bluuebunny/crossref_metadata_2025 huggingface dataset:
Ion-Solvent Interaction of Tetraalkylammonium Ions in Dimethyl Sulphoxide from Electrolytic Conductivity Data
Authors: Jha Jai Shanker , Singh Sudha , Gopal Ram
Published: July 2006

Ion-solvent interaction of some tetraalkylammonium ions in dimethyl sulphoxide has been studied in this communication from the point of view of electrolytic conductivity and the derived Walden product. The R4N+ ions do not appear to interact strongly with this solvent; further, the salts examined appear to be completely dissociated in the concentration range studied here.
The Thermal Decomposition Reactions of Bivalent Metal Succinates in the Solid State
Authors: Yokobayashi Hiroko , Nagase Kenzo , Muraishi Kazuo
Published: July 2006

The thermal decomposition reactions of MC4H4O4 (M : Mg(II), Co(II), Ni(II), Cu(II), Zn(II), and Pb(II)) in nitrogen or helium were investigated by means of TG-DTA, X-ray diffraction measurements, gas chromatography, and combustion analysis for carbon. The decomposition residues of the Mg and Zn salts were composed of the corresponding metal oxides and some carbon, while those of the Co, Ni, Cu, and Pb salts were composed of the corresponding metals and some carbon. H2, O2, CO, CO2, H2O, CH4, C2H2, C2H4, HCOOCH3, HCOOC2H5, CH3COOC2H5, C2H5COOC2H5, and (CH2CO)2O were identified as the gaseous decomposition products; the compositions of the gaseous mixtures varied a great deal with the metals. Possible reaction mechanisms were discussed mainly on the basis of the decomposition products.
The Gas-chromatographic Determination of Selenium in Copper Metal and Copper Salts with 4-Nitro-o-phenylenediamine
Authors: Shimoishi Yasuaki
Published: July 2006

The gas-chromatographic method using an electron-capture detector has a high sensitivity for the determination of selenium. Moreover, as the reaction of selenium(IV) with 4-nitro-o-phenylenediamine is scarcely disturbed by other elements, the chemical separation from the matrix element is not necessary. The direct determination of very small amounts of selenium in copper and copper salts has been investigated. A mixture of equal volumes of nitric acid, hydrochloric acid, and perchloric acid dissolves the copper sample and also oxidizes the selenium to the quadrivalent state quantitatively. No loss of selenium was observed upon this treatment. The proposed method can determine the selenium in copper samples in amounts as low as 0.005 μg/g.
Isomerism of the Metal Complexes Containing Multidentate Ligands. VI. Geometric and Optical Isomers of the Tris(meso-2,3-butanediamine)-cobalt(III) Complex
Authors: Kojima Masaaki , Funaki Hiromi , Yoshikawa Yuzo , Yamasaki Kazuo
Published: July 2006

The tris(meso-2,3-butanediamine)cobalt(III) complex was prepared, and four possible isomers, mer-Λ, mer-Δ, facial-Λ, facial-Δ, were isolated by column chromatography on SP-Sephadex in the formation ratio of 1.4 : 1.4 : 1.0 : 1.0. The configurations and conformations of these isomers were proposed on the basis of the electronic, the circular dichorism, and the PMR spectra.
The Kinetics and Mechanisms of Reaction of Iodine with Bis(N,N-diethyldithiocarbamato)dimethyltin(IV) and Related Compounds
Authors: Kita Hidetoshi , Tanaka Koji , Tanaka Toshio
Published: July 2006

The reactions of Me2SnL(S2CNEt2) (L=S2CNEt2 (1) and I (2)) with iodine in cyclohexane were investigated employing a stopped-flow technique. The kinetic data indicate that the reaction in the presence of a large excess of 1 or 2 proceeds via a charge-transfer complex of Me2SnL(S2CNEt2)·I2, which decomposes in the ratedetermining step to yield Me2SnI(L) and unstable I(S2CNEt2). This unstable intermediate reacts with the excess 1 or 2 to afford Me2SnI(L) and tetraethylthiuramdisulfide (3). The reaction of 1 with a large excess of I2was also kinetically studied to reveal the formation of the 1 : 2 complex, Me2Sn(S2CNEt2)2·2I2, as an intermediate; this intermediate then undergoes a simultaneous degradation to afford Me2SnI2 and 3. The transition state in the reaction is discussed.
Effects of Solvents and Added Amines on the Selective Hydrogenation of 2-Naphthol over Urushibara Nickel and Cobalt Catalysts
Authors: Kajitani Masatsugu , Watanabe Yoshio , Iimura Yutaka , Sugimori Akira
Published: July 2006

The selective hydrogenation of 2-naphthol (NL) was investigated with Ni (U-Ni-B, U-Ni-A, and R-Ni) and Co (U-Co-B, U-Co-A, and R-Co) catalysts in various solvents at elevated temperatures and pressure (50 kg/cm2). U-Ni-B and U-Ni-A exhibited a high selectivity for the formation of 1,2,3,4-tetrahydro-2-naphthol (ac-TL), expecially in alcoholic solvents, while the hydrogenation with R-Ni in Et2O, i-PrOH, and benzene solvents gave preferentially 5,6,7,8-tetrahydro-2-naphthol (ar-TL). The ar-TL formation over Ni catalysts decreased in the following order, irrespective of the catalysts. i-PrOH>EtOH>MeOH and Et2O> benzene. However, the selectivity over Co catalyst was influenced to a lesser extent by the solvents. The addition of amines promoted the hydrogenation of NL to ar-TL in the following order: prim->sec->tert-amine in EtOH over Ni and Co catalysts. In general, Ni catalysts are more susceptible to the effects of solvents and added amines than Co catalysts.
The Finkelstein Reaction in Acetonitrile–Alcohol Mixtures. An Approach to an Anion Solvation by Means of a Multi-step Solvation Model
Authors: Kondo Yasuhiko , Kato Toshio , Tokura Niichiro
Published: July 2006

The rate constants were determined for both processes of the Finkelstein reaction in acetonitrile–alcohol mixtures at 30 °C:

