bluuebunny/crossref_metadata_2025 huggingface dataset:
Mechanism of Racemization of Octahedral Silicon(IV) Complexes with Various β-Diketones in Organic Solvents
Authors: Inoue Tomoaki , Fujita Junnosuke , Saito Kazuo
Published: July 2006

Silicon(IV) complexes of 4 kinds of β-diketonate have been resolved and their racemization has been kinetically studied in 1,1,2,2-tetrachloroethane (TCE) and acetonitrile (AN) at 30 to 80 °C. Ultra-violet absorption spectroscopy and isotopic exchange studies with labelled ligands verified intra-molecular mechanism. A similar rate formula to that for the tris(acetylacetonato)silicon(IV) was obtained: k0=k1+k2[acid or base]. Increase in basicity of the ligand decreases the rate. Introduction of methyl group on the central carbon of the six-membered chelate ring markedly enhanced the racemization. It seems as if the intermediate species with a unidentate ligand tends to take trans form around the C=C axis and retards the recombination, giving rise to bigger k values. Mechanism of acid and base catalysis was also discussed.
Furan Derivatives. I. On the Methods of Synthesizing Some Naphtho[1,8-bc]furans
Authors: Horaguchi Takaaki , Shimizu Takahachi , Suzuki Tsuneo
Published: July 2006

Two kinds of methods of synthesizing naphtho[1,8-bc]furans (Vla–VId) are described. In the first method, naphtho[1,8-bc]furans (Vla–VId) were obtained by the decarboxylation of IIa–IId, which had previously been prepared from Ia-Id and ethyl bromoacetate. The yields of IIa–IId from Ia–Id were 45, 43, 49, and 46% respectively. In the second method, VIa–VId were obtained by heating Va–Vd with acetic anhydride and sodium acetate. The yields of VIa–VId were 34, 46, 46, and 70% respectively.
Crystallographic Studies of Interaction between Nucleotides and Metal Ions. I. Crystal Structures of the 1:1 Complexes of Cobalt and Nickel with Inosine 5′-Phosphate
Authors: Aoki Katsuyuki
Published: July 2006

The crystal structures of the 1:1 complexes of inosine 5′-phosphate with cobalt (C10H11O8N4PCo,7H2O) and inosine 5′-phosphate with nickel(C10H11O8N4PNi,7H2O) have been determined from single-crystal X-ray data collected on an automated diffractometer. The both isomorphous crystals belong to orthorhombic system, space group P212121 with four formula units in the unit cell of dimensions a=10.859, b=25.987, c=6.845 Å for the cobalt complex and a=10.812, b=25.898, c=6.845 Å for the nickel complex respectively. The structure of the cobalt complex was determined by three-dimensional Patterson and Fourier methods and that of the nickel complex was elucidated from that of the cobalt complex. Both were refined by the block-diagonal least-squares method including anisotropic temperature factors. The final R values were 0.051 and 0.075 for the cobalt and nickel complexes, respectively. All of the 25 hydrogen atoms in the case of the cobalt complex and 22 hydrogen atoms in the case of the nickel complex were found. The hypoxanthine bases related by the two-fold screw axis parallel to c are extensively overlapped at a distance of 3.42 Å for both complexes. The nucleotides have the preferred anti conformation about the glycoside linkage with the ribose ring showing the C(3′)-endo pucker. The torsion angles around the C(5′)–O(5′) bond are 161.6° (cobalt complex) and 162.0° (nickel complex). In the both complexes, therefore, the phosphate group has the extended conformation. The metals are not directly bonded to the phosphate oxygen atoms but are bonded to the nitrogen atom N(7) of the base and to five water oxygen atoms. There is extensive hydrogen bonding involving the hypoxanthine ring, the phosphate anion, the hydroxyl groups of the furanose ring and seven water molecules in the crystal.
Selective Dimerization of Propene to 4-Methyl-1-pentene by Potassium–Copper based Catalysts
Authors: Yamashita Junzo , Sasaki Kiyoshi , Kawamura Takao , Higuchi Koichi , Miura Shotaro , Hashimoto Harukichi
Published: July 2006

