponding acyl chlorides and alcohols in the presence of silver cyanide. The method is superior to the conventional acyl chloride–alcohol–pyridine method as regards yield and the rapidity of reaction.
The Simulation of the ESR Spectra of the Perylene Cation on Solid Surfaces
Authors: Ueda Hisashi 
Published: July 2006

Abstract
The simulation of the ESR spectra of the perylene cation formed on the surface of silica gel (with MoO3), silica–alumina, and γ-alumina (with MoO3) was studied. These oxides were pretreated in a vacuum of 10−5 Torr and at 300 °C, and were then brought into contact with a purified perylene solution in benzene. The main parameters which determine the shape of spectra were investigated. By comparing the experimental spectra with the simulated ones, it was concluded that unpaired electron-spin densities on the carbon atoms of the perylene cation are identical to those of the perylene cation in the H2SO4 solution. However, the number of γ-protons which have spin-nuclear interactions with the unpaired electron is three or less. It was found that a considerable part of the line-width is caused by g-unisotropies. If the perylene cation is bound more strongly on the surface, more g-unisotropy is observed and the half-width becomes wider. When the perylene cation is prepared in the air, O2 and H2O molecules coordinate to the perylene cation formed. It was found that the complex cations thus formed have different g-unisotropies and that the ESR spectrum of this cation mixture is structureless, smooth, and a continuous curve.
Heterogeneous Catalysis in Liquid-Phase Oxidation of Olefin. I. Activity of Vanadium System Catalysts for Oxidation of Cyclohexene
Authors: Takehira Katsuomi , Ishikawa Toshio 
Published: July 2006

Abstract
The catalytic activities of various binary oxides containing vanadium for the liquid-phase oxidation of cyclohexene have been studied, in comparison with those of one component oxides and soluble metal acetylacetonates. The reaction was carried out at 60 °C in benzene solvent. The distribution of reaction products suggests the occurrence of autoxidation and epoxidation when vanadium system catalysts are used. Among the binary catalysts, V–Cr and V–Mo systems showed relatively high specific activities, especially high activity being obtained by the former systems calcined at a low temperature. It seems that cyclohexene oxide is formed mainly by two successive catalytic processes, i.e., the formation of cyclohexenyl hydroperoxide by autoxidation and the selective oxidation of cyclohexene with the hydroperoxide. The machanism of epoxidation was confirmed by the reaction of cyclohexene with t-butyl hydroperoxide in the presence of V–Cr catalyst.
The Thermodynamics of Nonstoichiometric Pr1−yGdyO1.5+δ
Authors: Endo Kazuhiro , Yamauchi Shigeru , Fueki Kazuo , Mukaibo Takashi 
Published: July 2006

Abstract
In order to contribute to the study of the thermodynamics of point defects in ionic crystals, the nonstoichiometry, δ, of Pr1−yGdyO1.5+δ (y=0, 0.1, 0.2, and 0.4) with a wide nonstoichiometric composition range was measured as a function of the oxygen partial pressure. Assuming that excess oxygen ions preferentially occupy Z-sites of the bixbyite structure and that the Pr3+ and Pr4+ ions are distributed on cationic sites at random, the equilibrium constant, K, was calculated for
2Pr^4++O_z^2-=2Pr^3++V_z+\frac12O_2
It was found that lnK changes with δ in the relation;
lnK=A+Bδ+Cδ^2
The parabolic dependence of lnK on δ is interpreted in terms of the changes in the energy of the defect formation and in the interaction energy between defects with the volume.
Thermal Decomposition of Dimethyl Ether in the Presence of Nitrogen Oxide
Authors: Tadasa Kohji , Imai Naomi , Inaba Tetsuo , Kubokawa Yutaka 
Published: July 2006

Abstract
The effect of NO addition on the thermal decomposition of CH3OCH3 has been studied at 500 °C. The rate of pyrolysis decreases markedly when the amount of NO is small, but increases linearly with increase in amount. Acceleration of pyrolysis was studied. Major reaction products are CH4, CH2O, CO, H2O, and N2, the minor ones being H2, N2O, and C2H6. The quantities of all the products were determined under different conditions except CH2O and H2O. It was found that the rate of formation is nearly of first order with respect to both NO and CH3OCH3. A reaction scheme is proposed. It is suggested that the rate of decomposition is nearly equal to that of the second order reaction NO+CH3OCH3→HNO+CH3OCH2.
Solid-state Properties of Evaporated Methyl Viologen
Authors: Murano Kentaro , Kamura Yusuke , Inokuchi Hiroo 
Published: July 2006