CH_3Br+I^-\oversetk_f\undersetk_r\ightleftarrowsCH_3I+Br^-

Theoretical equations were derived describing the dependence of the rate constant on the composition changes in the solvent mixtures. These equations describe the change in the rate constant in terms of changes in the activity coefficient. The results were analyzed by means of the equations; they lead to the conclusion that anions have multiple solvation equilibria with alcohols. The relative magnitudes of the step-by-step association constants and of the solvation numbers thus determined agreed with the results determined spectrophotometrically.
Selective Homogeneous Hydrogenation of 3-Oxo-1,4-diene Steroids. III. On the Formation of Saturated 5α-Ketone in the Hydrogenation Catalyzed by Dichlorotris(triphenylphosphine)ruthenium
Authors: Nishimura Shigeo , Ichino Tomio , Akimoto Akira , Tsuneda Kiyoshi , Mori Hiromu
Published: July 2006

Hydrogenation of 1,4-androstadiene-2,17-dione (1) with RuCl2(Ph3P)3 gives some saturated 5α-ketone together with 4-androstene-3,17-dione (2). The ratio of 2 to the saturated ketone formed increases almost in proportion to hydrogen pressure. The rate dependence upon hydrogen pressure has been shown to be first-order for formation of 2 and zero-order for formation of the saturated ketone. A mechanism which involves a 1,5-hydride shift at an intermediate species is proposed for the stereoselective formation of the 5α-ketone.
An Attempt to Predict Thermal Pericyclic Reactions by a Sequential Nucleophilic Scheme
Authors: Ito Suketaka , Kakehi Akikazu , Tanaka Yumo
Published: July 2006

A simple, mnemonic method for predicting pericyclic reactions in ground states has been worked out by treating a multi-center reaction as a sequence of one-center reactions analogous to nucleophilic substitution type reaction. The analysis of reaction is carried out by illustrating localized MO’s and their stepwise transformation. This method can lead to predictions for thermal pericyclic reactions in agreement with the Woodward-Hoffmann rules and the HOMO-LUMO interaction method. A simple modification of this method is applicable to reactions in excited states.
Chemical Structure and Some Properties of Roseoflavin
Authors: Kasai Sabu , Miura Retsu , Matsui Kunio
Published: July 2006

Roseoflavin (I) is identified as 7-methyl-8-dimethylamino-10-(1′-d-ribityl)-isoalloxazine (IX) by comparing I with four diastereoisomers of 7-methyl-8-dimethylamino-10-d-n-pentitylisoalloxazine, which were synthesized from 2-dimethylamino-4-amino-toluene, d-pentoses, and violuric acid. The coincidence of chemical and physical properties—elemental analysis, UV-visible absorption spectrum, melting point, optical rotation, Rf value in thin layer chromatography, and NMR spectrum—of free and acetylated I with those of the free and acetylated IX, respectively, verified the identity. Some of the properties of I and acetylated I (pKa, oxidation-reduction, absorption spectra, and extinction coefficients of various ionic species, and photosensitivity) are also described.
The Role of Nucleophilic Solvents in the Acid-Catalyzed Cyclization of a Cross-Conjugated Cycloalkadienone
Authors: Noyori Ryoji , Ohnishi Yasushi , Katô Masao
Published: July 2006

In acetic acid or methanol containing a trace amount of H2SO4, 2,8-cyclononadienone cyclizes readily to give bicyclic ketones; the mechanism including the role of the nucleophilic media is discussed.
New Syntheses of Fervenulin (1,3-Dimethyl-7-azalumazine) and Analogs
Authors: Yoneda Fumio , Nagamatsu Tomohisa
Published: July 2006

A new, convenient method for the synthesis of fervenulin and its derivatives on the basis of the condensation of 6-amino-5-nitrosouracils and aldehyde hydrazones is described. A transformation of toxoflavins into fervenulins via 1-demethyltoxoflavins is also described. The alkylation of 1-demethyltoxoflavin with several alcohols in the presence of diethyl azodicarboxylate and triphenylphosphine gave the corresponding fervenulin homologs.
The Hydroxyphenylation of Methylstyrenes with Phenylpalladium Chloride
Authors: Horino Hiroshi , Inoue Naoto
Published: July 2006

The reaction of α- or β-methylstyrene with phenylpalladium chloride in aqueous acetone were studied. From cis- or trans-β-methylstyrene, a mixture of erythro and threo isomers of hydroxyphenylation products PhMeCHCHOHPh (VIa, VIb) and chlorophenylation products PhMeCHCHClPh (IVa, IVb) were obtained accompanying the phenylated olefins (I, II, and III). The main reaction product was the tertiary alcohol PhCH2C(OH)MePh (V). The reaction of α-methylstyrene with phenylpalladium chloride gave V exclusively. Phenylpalladium acetate and phenylpalladium bromide were used as phenylating agents. The yields of hydroxyphenylation products are in decreasing order: chloride>bromide>acetate.
Preparation and Application of Some New Disperse Anthraquinone Dyes
Authors: Metwally Saoud A M , Bredereck Karl
Published: July 2006

A series of anthraquinone derivatives free from water-solubilising groups were prepared. These compounds were found to be valuable for dyeing synthetic fibers with different shades of good fastness properties.
Structure of a Main Metabolite of Piroheptine Excreted in Urine of Rabbits; X-Ray Analysis of Its Hydrobromide
Authors: Tokuma Yoji , Koda Shigetaka , Tsubouchi Shinji , Morimoto Yukiyoshi
Published: July 2006

The structure of a main metabolite of piroheptine excreted in urine after administered to rabbits has been determined by X-ray analysis of its hydrobromide, C22H26NOBr. The crystals are monoclinic with space group P21/n, the unit-cell dimensions are: a=14.28, b=12.50, c=10.97 Å, β=96.06°. The intensities were estimated visually from multiple-film equi-inclination Weissenberg photographs. The structure was solved by the heavy atom method. The atomic parameters were refined by the block-diagonal least-squares method, and the final R index was 0.11. The established structure is shown by the following formula (hereafter, named as piroheptine metabolite HBr)

(Remark: Graphics omitted.)