The dimerization of propene by potassium catalyst was carried out at 180 °C in n-heptane to give 4-methyl-1-pentene as a major product. The effects of the addition of metal powders, potassium alkoxides and tertiary amines were investigated. The selective production of 4-methyl-1-pentene on adding metal powders increased in the order of Cu, Ag>Mg, Co>Al, Fe, Ni, Zn. When long-chain alkoxides were added to the potassium–copper catalyst system, potassium catalyst was observed to be dispersed, the relative reaction rates increased, and the isomerization of 4-methyl-1-pentene formed was retarded. Thus, the selectivity increased more than 90% after 40% conversion of propene. The potassium–copper–aliphatic tertiary amine-catalyst system caused the yield of 4-methyl-1-pentene to increase in a similar manner to the potassium–copper–alkoxide-catalyst system and inhibited the formation of the carbonaceous substance covering the surface of the catalyst, and the selectivity was not lowered after a higher conversion of propene.
The Reaction of Cycloalkanones with Copper(II) Halides. I. The Reaction of Cyclohexanones with Copper(II) Chloride
Authors: Nishizawa Kyoko , Satoh J Yasuo
Published: July 2006

The reaction of cyclohexanones with copper(II) chloride gave polychlorinated cyclohexanediones directly in fairly good yields. With methylcyclohexanones, in general the type of product depends on the number of methylene groups between the carbonyl group and the methyl-substituted carbon in the starting material. A possible mechanism for the reaction is discussed.
Vinyl Polymerization. 327. Determination of the Initiating Radical Species in Polymerization with a Dimethylmercury and Copper(II)-Ion System
Authors: Imoto Minoru , Nakamura Yoshiaki , Ouchi Tatsuro
Published: July 2006

Dimethylmercury was found to give a methyl radical (·CH3) by the reaction with Cu(II)-ion in the presence of water. Generation of ·CH3 was proved by scavenging with 1,3,5,-triphenylverdazyl. Radical polymerization of methyl methacrylate and acrylonitrile was carried out with the system dimethylmercury/water/Cu(II)or Fe(III)-ion.
A-Substituted 5β-Steroids. VII. The Polyhalogenation of 5β-Cholestan-2-one
Authors: Satoh J Yasuo , Horiuchi C Akira , Hagitani Akira
Published: July 2006

The polyhalogenation of 5β-cholestan-2-one (I) in acetic acid containing hydrogen halide occurs in this positional order: C1→C3→C3 and finally at C1, which has the largest steric hindrance. The tetrahalogenation of the ketone (I) yields 1,1,3,3-tetrachloro-5β-cholestan-2-one (IXb), but fails to give the tetrabromo derivative; rather, it yields 1β,3,3-tribromo-5β-cholestan-2-one (Va), 1,1,3-tribromo-5β-cholest-3-en-2-one (VIIIa), and 1β,3-dibromo-5β-cholest-3-en-2-one (VIa). The conformations of the dihalo-, the trihalo-, and the tetrachloroketone derivatives are discussed in connection with the ORD, CD, IR, and NMR spectra.
The Effects of Substituents and Solvents on the Structure of Fluorenyl and Cyclopentadienyl Salts
Authors: Tomoi Masao , Yoneyama Toshio , Kakiuchi Hiroshi
Published: July 2006

The electronic spectra of 9-(ω-methoxyalkyl) and 9-(ω-dimethylaminoalkyl)fluorenyl salts of alkali cations were measured in ethereal solvents. The relative amounts of the contract ion pairs connected with the 9-substitu-ents (R) decreased in this order: R=(CH3)2N–(CH2)2–>CH3O–(CH2)2–>CH3O–(CH2)3–>(CH3)2N–(CH2)3–>>CH3O–(CH2)4−≈n-C4H9−. This behavior was explained in terms of the formation of an intramolecular association between the hetero atoms in the substituents and the counter ions; such an association favored the formation of the contact ion pair. The interaction of magnesium fluorenide and cyclopentadienide with hexamethylphosphoramide (HMPA) was studied by means of NMR spectroscopy in ether or tetrahydrofuran. The fluorenide changed from a covalent type to a solvent-separated ion pair by the coordination of three HMPA with the magnesium. The cyclopentadienide was proposed to change from a contact ion pair to a solvent-separated ion pair by means of two-step process in which the cyclopentadienyl ions became successively separated from the magnesium ion.
Photosensitized Polar Addition of Acetic Acid to 4-Homoadamantene: The Behavior of the 4-Homoadamantyl Cation
Authors: Yamagughi Ryohei , Kawanisi Mituyosi
Published: July 2006