Abstract
The methyl viologen film evaporated at about 250 °C has a violet color, and its electronic absorption spectrum resembles that of the enzymatically reduced methyl viologen. The evaporated film becomes colorless upon the introduction of air. By means of the photoemission spectroscopical method, a very low ionization potential, 3.6 eV, was obtained for the evaporated methyl viologen film. The character of the evaporated methyl viologen is a free-radical one, and its specific resistivity is very low as compared with other organic radicals.
The Pressure and Temperature Dependences of the Second Virial Coefficients and the Chain Dimensions of Polydimethylsiloxane Solutions
Authors: Kubota Kenji , Kubo Kenji , Ogino Kazuyoshi 
Published: July 2006

Abstract
A new light-scattering optical cell was designed in order to perform light-scattering measurements at various temperatures and under pressures up to 400 kg/cm2. The second virial coefficients and the radii of gyration were determined at high polymer dilutions for polydimethylsiloxane in cyclohexyl bromide at 27.0, 36.5, 47.2, and 56.2 °C, in benzene and toluene at 27.0 °C, and in chlorobenzene at 30.0 °C. The method employed to determine the dimensions of the polymer is described. By a series of measurements of polydimethylsiloxane solutions, it is shown that the second virial coefficients, the radii of gyration, and the fundamental thermodynamic properties of the solutions depend on the pressure. The correlation between values of A2 and 〈S2〉1⁄2 shows that pressure influences these quantities through its effect on the polymer-solvent interaction parameter, χ or z. The values of the relative partial molar excess volume were calculated directly from the data. The obtained data were compared with the excluded volume theories and the corresponding state theories; the agreement was fair.
The Neutron Activation Analysis of Mercury in Soil
Authors: Nakano Souichi , Honboh Jukichi , Urabe Noriake 
Published: July 2006

Abstract
A radiochemical neutron activation procedure has been designed for the determination of mercury in soils. After the irradiation of 100 mg of soil it was decomposed with a hydrofluoric and perchloric acid mixture in a platinum crucible, and the mercury was separated radiochemically by solvent extraction from sulfuric acid·potassium iodide media into toluene, followed by precipitation as a sulfide. The radioactivity of 197Hg was measured by using a Ge(Li) detector. The chemical yield, as determined by atomic absorption spectrophotometry, was high enough, and the precision was satisfactory. The detection limit is estimated to be 1–2 ppb [(1–2)×10−10 g] by this method. The above procedure was applied to the determination of mercury in soils sampled in the Kumamoto and Minamata districts and in between.
The Syntheses and Properties of Bis(3-hydroxy-2-methyl-4-pyronato) Complexes of Bivalent Metal Ions
Authors: Morita Hideyoshi , Shimomura Shigeru , Kawaguchi Shinichi 
Published: July 2006

Abstract
Bis(3-hydroxy-2-methyl-4-pyronato) complexes of cobalt(II), nickel(II), copper(II), and zinc(II) have been prepared: CoL2(OH2)2, NiL2(OH2)2, CuL2, and [ZnL2(OH2)2]·1/2H2O. The 2,2′-bipyridine-(bpy) and 1,10-phenanthroline(phen) adducts of these complexes were also synthesized: CoL2(bpy), CoL2(phen), NiL2(bpy), ZnL2(bpy), and ZnL2(phen). Based on the magnetic, spectral, and thermogravimetric data, the structures of these complexes are proposed: all of the cobalt(II), nickel(II), and zinc(II) complexes are octahedral, and CuL2 is square planar. The NMR spectra of the zinc(II) complexes are discussed.
The Photolysis and Thermolysis of 3-(Diphenylhydroxymethyl)-4-(diphenylmethylene)-2-cyclobuten-1-one and Its 2-Bromo Derivative
Authors: Toda Fumio , Todo Eishiro 
Published: July 2006