It has been cleared that the hydroxylation in the metabolic process takes place at the 2-position in the benzene ring located far from the N-ethyl group on pyrrolidine ring, and piroheptine metabolite HBr and piroheptine HBr differ considerably in their conformations in the crystalline state.
Friedel-Crafts Benzylation of Toluene with Benzyl Chloride Catalyzed by Metal Oxides
Authors: Arata Kazushi , Azumi Norio , Sawamura Hiromitsu
Published: July 2006

Metal oxides were found to catalyze significantly the Friedel-Crafts type benzylation of toluene with benzyl chloride with a selectivity similar to that occurring with metal sulfates.
The Crystal and Molecular Structure of Emericellin, A Metabolite of Aspergillus nidulans
Authors: Fukuyama Keiichi , Tsukihara Tomitake , Kishida Shunji , Katsube Yukiteru , Ishida Masayoshi , Hamasaki Takashi , Hatsuda Yuichi
Published: July 2006

The crystal and molecular structure of emericellin has been determined by the X-ray diffraction method. The compound crystallizes in the space group P\bar1, with a=8.667, b=14.665, c=9.157 Å, α=88.29, β=113.10, and γ=91.61°. The structure was refined to an R value of 0.086 for 2151 non-zero reflections. There are two intramolecular hydrogen bonds.
The Apparent Solvent Effect on the Fluorescence Efficiency of 9-Methyl-10-(chloromethyl)anthracene
Authors: Tanaka Fujio , Osugi Jiro
Published: July 2006

9-Methyl-10-(chloromethyl)anthracene (I) is immediately transformed into 9-methyl-10-(ethoxymethyl)-anthracene (II) in ethanol, and a very strong fluorescence of II is observed. While I is practically nonfluorescent, II fluoresces strongly in all solvents. These facts explain well a phenomenon misinterpreted by Melhuish as a remarkable solvent effect on the fluorescence efficiency of I.
The Reaction of Water Vapor and Carbon Vapor Produced by Laser Irradiation
Authors: Kim Pil Hyon , Taki Ko , Namba Susumu
Published: July 2006

The carbon vapor produced by laser irradiation was found to react with the water vapor. The main products were carbon monoxide, hydrogen, and acetylene, the last of which is not found in the water-gas. Acetylene is considered to be formed by the reaction of the C2 species of the carbon vapor.
The Redox Acidity Function, Ro(H) in Glycols and Their Aqueous Mixtures
Authors: Srinivas Rao V , Kalidas G
Published: July 2006

The variation of the redox acidity function, R0(H) , based on ferrocene redox couple has been studied at 25 °C as a function of solvent composition in diethylene glycol–water and ethylene glycol–water mixtures and compared with the H0 variation in these solvents. Further, the redox function for sulfuric acid has been reported upto 6 molal in 50 wt% diethylene glycol–water mixture as the solvent.
Hydration of Perchlorate Anion in Nitrobenzene by Means of Cryoscopic Measurements
Authors: Tarui Takao
Published: July 2006

By means of cryoscopic measurements, hydration of the perchlorate anion in nitrobenzene was examined and the value of the first hydration constant was determined.
An Equilibrium Study of the Formation of Mixed-Ligand Nickel(II)-Aminopolycarboxylate Complexes
Authors: Kodama Mutsuo
Published: July 2006

The equilibria for the formation of 1 : 1 : 1 ratio mixed-ligand complexes of nickel (II)–NTA, HIDA, and –emylenediamine-N,N′-diacetate (EDDA) complexes with the glycinate (Gly), glutamate (Glut), and aspartate (Asp) anions were studied by determining the effects of the Gly, Glut, and Asp anions on the rates of the substitution reactions of nickel(II)–NTA, –HIDA, and –EDDA complexes with EDTA-OH or DTPA.
Kinetic Studies of the Electron Transfer Reaction in Iron(II) and Iron(III) Systems. VII. The Electron Transfer Reaction in Solid Dimethyl Sulfoxide
Authors: Wada Goro , Tabira Mikiko
Published: July 2006

The electron transfer reaction between Fe(II) and Fe(III) in dimethyl sulfoxide (DMSO) was investigated in the solid phase, and compared with the case in the liquid. In the temperature range between the freezing point (TM) and the eutectic point (TE), the reaction actually proceeds in the liquid phase where the reactants are concentrated due to the partial separation of pure DMSO solid, while below TE the reaction occurs in the solid phase at considerable reaction rates, with a lower activation energy, 4 kcal/mol, than that in the liquid. This indicates a different probable mechanism in solid DMSO.
Kinetics and Mechanism of the Reaction of Copper(II) with Hydroxylamine in the Presence of Bathocuproine Disulfonate
Authors: Imamura Taira , Fujimoto Masatoshi
Published: July 2006

The stoichiometry and the mechanism of the electron-transfer reaction of Cu(II) with hydroxylamine are investigated by measuring a fast complex formation of Cu(II) with bathocuproine disulfonate. The data are evaluated for the rate-determining step involving a radical species.
Organische Metallkomplexe. VIII. Notiz über die Kupfer(II)- raid Nickel(II)chelate der N,N′-Bis(2-phenylhydrazono-1-methyläthyliden)-α,ω-alkandiamine
Authors: Ohta Hiroshi , Kodera Yasushi , Mori Fumie , Koyama Mitsue , Ishibashi Sumie
Published: July 2006

Es wurden die Synthesen der neuen Ghelatbildner, N,N′-Bis (2-phenylhydrazono-1-methyläthyliden)-1,2-äthandiamin und -1,3-propandiamin sowie ihrer Kupfer(II)- und Nickel (II) chelate beschrieben.
A Convenient Method for the Preparation of Aryl and Alkyl Isothiocyanates Using Amines, Carbon Bisulfide, and a Grignard Reagent
Authors: Sakai Shizuyoshi , Fujinami Tatsuo , Aizawa Toshiyuki
Published: July 2006

The thermal decomposition of bromomagnesium N-aryl- or N-alkyl-N-bromomagnesio-dithiocarbamate (3), prepared in situ from amines, carbon disulfide, and a Grignard reagent, is a new and convenient method for the preparation of aryl or alkyl isothiocyanate.
Derivatives of 1,2-Dithiole-3-thione. XI. A Kinetic Study of the Reduction of N-Phenylsulfonyl Thione S-Imide with Halide
Authors: Tamagaki Seizo , Sakaki Keishi , Oae Shigeru
Published: July 2006

N-Phenylsulfonyl thione S-imide(I) was reduced with tetra-n-butylammonium bromide and iodide in the presence of trichloroacetic acid to yield benzotrithione and the sulfonamide in good yields. The kinetics of the reaction was performed, and the mechanism was discussed in detailed.
The Volatilization of Cadmium from Polyvinyl Chloride–Cadmium Mixtures on Heating
Authors: Tsunoda Ryoichi
Published: July 2006