The photosensitized polar addition of acetic acid to 4-homoadamantene (I) gave 2,4-dehydrohomoadamantene (II), 2-adamantylmethyl acetate (IIIa), and 4-homoadamantyl acetate (IVa). The same treatment of I in pivalic acid gave analogous products, II, 2-adamantylmethyl pivalate (IIIb), and 4-homoadamantyl pivalate (IVb). It was shown that II and III were derived from the 4-homoadamantyl cation (V). On the other hand, the diazotization of 4-homoadamantylamine (XV) in the presence of acetic acid gave I, II, and IVa, whereas it has been reported that a buffered acetolysis of 4-homoadamantyl tosylate (XIV) gave I and IVa, but not II. The formation of II may be explained by assuming a different energy state of V of different origin; it proves a vibrationally excited nature of V generated in the photosensitized polar addition reaction.
The Catalytic Action of Fe(III) in the U(IV)–U(VI) Electron Exchange Reaction
Authors: Tomiyasu Hiroshi , Fukutomi Hiroshi
Published: July 2006

The catalytic action of ferric ions in the U(IV)–U(VI) electron exchange reaction has been studied in the presence of a high concentration of hydrochloric acid. The exchange rate is found to be accelerated by the addition of ferric ions; the observed rate law is given by:

R=k_0[U(IV)][U(VI)]+k_c[Fe(III)]_0\sqrt[U(IV)][U(VI)]

An activation energy of 19.7 kcal/mol was calculated for the iron-catalyzed reaction in the U(IV)–U(VI) electron exchange reaction. This value is much smaller than that of 32.2 kcal/mol, which was found in the non-catalytic reaction. The kinetics and equilibrium of the reaction between Fe(III) and U(IV) have also been studied in order to investigate in detail the mechanism of the catalytic reaction. A one-electron-transfer mechanism producing U(V) as an intermediate is estimated from the rate law and supported by the kinetics and equilibrium studies of the Fe(III)–U(IV) reaction.
The Formation of Crystalline Complexes between Inosine and Several Hydroxybenzoic Acids
Authors: Suzuki Yoshihisa , Hara Kentaro
Published: July 2006

Inosine was found to form 1 : 1 crystalline complexes with 2,4-, 2,5-, 2,6-, 3,4-, 3,5-dihydroxybenzoic acids, and with 3,4,5-trihydroxybenzoic acid, but was found to give no crystalline complex with benzoic acid, o-, m-, p-hydroxybenzoic acids, 2,3-dihydroxybenzoic acid, or 2,3,4-trihydroxybenzoic acid.
On the Melting Point of N-Methylacetamide–Silver Nitrate Adduct
Authors: Matsubara Takaharu , Tanaka Toshio
Published: July 2006

The melting point of N-methylacetamide–silver nitrate adduct AgNO3·2NMA was found to be 46–47 °C which is in large disagreement with that reported by Paul and Chadha. The discrepancy was interpreted to result from the tendency of the adduct to lose NMA at high temperatures or at low partial pressures of NMA.
α,β-Unsaturated Carboxylic Acid Derivatives. VII. Reaction of Ethyl α,β-Unsaturated α-Cyanocarboxylates with Triethyl or Diethyl Phosphonate
Authors: Shin Chung-gi , Yonezawa Yasuchika , Sekine Yasuo , Yoshimura Juji
Published: July 2006

The reaction of ethyl α,β-unsaturated α-cyanocarboxylates with triethyl phosphonate gave ethyl α-cyano-β-diethoxyphosphinyl-carboxylates in about 50% yields.
Electronic Structures and Spectra of Quinarene Molecules
Authors: Yamaguchi Hiroyuki , Nakajima Takeshi
Published: July 2006

The electronic structures and spectra of fundamental quinarene molecules, 1–9 (Fig. 1) and some of their diphenyl derivatives (Fig. 2) have been studied by using the variable bond-length SCF LCAO-π-MO CI method.
The Allylic Rearrangement. IV. New Synthesis of 4-Hexenoic Acid
Authors: Tsuboi Sadao , Takeda Akira
Published: July 2006

rans-4-Hexenoic acid, a useful starting material for the synthesis of racemic 4R : 5S and 4S : 5R 4,5-dihydroxyhexanoic acid γ-lactone, one component of the aroma extracts from one Galifornian and two Spanish flor sherries, has been conveniently prepared by the Favorskii-type rearrangement of 5-chloro-3-hexen-2-one.
Potential Antitumor N-Carbamoyl-N′-methyl-N′-nitroso Derivatives of Amino Acids
Authors: Machinami Tomoya , Suami Tetsuo
Published: July 2006

N-Carbamoyl-N′-methyl-N′-nitroso derivatives of amino acids have been prepared by treating the amino acids with methyl isocyanate followed by nitrosation with sodium nitrite in dilute acetic acid solution.
Catalytic Transformation of Cyclohexene Hydroperoxides to Epoxy Alcohols with Vanadyl Acetylacetonate
Authors: Itoh Takashi , Kaneda Kiyotomi , Teranishi Shiichiro
Published: July 2006