Abstract
The photolysis of the title methylenecyclobutenone (1) and 2-bromomethylenecyclobutanone (9) in MeOH afforded 4,4-diphenyl-3-(2,2-diphenylvinyl)-2-buten-4-olide (5) and 3,3,5-triphenyl-1,3-dihydronaphtho[1,2-c]-furan-2-one (11) respectively. The photolysis of 1 and 9 in benzene, however, afforded 4,4-diphenyl-3-(diphenylvinylidene)-4-butanolide (2), and bromo-derivative of 5 (8) and 11 respectively. The thermolysis of 1 and 9 in o-xylene afforded 2 and 2-bromo derivative of 5(10) respectively. The mechanisms of these reactions were discussed. The solvent effect on the photolysis of 1 and 9 was also discussed.
Aminosugars. XXV. Synthesis of Benzyl 2-Acetamido-2-amino-2,3,4-trideoxy-α-d-arabino-hexopyranoside
Authors: Yoshimura Juji , Iwakawa Masaharu , Ogura Yoshio 
Published: July 2006

Abstract
As the attempted substitution of methyl 4-deoxy-2,3-di-O-mesyl-6-O-trityl-α-d-xylo-hexopyranoside with sodium azide gave the unsaturated compound: methyl 2,3,4-trideoxy-6-O-trityl-α-d-glycero-hex-2-enopyranoside (4), benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-α-d-mannopyranoside was used as the starting material, which was converted into benzyl 2-acetamido-2-deoxy-3-O-mesyl-6-O-trityl-α-d-mannopyranoside (10). For the deoxygenation of C-4 position, chlorination of 10 with sulfuryl chloride gave unexpectedly benzyl 3′-O-mesyl-6′-O-trityl-α-d-talopyranosid [2′,3′,4′; 4,5,6]-2-methyl-4,5-dihydro-6H-oxazine, due to the anchimeric effect of the C2-axial acetamido group. However, previous change of the conformation of 10 by the substitution of C3-mesyl group with azido group gave successfully the corresponding chloro derivative (13). Reduction of 13 with tributyltin hydride gave the corresponding 3,4-epimino derivative (14), due to participation of initially hydrogenated azido group, but, catalytic hydrogenation of 14 gave the title compound as the main product.
A New Type of Induced Decomposition. II. Decomposition of Phenylpropioloyl Peroxide and t-Butyl Phenyl-peroxypropiolate in Solution
Authors: Muramoto Nobuyuki , Ochiai Tameichi , Yoshida Masayuki , Simamura Osamu 
Published: July 2006

Abstract
Decomposition of phenylpropioloyl peroxide and t-butyl phenylperoxypropiolate in cumene, toluene, and cyclohexane was investigated. Product analysis and kinetic study together with the findings that radicals separately generated caused the decomposition of these peroxides demonstrate of a new type of induced decomposition involving radical attack on the triple bond of these peroxides and subsequent β-scission.
A New Type of Induced Decomposition. III Induced Decomposition of Cinnamoyl Peroxide, t-Butyl Peroxycinnamate and t-Butyl 2,3-Diphenylperoxypropionate in Solution
Authors: Ochiai Tameichi , Usuda Yoshitsugu , Yoshida Masayuki , Simamura Osamu 
Published: July 2006

Abstract
Phenyl and benzyl radicals were found to induce decomposition of cinnamoyl peroxide or t-butylperoxycinnamate to give stilbene and 1,3-diphenylpropene, respectively. Similarly, t-butoxyl radicals caused t-butyl 2,3-diphenylperoxypropionate to decompose affording stilbene. A mechanism is proposed which involves a radical atttack on a substrate peroxide producing a radical carrying an odd electron on the carbon atom β to the carboxyl group and its subsequent collapse to final products by way of β-scission.
The Decomposition of t-Butyl erythro- and threo-2,3-Diphenylperoxybutyrate in Solution. The Product Analysis and the Cage Effect
Authors: Ochiai Tameichi , Yoshida Masayuki , Simamura Osamu 
Published: July 2006

Abstract
Decomposition of t-butyl erythro- and threo-2,3-diphenylperoxybutyrate was examined in solution at 60 °C; there was no indication of induced decomposition taking place as is the case with t-butyl 2,3-diphenylperoxypropionate. Various hydrocarbons resulting from the reaction of the 1,2-diphenylpropyl radical in a variety of ways were identified in the product, and t-butyl 1,2-diphenylpropyl ether was found to be formed as cage recombination product in the threo/erythro isomeric ratio which depended on the stereochemistry of the starting peroxybutyrate.
Multifunctional Hydrolytic Catalyses. V. The Reaction of o-Substituted Benzohydroxamic Acids and p-Nitrophenyl Acetate
Authors: Kunitake Toyoki , Okahata Yoshio , Ando Reiko , Hirotsu Sumio 
Published: July 2006