The volatilization of cadmium from a PVC–cadmium stearate mixture on heating was studied by the X-ray diffraction analysis of the products volatilized, which were identified as CdCl2 in air metal Cd and CdCl2 in N2.
Trans-Gauche Equilibrium of 1,2-Dibromoethane and Dipole-interactions in Solutions
Authors: Kakimoto Masao , Fujiyama Tsunetake
Published: July 2006

The relative absorption intensities of the scissoring vibration bands of trans- and gauche-1,2-dibromoethanes were measured in pure liquid and in solutions of cis-1,2-dichloroethylene or tetrachloroethylene at various concentrations. The relative populations of the rotational isomers were determined from the intensity data. An attempt was made to describe quantitatively the observed concentration-dependence of the relative population on the basis of a semi-molecular theory of dipole-interaction. An equation is proposed for the averaged interaction energy of a molecule with its surrounding molecules, which is expressed in terms of the dipole moments and the polarizabilities of the solute and the solvent molecules.
Coagulation-dispersion and Precipitation-flotation Behavior of Bentonite and Cadmium-ion Flotation
Authors: Inakazu Toyono , Kobayashi Koichi , Sasaki Tsunetaka
Published: July 2006

The states of dispersion and the precipitation-flotation behavior of bentonite particles in an aqueous solution of hexadecyltrimethylammonium chloride (HTAC) were studied, and the effect of the HTAC on the coagulation and dispersion was discussed in connection with its adsorption on bentonite. The coagulation precipitation of bentonite began to occur at the ratio of the adsorbed amount to an exchange capacity, A⁄T, of about 0.05. It changed to coagulation flotation in the vicinity of A⁄T=1.2. The change was very sharp. The results suggest that the change from precipitation to flotation is produced by the adsorption of HTAC a little in excess of the first-layer formation, where a slight hydrophilization begins. It seems likely that, in the above state, the bubbles are easily accessible to bentonite particles because the agglomerates assume an open structure. The redispersion occurred near the point of sufficient hydrophilization of bentonite particles because of the adsorption of the second layer of cationic surfactant molecules.
The cis-trans Isomerization of 2-Butenes Photosensitized by Adsorbed Acetone
Authors: Otsuka Kiyoshi , Morikawa Akira
Published: July 2006

The anomalous acceleration of the rate of the cis-trans isomerization of 2-butenes is observed in the photosensitization of acetone adsorbed on porous Vycor glass. The anomaly is explained by means of a chain mechanism which is compatible with the triplet-triplet energy transfer mechanism. The chain carrier may be radicals formed by the dissociation of the lowest triplet acetone, resulting from the less efficient quenching of the triplet acetone by butenes at lower butene pressures. The preferential quenching of the acetone by the cis isomer to by the trans isomer of 2-butenes suggests that the geometrical factor plays a significant role in the reaction in the adsorption phase.
CNDO/2 Difference Electron Density Contours in Saturated Three-membered Rings
Authors: Ito Tetsuzo
Published: July 2006

Theoretical difference electron density contours in the NCC, CCC, and OCC ring planes of ethyleneimine quinone, cis-1,2,3-tricyanocyclopropane and tetracyanoethylene oxide molecules, respectively, were calculated by the CNDO/2 molecular orbital method. They are qualitatively in good agreement with the experimental contours, and have reproduced the most characteristic features of the observed electron distributions in the bent bonds in the three-membered rings. The theoretical difference contours in the three-membered ring planes of aziridine, cyclopropane and oxirane molecules have shown essentially the same bonding electron distributions as the corresponding contours in the more complex molecules mentioned above.
Electron Scavenging by Bromobenzene in the Radiolysis of Heptane, 1-Hexene and Their Mixtures
Authors: Baba Masatoshi , Fueki Kenji
Published: July 2006

A quantitative study has been made of electron scavenging by bromobenzene in the radiolysis of heptane, 1-hexene and their mixtures. Experimental data were analyzed using Schuler’s scavenging function. It has been found that the total ion yields are 4–5 G units in these liquids and the value of the reactivity parameter decreases with increasing fraction of 1-hexene. Further analysis of the data was made in terms of the exponential spatial distribution function for the electrons. A discussion is given to physical parameters derived from such analysis.
Chemical Reaction of Electron Donor–Acceptor System: A New Mechanism for the Tricyanovinylation Reaction of Some Aromatic Amines with Tetracyanoethylene
Authors: Nogami Takashi , Hasegawa Yoshiki , Shirota Yasuhiko , Mikawa Hiroshi
Published: July 2006

The tricyanovinylation reactions of several aromatic amines with tetracyanoethylene (TCNE) were investigated kinetically by observing the change of the absorbance of the charge-transfer (CT) band in 1,2-dichloroethane. The pseudo first order rate coefficient of the decay of the CT-complex (kobsd) was found to obey the relation, kobsd=kKDn⁄(1+KD) (K: association constant of CT-complex; D: initial concentration of donor molecule), where n=1 in N,N-diethylaniline (DEA)–TCNE and N,N-di-n-butylaniline (DBA)–TCNE systems and n=2 in N-methyl-N-ethylaniline (MEA)–TCNE system. Since the currently accepted mechanism for the tricyanovinylation reaction cannot explain the case of n=1, we have proposed a new reaction mechanism which can explain all the kinetic data reported hitherto. Two characteristic points are involved in the new mechanism, i.e., one is the unimolecular reaction of the CT-complex or the bimolecular reaction between reactants to form the σ-complex, and the other the decomposition of the σ-complex back to the component molecules. The reactions of MEA, DEA, and DBA with TCNE were discussed based on the new mechanism.
Pulse Radiolysis of Hg(CN)2 in Aqueous Solutions
Authors: Fujita Shin-ichi , Horii Hideo , Mori Toshiaki , Taniguchi Setzuo
Published: July 2006

The reduction of Hg(CN)2 in deaerated aqueous solutions was studied by the pulse radiolysis technique. Hg(CN)2 reacts with the eaq with k(eaq+Hg(CN)2)=(1.3±0.1)×1010 M−1 s−1 to yield a transient species of HgCN having an absorption maximum at 285 nm. Hg(CN)2 is also reduced by CO2− with k(CO2−+Hg(CN)2)=(3.4±0.2)×109 M−1 s−1. The extinction coefficient of HgCN at 285 nm was determined as (3.8±0.1)×103 M−1 cm−1. HgCN recombines with 2k=(3.4±0.5)×109 M−1 s−1 to produce another absorption species, assigned as (HgCN)2, in an unstable state. The decay rate of the dimer was accelerated by some additives, such as alcohols and sodium formate. Making use of a proposed mechanism, (HgCN)2→Hg(aq)+Hg(CN)2, the absorption coefficient of atomic mercury in water was evaluated as (2.8±0.1)×103 M−1 cm−1.
Electron Scavenging by Benzene Derivatives in Alcohol Glasses
Authors: Namiki Akira , Noda Masato , Higashimura Takenobu
Published: July 2006