Cyclohexene hydroperoxide and its methyl derivatives undergo rearrangement in the presence of the vanadyl acetylacetonate catalyst to the corresponding epoxyalcohols with high cis-stereoselectivity in high yields.
The Catalytic Hydrogenation of Ethylene over Calcium Hydride and the Role of the Hydrogen of the Hydride
Authors: Yamaguchi Masaru , Hiraki Yozaburo , Wada Masatada , Tarama Kimio
Published: July 2006

The catalytic hydrogenation of ethylene over the non-stoichiometric calcium hydride (CaH2−δ) prepared by means of high-temperature evacuation was studied. The order of introducing gases had no effect on the rate of ethylene hydrogenation. The rate expressions for the initial stage were ν=k  PH0.8–1.0 PE and ν′=k′ PH0.8–1.0 PE0 in the lower and higher pressure ranges of ethylene respectively. The amount of hydrogen bound initially to CaH2−δ and participating in the reaction was estimated from the results of the D2–CaH2−δ exchange and H2–D2 equilibration reactions. From these results, the mechanism of ethylene hydrogenation over calcium hydride and the role of the hydrogen of the hydride were discussed. The poisoning caused by water and acetylene was also studied. Furthermore, the catalytic activity of calcium hydride was compared with that of three metallic hydrides.
Polarographic Reduction of Ubiquinone-10 Solubilized in Micelles
Authors: Erabi Tatsuo , Hiura Hisahide , Tanaka Masaya
Published: July 2006

Ubiquinone-10 solubilized in an aqueous solution containing sodium dodecyl sulfate as an anionic surfactant was polarographically investigated. Ubiquinone-10 solubilized in micelles shows a well-defined, diffusion-controlled, pH-dependent wave. Diffusion coefficient and apparent particles radii were calculated. The surfactant concentration dependence of the diffusion coefficient and of the apparent particle radii was also determined.
Polarography of Dialkylthallium(III) Compounds. I. Polarography of Dibutylthallium(III) Compounds
Authors: Murayama Teisuke , Kikuchi Kenji
Published: July 2006

Electrochemical reduction of three dibutylthallium(III) cations has been studied through the use of polarographic methods. Reduction at a dropping mercury electrode occurs in two steps for the di-n-butylthallium (DNBT) and diisobutylthallium (DIBT) cations in alkaline solutions, and for the di-sec-butylthallium (DSBT) cation in all pH ranges examined. The first and second waves of the DSBT cation in alkaline solutions correspond to, respectively, no-proton one-electron and two-proton two-electron processes. The DNBT and DIBT cations produce a single wave in acid solutions, consuming two protons and three electrons. On polarograms recorded with Kalousek’s switching circuit a product and two kinds of intermediates were observed for the reduction of the DNBT and DIBT cations, and a product and one kind of intermediate for the reduction of the DSBT cation. A reaction scheme is proposed for the polarographic reduction of dibutylthallium cations.
The T←S0 Absorption of the Acetophenone Crystal
Authors: Tanimoto Yoshifumi , Azumi Tohru , Nagakura Saburo
Published: July 2006

The polarization and Zeeman splitting of the T←S0 absorption were measured with the acetophenone single crystal at 4.2 K. From the analyses of the polarization behavior and the Zeeman splitting pattern, it is concluded that the 26110 cm−1 band is in-plane polarized and has the character of the n,π* type transition.
The Quenching of the Cadmium Resonance Radiation at 326.1 nm by Some Aliphatic Amines and the Cadmium-sensitized Luminescence of These Amines
Authors: Yamamoto Shunzo , Sato Shin
Published: July 2006

From the pressure dependence of the intensity of the 326.1 nm resonance line, the efficiencies of the quenching of the resonance line by methylamine, ethylamine, n-propylamine, n-butylamine, sec-butylamine, tert-butylamine, diethylamine, and triethylamine were estimated to be 14.2, 36.0, 58.6, 71.2, 116.7, 434.5, 69.6, and 66.0 respectively, the efficiency of ammonia being assumed to be unity. The relative values of rate constants for the formation of excited complexes between the excited cadmium atoms and the amines, and the wavelengths at the peaks of the emission bands from the complexes, were measured. The quantum yields of luminescence were also measured by comparing the integrated intensities of the emission bands with the decrease in the intensities of the resonance line at 326.1 nm upon the addition of amines. From the relationship between these values and the structure of the amines, it is concluded that the complexes are of the charge-transfer type.
Resonance Raman Spectra of Methylorange Bound to Proteins and Cationic Surfactants
Authors: Kim Bak-Kwang , Kagayama Akira , Saito Yutaka , Machida Katsunosuke , Uno Toyozo
Published: July 2006