Abstract
Salicylohydroxamic acid(SHA), N-methylsalicylohydroxamic acid(MSHA), and N-methylphthalohydroxamic acid(MPHA) were prepared and their acylation reactions with p-nitrophenyl acetate were studied in aqueous ethanol at 30 °C. Both the acidity and nucleophilicity of the hydroxamic acid group were affected by the functional ortho-substituents(–OH, –COOH). In particular, the undissociated hydroxamic acid group in the MPHA monoanion possessed nucleophilic reactivity. This was brought forth by the general base assistance of the adjacent carboxylate group, as confirmed by the presence of the solvent isotope effect of kH⁄kD=2.5. Only the hydroxamate anion acted as the nucleophile in all other cases.
Dehydroaunulenes. VI. Synthesis and Properties of 1,6,12,17-Tetraphenyl-2,4,13,15-tetrakisdehydro[22]annulene
Authors: Akiyama Shuzo , Nomoto Tateo , Iyoda Masahiko , Nakagawa Masazumi 
Published: July 2006

Abstract
1,6,12,17-Tetraphenyl-2,4,13,15-tetrakisdehydro[22]annulene has been synthesized. The sparlingly soluble tetrakisdehydro[22]annulene was found to be conformationally stable and strongly diatropic.
Spin Trapping of Benzoyloxycyclohexadienyl Radicals by 2,3,5,6-Tetramethylnitrosobenzene (Nitrosodurene) in the Decomposition of Dibenzoyl Peroxide in Benzene
Authors: Suehiro Tadashi , Kamimori Mariko , Sakuragi Hirochika , Yoshida Masayuki , Tokumaru Katsumi 
Published: July 2006

Abstract
The aroyloxycyclohexadienyl radicals (VIII), the key intermediates iates in the homolytic aromatic aroyloxylation, were detected and identified in the decomposition of dibenzoyl peroxide, bis(4-methylbenzoyl) peroxide, and bis(4-methoxybenzoyl) peroxide in benzene-d6 as spin adducts of nitrosodurene.
Reactions of Aroylhydrazones. II. Oxidative Cyclization of Benzil Bis(aroylhydrazones) to Substituted 1,2,3-Triazoles
Authors: Shaban Mohammed A E , Nassr Mahmoud A M 
Published: July 2006

Abstract
Benzil bis(aroylhydrazones) were oxidized with iodine and yellow mercury(II) oxide to 1-(1-α-aroyloxyaryl-ideneamino)-4,5-diphenyl-1,2,3-triazoles. The structure of the prepared compounds was determined by studying their chemical and spectral properties.
Molecular Rearrangements. VII. N-Alkylarylamines (III). Thermal Rearrangement of Secondary Arylamines
Authors: Osman A M , Badr MZA , Abdel-Rahman A E 
Published: July 2006

Abstract
Heating of N-benzyl-o- and p-toluidines resulted in migration of the benzyl group to the corresponding toluidine nucleus. The pyrolysis of N-benzyl-o-toluidine produced ammonia, toluene, bibenzyl, trans-stilbene, o-toluidine together with 4-amino-3-methyldiphenylmethane and 2,3-diphenyl-7-methylindole. N-benzyl-p-toluidine resulted into the same neutral products together with ammonia, p-toluidine, 2,3-diphenyl-5-methylindole together with 2,7-dimethyl-9-phenylacridine. Using phenol or quinoline as solvents, the normal rearranged products were accompanied with 2- and 4-benzylphenols and 2- and 4-benzylquinolines. It was concluded that the pyrolysis of the secondary amines proceeds through their homolytic fission to benzyl and the corresponding toluidino free radicals. Homolysis of some primary products was also observed.
The Preparation of Tetramethylphthalic Anhydride
Authors: Chiba Koji , Endo Eiji , Sakamoto Tokio , Sato Eiji , Fukuhara Ryoichi , Kobayashi Toshiko 
Published: July 2006