Electron scavenging efficiencies by benzene derivatives in alcohol glasses were studied by employing gamma radiolysis at 77 K. Scavenging efficiencies, 1/[S]1⁄2, were quasi-linear with the adiabatic electron affinities (EA) of the acceptors and they increased as the solvation time of the trapped electron became long. Electron scavenging was explained as a tunneleing of the unsolvated electron; the pre-exponential factor in the tunneling rate was calculated by employing the Morse function developed by Wentworth et al. in the gas phase, which gave an EA dependence in accordance with the experimental results.
The Catalytic Action of TiO2 for the Isomerization of Butenes
Authors: Morishige Kunimitsu , Hattori Hideshi , Tanabe Kozo
Published: July 2006

The isomerization of 1-butene or cis-2-butene and the co-isomerization of cis-2-C4H8 and cis-2-C4D8 were carried out at 120 °C over TiO2 calcined in air. It has been found that induction period appeared and the ratio of cis-2-butene to trans-2-butene in the isomerization of 1-butene was unusually high (5–20). The double bond migration and cis-trans isomerization occurred by an intramolecular hydrogen transfer reaction and the kinetic isotope effect (kH⁄kD) was 4–5. The activity was completely or almost lost by poisoning with pyridine or nitric oxide. The isomerization was concluded to proceed by a π-allyl anion mechanism, where the cis-trans interconversion is highly restricted and the C–H bond cleavage is involved in the rate-determining step of the double bond migration. Main active sites were suggested to consist of both Lewis acid sites and basic sites (surface oxygen ion, O2−).
The Radiation Synthesis of Hydrogen Cyanide from the Nitrogen–ethylene System. The Effect of Fission-fragment Irradiation
Authors: Ikezoe Yasumasa , Sato Shoichi
Published: July 2006

Upon irradiation by (FF+n+γ), the G(HCN) value from the nitrogen-ethylene system increased with the rise in the pressure, while upon y and (n+γ) radiations it decreased. This pressure effect was explained in terms of the high concentration of the active species in the FF tracks. At a high pressure, Reaction (5) is considered to take place in the tracks;

&N_2^++e^-→2N\ ag5

\intertextAt low pressures, Reaction (6) predominates, as in the γ-ray radiolysis, over Reaction (5) even in the FF tracks,

&N_2^++C_2H_4→N_2+C_2H_4^+\ ag6

and nitrogen molecule cations do not contribute to the formation of hydrogen cyanide.
The Preparation and Absorption Spectra of the Cyanocarbonatotriammine-and Cyanooxalatotriammine-type Complexes of Cobalt(III)
Authors: Nakashima Shoji , Shibata Muraji
Published: July 2006

The complexes of the [CoCN(O–O)(N)3] type (O–O represents CO32− or C2O42−, and (N)3 represents three NH3, one NH3 plus one en, or one dien) have been prepared starting from the [Co(CO3)3]3− complex, and their characterization has been achieved on the basis of the absorption and PMR spectra. Among these, each of the fac(N) isomers of the carbonato complexes shows a shoulder in the second absorption band and no shoulder in the first absorption band. In contrast, each of the corresponding fac(N) isomers of the oxalato complexes shows no such shoulder in the second absorption band, but does show a shoulder in the first absorption band. The same phenomena have been found in the spectra of the trans(N)-[Co(O–O)(mda)(NH3)]− complexes (mda stands for the methyliminodiacetate ion).
Syntheses of Indolo[2,3-b]tropones and Benzo[b]-1-azaazulenes from 2-Hydrazinotropones
Authors: Nozoe Tetsuo , Sin Je-Kyun , Yamane Kameji , Fujimori Kunihide
Published: July 2006

The application of Fischer’s indole synthesis to cyclohexanone 2-troponylhydrazone gave 1,2,3,4-tetrahydroindolo[2,3-b]tropone (II), which was then dehydrogenated to indolo[2,3-b]tropone (III). 8-, 10-Isopropyl-, and 7-bromoindolo[2,3-b]tropone (XIIa–c) were also obtained by a similar method. The treatment of 2-troponylhydrazones of cycloheptanone and N-benzylpiperidone with dilute sulfuric acid or PPA gave 2,3-pentamethylenepyrrolo[2,3-b]tropone (XIII) and 2-benzyl-1,2,3,4-tetrahydrocyclohept[b]pyrido[3,4-d]pyrrol-6(5H)-one (XIV) respectively. The reaction of III with phosphoryl chloride or thionyl chloride yielded 8-chlorobenzo[b]-1-azaazulene (XV), which was subsequently converted into a hydrazino derivative (XVI). The oxidative decomposition of XVI with copper sulfate in acetic acid afforded benzo[b]-1-azaazulene (XVII).
The Structure of Polyvanadotungstates. II. The Crystal Structure of K7V5W8O4·12H2O
Authors: Nishikawa Keiko , Kobayashi Akiko , Sasaki Yukiyoshi
Published: July 2006

Crystals of K7V5W8O40·12H2O are cubic, with the space group of P\bar43m and with the cell dimension of a=10.62(1) Å. The structure was determined by the single-crystal X-ray diffraction technique. All the non-hydrogen atoms were located, and the final R value was 0.057. The V5W8O407− anion has the Keggin structure, with a central VO4 tetrahedron. The twelve outer metal positions are randomly occupied by four vanadium and eight tungsten atoms. A detailed discussion of the configuration isomers is impossible because of the orientational disorder. The present work, and the former X-ray structure determination of V2W4O194− show that polyvanado-tungstates can be regarded as substituted homologues of isopolytungstates: VnW6−nO19(n+2)− (n=1,2) has a hexanipbate-type structure, and VtVnWn−12O40(n+3)− (n=2,3,4), the Keggin structure, where Vt represents the central vanadium atom.
Chemical Vapor Growth of Titanium Diboride Whisker
Authors: Motojima Seiji , Sugimori Fumio , Takahashi Yasutaka , Sugiyama Kohzo
Published: July 2006