Resonance Raman spectra of methylorange were recorded for aqueous solutions containing various proteins and cationic surfactants. The base form of methylorange was found to retain its trans-azo structure on the interaction with human serum albumin and with cetyltrimethylammonium bromide. The relative intensities of the Raman bands at 1420 cm−1 and at 1155 cm−1 of methylorange change appreciably along with the shift of the absorption maximum in the visible and ultraviolet region on addition of proteins and surfactants.
Studies of Aqueous Sodium Dodecyl Sulfate Solutions by Activity Measurements
Authors: Sasaki Tsunetaka , Hattori Michihiro , Sasaki Jun , Nukina Kenji
Published: July 2006

The activities of surfactant ions (aD) and counterions (aNa) were directly obtained by the EMF measurement of a concentration cell with an ion-exchange membrane and by pNa measurements respectively for aqueous solutions of sodium dodecyl sulfate (NaDS) below and above the CMC. The mean activity and activity coefficient were also calculated. From these data, together with the surface tension (γ) measured by the Wilhelmy method and the amount of adsorption (Γ) measured by the radiotracer method, the following results were obtained: (1) Mean activity was not constant, but increased with the concentration above the CMC. (2) The Gibbs adsorption isotherm was directly verified from the aD and aNa  vs. concentration relations. (3) The decrease in γ observed above the CMC was in agreement with that calculated from the activity data. (4) The logaD  vs. logaNa plots above the CMC showed a linear relation, indicating the validity of the charged phase separation model as the mechanism of micelle formation. The degree of the counterion attachment of the micelles was found to be 0.73 up to about 80 mmol/l. (5) The intermicellar concentrations of Na+ and DS− ions were calculated; the former increases, while the latter decreases with the concentration. (6) The product of the concentration with an osmotic coefficient was linear with the concentration above the CMC, tangent of the slope being about 0.7.
The Specific Refractive Index Increment and the Partial Specific Volume of Atactic Poly (2-vinylpyridine)
Authors: Arichi Shizuo , Yoshida Masafumi , Ogawa Yoshihiro
Published: July 2006

The specific refractive index increment, dn⁄dc, of atactic poly(2-vinylpyridine) was measured in 18 solvents with 436 nm light at 25 °C. Using these data, the partial specific volume, \barν2, of the polymer in these solvents was then evaluated by means of the method proposed by Heller. A sufficient agreement was found between the values of \barν2 thus obtained optically and those determined directly by the density measurement of solutions in several solvents. It was found that \barν2 varies considerably with the kind of solvent and that, in some solvents, such as methanol and ethanol, it takes an extremely lower value than that of bulk crystalline isotactic poly(2-vinylpyridine). The results were discussed in terms of thermodynamic interactions between the polymer and the solvent, the molar volume, and the compressibility of the solvent molecule. The relationship between dn⁄dc and the refractive index of a solvent, n1 for 436 nm light is expressed by dn⁄dc=0.900× (1.628–n1).
Studies on Mass Spectrometry of Metal Chelates. IV. Synthesis and Mass Spectrometry of Cobalt(III) Mixed Ligand Chelates
Authors: Kidani Yoshinori , Naga Shinobu , Koike Hisashi
Published: July 2006

The ligand substitution reaction of Co(acac)3 proceeded with other ligands L (L=oxine, 2-Me-oxine, 4-Me-oxine, 5-Me-oxine, and 7-Me-oxine), to afford mixed ligand chelates, Co(acac)2(L) and Co(acac)(L)2. Their mass spectra gave the following fragmentation patterns. The Co(acac)2(L) type chelate gave a fragment ion Co(acac)(L), produced by the loss of one molecule of acac from the molecular ion. At the same time it produced another fragment ion, Co(acac)2, by the loss of L from the molecular ion. From this fragmentation pattern it was confirmed that the compound is a mixed ligand chelate having the binding ratio Co: acac: L=1: 2: 1. The Co(acac)(L)2 type chelate produced a fragment ion, Co(acac)(L), by the loss of one molecule of L from the molecular ion, and another fragment ion of Co(L)2 by the loss of acac from the molecular ion. From this fragmentation pattern it was confirmed that the compound is another mixed ligand chelate having the binding ratio Co: acac: L=1: 1: 2.
Electrical Properties of TeO2. I.
Authors: Doi Kazuo , Sasaki Tomoaki , Hijikata Kenzo
Published: July 2006