Abstract
The alkaline hydrolysis of bis(nitromethyl)prehnitene (1) with aqueous sodium hydroxide gave almost quantitatively disodium tetramethylphthalate (11). Under milder conditions the sodium salts of tetramethylphthalimide (8), N-hydroxytetramethylphthalimide (10), and 2-hydroxy-3-hydroxyimino-4,5,6,7-tetramethylphthalimide (9) were fo were formed, probably as intermediate products of the above reaction. But, pentamethylphenylnitromethane (14) and bis(nitromethyl)isodurene (15) were not hydrolyzed in an aqueous base. From the above results, it is recognized that the sodium nitronate from 1 is unstable in a different way from general nitronates such as the sodium salt of 14 or 15. It appears that the instability of 1 arises from the two adjacent nitromethyl groups on the benzene ring.
Hartree-Fock-Slater Calculations of the ESCA Chemical Shifts for Transition Metal Atoms
Authors: Tatsumi Kazuyuki , Fueno Takayuki 
Published: July 2006

Abstract
Hartree-Fock-Slater calculations have been carried out for inner-shell orbitals of some transition metal atoms (Ni, Rh, and Pt), and the core ionization energies computed by the transition state approximation. It is found that the ionization energy shifts do not conform to the conventional charge-potential approximation; the electron populations in individual valence d and s orbitals need to be considered separately.
Fouling Mechanism in Liquid Phase Oxidation of Carbon Monoxide Catalyzed by Palladium(II) Salts in Acetic Acid Solvents
Authors: Imanaka Toshinobu , Matsumoto Tetsuo , Kimura Toshio , Sakurai Katsumi , Teranishi Shiichiro 
Published: July 2006

Abstract
The fouling mechanism during catalytic activity in the liquid phase oxidation of carbon monoxide has been investigated using catalytic acetic acid solutions containing palladium(II) salts and lithium nitrate as oxidants. The fouling phenomenon becomes understandable upon the recognition that the active palladium catalysts react with the nitrite ion formed during the oxidation reaction to produce inactive-stable complexes.
Molar Volume Equations of Several Molten Binary Systems
Authors: Mochinaga Junichi , Igarashi Kazuo , Kuroda Hideo , Iwasaki Hironori 
Published: July 2006

Abstract
The molar volumes of YCl3–KCl, YCl3–NaCl, YCl3–CaCl2, PrCl3–KCl, PrCl3–NaCl, PrCl3–CaCl2, NdCl3–KCl3 NdCl3–NaCl, and NdCl3–CaCl2 systems in molten state were measured. The results are represented by empirical equations as functions of both temperature and composition. The calculations were carried out by using the methods of least squares and Powell’s procedure.
A New Type of Induced Decomposition. IV. Pyrolysis of t-Butyl Peroxy-3-butenoate in the Gas Phase
Authors: Ochiai Tameichi , Yoshida Masayuki , Simamura Osamu 
Published: July 2006

Abstract
t-Butyl peroxy-3-butenoate decomposes in the gas phase at 115 °C to give carbon dioxide, 1-butene, acetone, 1,5-hexadiene, methane, and ethane. Experiments with iodine, an efficient radical scavenger, indicate the operation of induced decomposition. The mechanism of the formation of 1-butene and 1,5-hexadiene is discussed in terms of a new type of induced decomposition.
Photochemical Conversion of Methoxyketene Intermediate into Methyl Ester in the Photolysis of 2-Methoxy-3-dijphenylmethyl-4-diphenylmethylene-2-cyclobuten-1-one
Authors: Toda Fumio , Todo Yozo , Todo Eishiro 
Published: July 2006

Abstract
The photolysis of methylenecyclobutenone in the presence of benzophenone or oxygen affords the one carbon diminished product, methyl 4,4-diphenyl-2-diphenylmethyl-2,3-butadienoate. The reaction pathway is discussed.
Syntheses of 4-(4-Hydroxy-2,6-dimethylphenyl)-1,2-butanediol and 4-(4-Hydroxy-2,6-dimethylphenyl)-2-butanol.
Authors: Uneyama Kenji , Sakumoto Hironori , Torii Sigeru 
Published: July 2006

Abstract
4-(4-Hydroxy-2,6-dimethylphenyl)-1,2-butanediol (3) and 4-(4-hydroxy-2,6-dimethylphenyl)-2-butanol (4) as precursors for a theaspirone synthesis have been synthesized starting from 3,5-dimethylphenyl methyl ether.