Titanium diboride whisker was grown by chemical vapor deposition from a gaseous mixture of TiCl4, BCl3, H2, and Ar. The relations between the growth conditions and the crystal morphologies were investigated. The predominant factors for whisker growth were found to be the substrate temperature and the kind of impurities painted on the substrate. The optimum temperature was determined as 1050–1070 °C where whiskers grew up to 250 μm in length and 0.1 to 1 μm in diameter for 30 min. Au, Pt, and Pd were found to be promissing impurities for whisker growth. From an observation of the droplet on whisker tip, the growth mechanism for the whiskers was supposed to be VLS mechanism. The form of whisker grown was tetragonal and hexagonal pillar, and the growth direction was determined as [100]direction.
Studies of the Ruthenium Complexes. XI. The Reaction Mechanism of the Base Hydrolysis of Halogenopentaammineruthenium(III) Complexes
Authors: Ohyoshi Akira , Sakamoto Hiroyuki , Makino Haruo , Hamada Keijiro
Published: July 2006

The base hydrolysis of halogenopentaammineruthenium(III) complexes, [RuX(NH3)5]X, (X=Cl, Br, and I), has been studied in a solution with a 0.03–0.2 M hydroxide ion concentration in order to clarify the reaction mechanism. Some deviations from the first-order rate plots were observed early in the reaction. By the analysis of these results, it was proved that the concentration change with time for each species participating in the reaction was expressed by a linear combination of two exponential functions. The reaction can be well accounted for by a mechanism involving SN2 CB and SN2 processes:

& [RuX(NH_3)_5]^2++OH^-\oversetk_1\undersetk_-1\ightleftarrows[RuX(NH_3)_4(NH_2)]^++H_2O

& [RuX(NH_3)_4(NH_2)]^++OH^-\oversetk_2\undersetH_2O→[Ru(OH)(NH_3)_5]^2++X^-+OH^-

& [RuX(NH_3)_5]^2++OH^-\oversetk_3→[Ru(OH)(NH_3)_5]^2++X^-

The rate constants, k1, k−1, k2, and k3, at 15 °C were determined to be 9.29×10−2 M−1 s−1, 2.65×10−2 s−1, 6.78×10−1 M−1 s−1, and 1.13×10−1 M−1 s−1 respectively for the chloropentaammine complex.
Thermal Dehydration Reactions of Bivalent Transition Metal Malonate Dihydrates in Solid State
Authors: Nagase Kenzo , Muraishi Kazuo , Sone Kozo , Tanaka Nobuyuki
Published: July 2006

The kinetics of the thermal dehydration reactions of MC3H2O4·2H2O(M=Mn(II), Fe(II), Co(II), Ni(II), and Zn(II)) were studied by the Freeman-Carroll and Coats-Redfern methods on the basis of the TG and DTG in nitrogen. The most reasonable reaction order for all the salts was found to be 2/3, indicating that the rate is controlled by the chemical process at a phase-boundary. This was also confirmed by the microscopic observations. The values of activation energy and frequency factor were 70–90 kJ mol−1 and 107–1010 s−1, respectively. The enthalpy changes for all the salts were determined to be 60–80 kJ mol−1 by the DSC measurements. The X-ray powder diffractograms, infrared absorption and diffuse reflectance spectra of the hydrates and anhydrous salts were also examined to obtain informations on their crystal and bonding structures.
Reactions of Vinyloxyboranes with Carbonyl Compounds, Nitriles, and Formates
Authors: Muraki Masayoshi , Inomata Katsuhiko , Mukaiyama Teruaki
Published: July 2006

A new vinyloxyborane derivative, Id, was found to be formed in reaction of phenyl di-n-butylthioboronite (II) with methyl vinyl ketone. In order to explore its utilization in organic synthesis, the reactivity of Id and other known vinyloxyboranes was variously examined. Id and Ie gave β-hydroxyketones (IVa–c, Va–d) in fairly good yields when they were allowed to react with carbonyl compounds. The reaction of Ia′ and Ib with nitriles, followed by hydrolysis, afforded β-iminothioates (VIa–c) and β-ketoesters (VIIa–d) respectively. It was also found that the borane (Ib) reacted with formates or formamides at room temperature to give ethyl α-formylhexanoate.
The Reaction of Alkyl Halides with Mercuric Thiocyanate in Tetrahydrofuran. The Solvent Incorporation and the Intermediacy of O-Alkyltetrahydrofuranram Ions.
Authors: Watanabe Nanao , Uemura Sakae , Okano Masaya
Published: July 2006

The reaction of alkyl halides with mercuric thiocyanate in tetrahydrofuran (THF) affords mainly the THF-incorporated products, R[O(CH2)4]nNCS and R[O(CH2)4]nSCN (mostly n=1 and 2), where the isomer ratios (N/S ratios) are nearly 1. The reaction of EtO(CH2)mBr (m=2–5) with mercuric thiocyanate in THF or n-Bu2O proceeds rapidly only in the case of m=4 to give EtO(CH2)4NCS and EtO(CH2)4SCN, the N/S ratio being also nearly 1, and gives EtNCS and EtSCN when m=5, while the reaction with potassium thiocyanate in DMF affords a good yield of EtO(CH2)mSCN (m=2–5) as nearly the only product. It is suggested that the titled reaction involves the initial formation of a five-membered oxonium ion, O-alkyltetrahydrofuranium ion, and a subsequent attack by XHg(SCN)2−.
Synthesis of d-Ribofuranosylpyrazolecarboxamides
Authors: Makabe Osamu , Nakamura Masakazu , Umezawa Sumio
Published: July 2006

Several carbamoylpyrazole-nucleosides were synthesized by fusion of 1-O-acetyl derivatives of ribofuranoses with pyrazole derivatives in the presence of bis(p-nitrophenyl) hydrogen phosphate as an acidic catalyst. NMR and UV spectral studies revealed the orientation in N-glycosylation of the substituted pyrazoles.
Photochemistry in Micellar System. II. Photochemical Reduction of β-Arylquinonesulfonates in the Presence of Cationic Surfactants.
Authors: Kano Koji , Takada Yuzo , Matsuo Taku
Published: July 2006