The electrical conductivity a of polycrystalline tellurium dioxide (paratellurite; purity: 6-nine) was measured as a function of the oxygen partial pressure (1–760 mmHg) at temperatures between 475 and 550°C. The relations between the experimental values of logσ and 1⁄T were well represented by straight lines, giving the apparent activation energy of about 1.36 eV. The oxygen-pressure dependence of the isothermal conductivity was well expressed by the σ∝Po21⁄6 relation; this may be interpreted by assuming that electron holes with fullyionized oxygen interstitials predominantly act as charge carriers. The p-type behavior in the conduction process was also confirmed by thermal emf measurements.
Studies on Electrode Processes of Oxovanadium(IV). I. Polarographic Behaviors and Photochemical Reaction in Potassium Oxalate Solution
Authors: Kitamura Mitsutaka , Imai Hideo
Published: July 2006

Oxovanadium(IV) was found to develop a fairly stable oxidation wave as well as a reduction wave at the dropping mercury electrode in an aqueous solution containing M potassium oxalate. The predominant entity in the solution was [VO(ox)2]2− , and both the oxidation wave with one-electron transfer, and the reduction wave with two-electron transfer were irreversible. The anodic transfer coefficient evaluated from the logarithmic plot and Tafel plot was 0.60–0.63, and the exchange current density estimated tentatively from the Tafel plot was 1.8×10−6 A/cm2. The effect of aerial oxidation of V(IV) to V(V) and the photochemical reduction of V(V) to V(IV) were investigated through the controlled potential electrolysis, absorption spectroscopy and ESR studies. The polarographic kinetic current of the oxidation process was observed under ultra-violet light irradiation. The apparent rate constant of the photochemical reduction evaluated from the kinetic current was (0.02–0.04)/εφI0s−1, where ε is the molecular extinction coefficient, φ the quantum yield and I0 the intensity of the incident light.
The Reactions of Tetrafluorobenzyne with Carboxylic Acids in Cyclic Ethers
Authors: Hayashi Sei-ichi , Ishikawa Nobuo
Published: July 2006

The reactions between tetrafluorobenzyne generated from tetrafluorobenzenediazonium-2-carboxylate and several carboxylic acids in cyclic ethers, such as THF and dioxane, were carried out. During these reactions, the cyclic ethers were cleaved and participated in the reactions to give acetate, benzoate, and salicylate esters of 4-(2′,3′,4′,5′-tetrafluorophenoxy)butanol and 2-[2′-(2″,3″,4″,5″-tetrafluorophenoxy)ethoxy]ethanol.
Reactivity of Electrogenerated Superoxide Ion. I. Autoxidation of 9,10-Dihydroanthracene
Authors: Tezuka Meguru , Ohkatsu Yasukazu , Osa Tetsuo
Published: July 2006

The superoxide ion, which was generated by means of electroreduction of the oxygen molecule dissolved in pyridine, abstracted the labile hydrogen from 9,10-dihydroanthracene and yielded anthraquinone and anthracene as the final products. From the products and their kinetics, the reaction was proposed to be a radical-chain autoxidation. Reactions with some other hydrocarbons were also carried out. The addition of ferrous or cobaltous phthalocyanine to the reaction system resulted in the increase of the reaction rate. A discussion of the effects led to the postulation of the intermediate formation of the superoxide ion-metal phthalocyanine complex.
Reduction of Nitro and Nitroso Compounds with Tetracarbonylhydridoferrate
Authors: Watanabe Yoshihisa , Mitsudo Take-aki , Yamashita Masakazu , Takegami Yoshinobu
Published: July 2006

An applicability of potassium tetracarbonylhydridoferrate as a reducing reagent to synthesis of primary amines from a wide variety of nitro and nitroso compounds has been examined. The reaction proceeds vigorously and exothermally at room temperature to give the corresponding amines in excellent yields. For nitroaryls, some substituents have interfering effect on the formation of amines. o-Nitrocinnamic aldehyde gives quinoline.
A Genferal Method for Evaluating the Resonance Energies of Monocyclic Conjugated Systems and Its Application to Heteroannulenes and Annulenones
Authors: Aihara Jun-ichi
Published: July 2006

The unit binding energy of a monocyclic conjugated system with an infinite number of the same unit structures can be employed as the reference energy in evaluating the resonance energy of a monocyclic conjugated system with a single unit structure. The latter system may be totally asymmetric in geometry. The resonance energy is then given as the difference between the π-energy of the system with the one-unit structure and the unit binding energy of the infinitely large system. This approach is justified by the proper prediction of the resonance energies for heteroannulenes and annulenones. The HMO theory was used in its simplest form.
Charge-Transfer Complexes of Thiopyrylium Cation with Aromatic Hydrocarbons and Olefins
Authors: Yoshida Zen-ichi , Sugimoto Toyonari , Yoneda Shigeo
Published: July 2006

Charge-transfer (CT) interaction of the thiopyrylium cation (1) with aromatic hydrocarbons and olefins has been investigated by electronic spectroscopy. It is noteworthy that 1 formed a CT complex with a monoolefin. The observed CT spectra in the 1–olefin system showed the following remarkable contrasts compared with those in the 1-aromatic system. 1) Although one CT absorption band was observed for the 1–aromatic hydrocarbon CT complex, while two CT absorption bands for the 1–olefin CT complex, and 2) the value of a in the equation of ΔECT=aIPD+b was 1.04 for the former complex and 0.27 for the latter complex. A detailed discussion on the difference between the two CT complexes is presented.
Synthetic Studies on Phosphorylating Reagent. I. The Phosphorylation of Alcohols by Means of N-[2-(Dihydrogen phosphoroxy)5-nitrobenzyl]pyridinium Hydroxide
Authors: Taguchi Yoshihiko , Mushika Yoshitaka , Yoneda Naoto
Published: July 2006

The phosphorylation of alcohols by means of N-[2-(dihydrogen phosphoroxy)-5-nitrobenzyl]pyridinium hydroxide (3), which was prepared from 2-(chloromethyl)-4-nitrophenyl phosphorodichloridate (1) through two steps, was demonstrated. Alcohol with a tertiary amino group in its alkyl moiety was readily phosphorylated with 3 to afford the aminoalkyl dihydrogen phosphate in good yield. On the other hand, the phosphorylation of the usual neutral alcohol proceeded only in the presence of a strong base such as triethylamine to give the corresponding alkyl dihydrogen phosphate (9). Thus, several alkyl dihydrogen phosphates 9 were prepared. In this phosphorylation, the formation of alkyl 2-hydroxy-5-nitrobenzyl ether (10) was also observed.
Inositol Derivatives. 9. Lithium Aluminum Hydride Reduction of Inositol Epoxides and Their Sulfonates
Authors: Suami Tetsuo , Ogawa Seiichiro , Funaki Yuji
Published: July 2006

The reduction of two dianhydroinositols: 1,2:3,4-dianhydro-5,6-O-cyclohexylidene-allo-inositol (1) and 1,2: 5,6-dianhydro-3,4-O-cyclohexylidene-allo-inositol (2), and four sulfonylated anhydroinositols: 1,2-anhydro-5,6-O-cyclohexylidene-3,4-di-O-mesyl-chiro-inositol (5b), 1,2-anhydro-5,6-O-cyclohexylidene-3,4-di-O-tosyl-chiro-inositol (5c), 1,2-anhydro-5,6-O-cyclohexylidene-4-O-tosyl-neo-inositol (6) and 2,3-anhydro-4,5-O-cyclohexylidene-1,6-di-O-mesyl-epi-inositol (8), with lithium aluminum hydride has been investigated.
N-Alkylideneanilines. IV. Kinetics and Mechanism for Site-Exchange of the Methyl Groups in N-Isopropylideneanilines
Authors: Iwamura Hiizu , Tsuchimoto Michiko , Nishimura Shigeo
Published: July 2006

The kinetics of the site-exchange of the methyl groups in twelve N-isopropylideneanilines have been studied by the coalescence point analysis of their proton NMR spectra. The free energies of activation at the coalescence temperature were found to be in the range 16.5 (at 53.5 °C for p-nitro) ∼22.4 (at 161 °C for p-amino derivative) kcal/mol. They give a Hammett σ−ρ plot with ρ=2.83 (r=0.976). The results are interpreted in terms of an in-plane inversion about the imine nitrogen for the site-exchange. Noticeable deviation of the points representing p-chloro and p-bromo compounds from the linearity indicates the destabilization of the transition state by the electron-releasing resonance effect of the substituents and is consistent with the inversion mechanism.
The Thermal Reaction of 3-Formylguaiazulene
Authors: Kurokawa Shinji , Safo Teruyo , Noguchi Toru , Yano Katsumi
Published: July 2006

When 3-formxlguaiazulene was heated at 200 °C for 1 hr, three new compounds were isolated in addition to S-guaiazulene (formed by loss of the formyl group). They were shown to be 2-formylguaiazulene, produced by migration of the formyl group, and dimers produced from two molecules of the starting material through dehydration between the formyl and the aromatic methyl groups. The observed elimination or migration of the formyl group was analogous to the behavior of 3-acylguaiazulenes which had been studied earlier. On the other hand, the extent of the loss of the acyl group and the formation of the dimers was peculiar to this substance. Moreover, migration of the formyl group was not reversible at 200 °C, but was at 250 °C.
The Segregation of Sodium Ions in KCl Minute Crystals
Authors: Sensui Yoshihiro , Tomura Kenji
Published: July 2006