The photochemical reduction of sodium 9,10-phenanthraquinone-3-sulfonate (PQ) and sodium 1,2-naphthoquinone-4-sulfonate (NQ) to the corresponding diols has been studied in water containing cationic surfactants. Photoreduction of PQ was markedly accelerated in the presence of cationic surfactants whereas that of NQ, was highly retarded. Both the acceleration and retardation of the photoreaction of these quinonesulfonates in the presence of cationic surfactants are explained as due to the formation of association complexes betwen the quinones and the surfactants.
Kinetics of the Thermal Decompositions of Diaryl and Dialkyl Disulfides
Authors: Miyashita Tokuji , Matsuda Minoru , Iino Masashi
Published: July 2006

A kinetic study of the thermal decomposition of diphenyl disulfide, its p-methoxy, p-methyl, and p-chloro derivatives, and di-n-butyl and di-t-butyl disulfides in tetralin was made. The rate of decomposition was followed by the decrease of disulfide and the spontaneous first-order rate constants for these disulfides at 196, 207, and 217 °C and the activation parameters were obtained. It was observed that the rates of the decompositions for diaryl disulfides are increased by p-substituents (CH3O>Cl\simeqCH3>H) and that that of di-t-butyl disulfide is comparable to diaryl disulfides, whereas, di-n-butyl disulfide shows no decomposition under these conditions. A reaction scheme of the decomposition including induced decomposition is proposed from the kinetic results and product analysis. Moreover, the properties of a thiyl radical in relation to the above results are discussed from the electronic and ESR spectra of the aryl thiyl radicals generated from the photolysis of corresponding thiols in a glass of 2-methyltetrahydrofuran at −196 °C.
The Asymmetric (Enantioface Differentiating) Hydrogenation of the C=O Double Bond with Modified Raney Nickel. XXIX.
Authors: Harada Tadao
Published: July 2006

In the asymmetric (enantioface differentiating) hydrogenation of methyl acetoacetate with modified Raney nickel catalysts, the effects of the modifying pH on the amounts of the modifying reagents adsorbed and the enantioface differentiating abilities of the catalysts were studied using glycolic acid, mandelic acid, and 2-hydroxy-3-phenylpropionic acid as the modifying reagents. The results indicate that the modifying pH governs the adsorption mode of the modifying reagent. Thus, the change in the adsorption mode of the modifying reagent with the change in the modifying pH results in changes in the amount of the modifying reagent adsorbed and in the enantioface differentiating ability of the catalyst.
Novel Synthesis of Anhydronucleosides via the 2′,3′-O-Sulfinate of Purine Nucleosides as Intermediates
Authors: Sowa Tsuneo , Tsunoda Kozo
Published: July 2006

The synthesis of 8,2′-O-anhydro(9-β-d-arabinofuranosyl)-8-hydroxyadenine (3c) and 8,2′-S-anhydro(9-β-d-arabinofuranosyl)-8-mercaptoadenine (3a) is described. The active intermediates, 2′,3′-O-sulfinyl 8-bromoadenosine (2a), 2′,3′-O-sulfinyl-8-hydroxyadenosine (2c), and 2′,3′-O-sulfinyl-8-bromoguanosine (2d), were prepared from the corresponding nucleosides (1a, 1c or 1d) by successive treatment with thionyl chloride in the presence of pyridine in acetonitrile and with water. The anhydronucleosides, 3a and 3c, were formed in good yields by heating the intermediates (2a or 2c) in n-butanol in the presence of thiourea or in N,N-dimethylformamide in the presence of sodium acetate. All attempts at the cyclization of Compound 2d failed. The reaction product of 8-mercaptoadenosine (1b) with thionyl chloride was identified as the bis(2′,3′-O-sulfinyl adenosin-8-yl) disulfide (2b), which could not be transformed to Compound 3a.
Azafulvenes. 2. Formation of Iminium Salt from Pyrrole- and Indolecarbaldehyde and Its Reaction with Bases
Authors: Kobayashi Takashi , Kajigaeshi Shoji , Kanemasa Shuji
Published: July 2006

Pyrrole- and indolecarbaldehyde reacted with secondary ammonium perchlorate to produce the corresponding iminium perchlorate, which did not afford azafulvene, but instead its dimer, in good yield by deprotonation. These results indicate that the iminium perchlorate from pyrrole- and indolecarbaldehyde appears to be a convenient precursor of azafulvene.
Ethylation and Transethylation of Naphthalene
Authors: Shimada Keizo , Nagahama Shizuo
Published: July 2006

Transethylation of naphthalene by ethylxylenes and ethylbenzene in the presence of AlCl3 as a catalyst was studied and compared with ethylation by ethyl bromide. When ethylxylenes were used, it was observed that the β-isomer of ethylnaphthalene initially formed (96.8%) was isomerized to the α-isomer. This was attributed to steric hindrance of the α-position in the transition state of reactions proceeding by the hydride abstraction mechanism. However, the formation of considerable proportion of the α-isomer (25%) was observed in the case of transethylation by ethylbenzene, as well as of ethylation with ethyl bromide (60% α-isomer). Thus, the SN2 mechanism should be operative, at least partly, in the transethylation by ethylbenzene. The rates of transethylation by ethylxylenes were found to be in the order: 1,2-diMe-4-Et-\overset·\underset·≈1,3-diMe-4-Et->1,4-diMe-2-Et->>1,3-diMe-5-5-Et-benzene. The equilibrium composition of ethylnaphthalene was found to contain 8.7–8.8% α-isomer.
Low-temperature NMR Studies of the Conformations of 3-Aryl-1,2,3-oxathiazolidine 2-Oxides
Authors: Yamada Fukiko , Nishiyama Tomihiro , Samukawa Hiroshi
Published: July 2006

A complete iterative NMR spectral analysis has been carried out for twelve 3-aryl-1,2,3-oxathiazolidine 2-oxides at several low temperatures over a range of 111 °C. The magnitudes of the two vicinal coupling constants either increased or decreased markedly with a decrease in the temperature. On the basis of the resulting vicinal coupling constants, the correlations between the ratios of the vicinal coupling constants and the corresponding torsion angles were obtained and made it possible to assign their twist-envelope conformations. From the experimental data, the parameters of the Karplus equation could be given:

Jvic=5.3-cos(135±θ)+4.3cos2(135±θ)

+45°≥θ≥-45°
Cyclic Dimerization of Ethyl 1-Arylethylidenecyanoacetates with Grignard Reagents
Authors: Hayashi Shoji , Anii Takami , Tamano Taizo
Published: July 2006

The treatment of ethyl 1-arylethylidenecyanoacetates (I) with Grignard reagents, especially mesitylmagnesium bromide, gave ethyl 2,4-diaryl-5-cyano-5-ethoxycarbonyl-6-imino-4-methyl-1-cyclohexenecarboxylates (II), a dimer of I.
Anomeric Effect Involving Carboxyl and Ethynyl Group in Sulfur-Containing Heterocycles
Authors: Arai Kazutaka , Iwamura Hiizu , Oki Michinori
Published: July 2006

Normal anomeric effect is found in 1,3-dithiane-2-carboxylic acid, 1,3,5-trithiane-2-carboxylic acid, and their esters, in contrast to a report that oxane-2-carboxylic acid derivatives exhibit reverse anomeric effect. The results are interpreted from the difference in bond lengths between oxanes and polythianes which affects the extent of 1,3-diaxial interaction. The anomeric effect is found to be larger in 1,3-dithianes than in 1,3,5-trithianes. The differences is discussed on the ground of the energy levels of available electrons. Phenylethynyl derivatives also show small but definite anomeric effect.
X-Ray Photoelectron Spectroscopy of EDTA—Metal Chelates
Authors: Yoshida Tooru , Sawada Shigemasa
Published: July 2006

Photoelectron spectra of metal chelates of ethylenediaminetetraacetic acid (EDTA) were measured. A nearly linear relationship holds between the chemical shifts of the N(ls) electron binding energies and the charge on the nitrogen atoms of the chelates, calculated by means of Pauling’s electronegativity concept.
The Catalytic Reduction of Nitric Oxide by Carbon Monoxide over a Fe2O3 Catalyst
Authors: Sugi Yoshihiro , Todo Naoyuki , Sato Toshio
Published: July 2006

When nitric oxide was admitted during the course of the reduction of N2O by CO, a discontinuous increase in the N2O pressure and a decrease in the NO pressure were observed. The reduction of N2O stopped completely, and only the reduction of NO to N2O proceeded.
Nuclear Magnetic Resonance Studies of Bicyclic Thiophene Derivatives. III. Through Space H–F Coupling over Seven Bonds
Authors: Hirohashi Toshiyuki , Inaba Shigeho , Yamamoto Hisao
Published: July 2006

Bicyclic thiophene derivatives, 1,5-dimethyl-(1) and 3,5-dimethyl-4-(o-fluorophenyl)-l,2-dihydrothieno[2,3-d]-pyrimidin-2-ones (3), 2-acetylamino-3-(o-fluorobenzoyl)-4-methylthiophene (5), and some derivatives (2, 4, 6, 7), have been prepared. 1H, 19F Spin couplings over seven bonds, 7JHF, attributable to a through-space mechanism have been observed in the 1H NMR spectra of these compounds.
Electronic Absorption Spectra of the Disulfone Radical Anion. Conjugative Effect of the Sulfone Group
Authors: Ito Osamu , Matsuda Minoru
Published: July 2006

Disulfone radical anions produced by γ-irradiation show a characteristic absorption band at a longer wavelength region (655–695 nm) than that of the monosulfone radical anion (ca. 400 nm). The former band is attributed to the charge-resonance originated from the delocalization of an unpaired electron between the linked two sulfone moieties.
Dipole Moments of the Iodine Compounds Complexed with Some Aliphatic Amines
Authors: Toyoda Koichi , Imai Motoo
Published: July 2006

The dipole moments of some iodine compounds complexed with some aliphatic amines in benzene solution were obtained: 6.81D for EtH2N–I2; 6.78D for Et2HN–I2; 6.72D for Me3N–ICl; 7.22D for Me3N–IBr; 6.46D for Me3N–ICN.
The Preparation of 1- and 2-Aminophenazine Derivatives
Authors: Tada Masao
Published: July 2006

The reactions of chlorophenazines and their N-oxides with sodium azide in dimethyl sulfoxide or dimethylformamide yielded the corresponding aminophenazine derivatives.
Reactions of Diazomethyl-1,3,5-triazines with Cyclohexane
Authors: Kumagai Akio , Sekiguchi Shizen , Matsui Kohji
Published: July 2006

Diazomethyl-1,3,5-triazines reacted with cyclohexane thermally and photochemically to give cyclohexylmethyl-1,3,5-triazines as the major product. The reactions took place via a carbene intermediate; however, the hydrogen abstraction products (methyl-triazines) were not obtained in these cases.
Iron Carbonyl-catalyzed Reactions of Allyl Ethers and Amines Involving Claisen-type Rearrangement
Authors: Kiji Jitsuo , Nishimura Satoshi , Yamamoto Kazuyoshi , Furukawa Junji
Published: July 2006

The iron carbonyl-catalyzed reaction of diallyl ether with morpholine gives 1,4-dienylamine. Diallylamine isomerizes to 4-aza-6-methyl-1,4-nonadiene.
The Fries Rearrangement of Acetoxybenzofuran Derivatives and the Synthesis of Furochromenonecarboxylic Acids
Authors: Nanbu Mutsumu , Yamaguchi Seiji , Sugimasa Yasuo , Miyaura Tatsuya , Kawase Yoshiyuki
Published: July 2006

The Fries rearrangement of 4-, 5-, 6-, and 7-acetoxy-2,3-dimethylbenzofurans was studied and the o-hydroxy-ketones obtained were converted to dimethylfuro derivatives of 4H-chromen-4-one-2-carboxylic acid.
An INDO Molecular-orbital Interpretation of the NMR of Several Protonated Heteroaliphatic Compounds
Authors: Ohkubo Katsutoshi , Tsughihashi Kohji , Yoshida Toshiaki , Okada Masahide
Published: July 2006

Several protonated alcohols, acids, and esters were investigated by means of the INDO-MO theory and in connection with their proton and carbon-13 NMR results. The relative stability of the protonated conformers as detected by the NMR spectroscopy, had a good coincidence with the MO-theory and the experimental results. The proton or carbon-13 chemical shifts and coupling constants also showed satisfactory linear correlations between the theory and the experiment; the proton and isotropic (13C) chemical shifts could be well explained by the linear correlation between the diamagnetic shielding constant and the electron density on the proton of the O–H bond and between the calculated paramagnetic shielding effect and the observed isotropic chemical shifts. The observed coupling constants of the proton and carbon-13 NMR had good overall parallelisms with those evaluated by means of the Fermi contact effect.