The surface accumulation of solute sodium ions in KCl crystallites was measured as a function of the annealing temperature, 250–450 °C. The minute crystals were baked out under 3×10−7 Torr, and their surface layers were dissolved successively with anhydrous ethyl alcohol. The contents of sodium and potassium were determined by instrumental neutron-activation analysis with the aid of a 50 cc-Ge(Li)-4K gamma spectrometer.
Infrared Spectra and Structures of Copper(II) and Zinc(II) Complexes of Glycylglycine in Aqueous Solution
Authors: Tasumi Mitsuo , Takahashi Seizo , Nakata Toshio , Miyazawa Tatsuo
Published: July 2006

The infrared spectra of the Cu(II) and Zn(II) complexes of glycylglycine were observed in D2O at various pD values. Large spectral changes in going from acidic to neutral solution were interpreted in terms of the equilibria among free and complexed forms of glycylglycine. In the Cu(II) complex formed for 3<pD<5 the metal-ligand bonding occurs through the amino nitrogen and peptide oxygen. As pD is increased further, the structure of the Cu(II) complex changes into a form in which the metal-ligand bonding occurs through the amino nitrogen, peptide nitrogen (deprotonated), and carboxyl oxygen. In contrast to the Cu(II) complex, no change of structure is found for the Zn(II) complex. The Zn(II) complex formed for pD>5 is similar to the Cu(II) complex present for 3<pD<5.
Crystal and Molecular Structure of (π-C5H5)Fe3(CO)7C2C6H5 Obtained from (π-C5H5)Fe(CO)2C≡CC6H5 with Fe2(CO)9
Authors: Yasufuku Katsutoshi , Aoki Katsuyuki , Yamazaki Hiroshi
Published: July 2006

The crystal structure of π-C5H5Fe3(CO)2(C2C6H5) obtained from the reaction of π-C5H5Fe(CO)2C2C6H5 with Fe2(CO)9 has been determined from single crystal X-ray diffraction data. The space group is P\bar1 and the cell constants are a=12.635, b=9.457, c=9.033 Å, α=94.64, β=109.10, and γ=99.60°, and Z=2. The refinement was carried out using block-diagonal least-squares calculation including anisotropic thermal factors for the nonhydrogen atoms and isotropic thermal factors for the hydrogens. The final R value for 2488 reflections is 0.035. The molecular configuration consists of an isosceles triangle of the three iron atoms, each two of which bonds to three terminal carbonyl groups and one bonds to the cyclopentadienyl ring. The phenylethynyl group is disposed above the iron plane and is σ-bonded to one iron atom with three carbonyls and α-bonded symmetrically to the other two iron atoms. The seventh carbonyl group is bridged asymmetrically between these two iron atoms, below the iron plane. The characteristic shortening in the Fe–C σ-bond and in the acetylenic C–C bond was observed.
Preparation of Reinforcing Fillers from Japanese Acid Clays with Lime and by Calcination. III. Elucidation of the Reinforcing Effects Based on the Investigation of Changes in the Structure, Physicochemical Properties and Morphology of N Hard Clay
Authors: Rai Hideki , Yamada Junkichi
Published: July 2006

In order to elucidate the reinforcing effects of the fillers prepared from Japanese acid clay with hydrated lime and by calcination and mechanical disintegration, N hard clay (CaO 3–60%; calcination 400–800 °C, 1–1.5 hr; wet ball-milling 18 hr) derived from Nakajo acid clay (N) were investigated on the structure, physicochemical properties and morphology in comparison with those of N, Dixie Clay and Silene EF. X-Ray diffraction, infrared spectroscopy and electron micrography were applied to the examination of the structural and morphological features. The physicochemical properties were determined on the surface properties such as hygroscopicity, pH and DPG adsorption together with the specific gravity and bulk density. The following results were obtained: (1) Treatment under the optimum conditions (CaO 6%, calcination 600 °C, 1.5 hr; wet milling 18 hr) caused a favorable change in the structure of the prepared filler, resulting in controlling the surface properties, reduction in the particle size and its distribution, a decrease in the specific gravity and an increase in the bulk density. (2) Deviation from the conditions, e.g., calcination at 400 °C for 1.5 hr remained too much residual adsorptivity to improve the great surface activity of N, whereas treatment at 800 °C for 1–1.5 hr afforded sintering, collapse and/or fusion yielding too hard aggregates to be disintegrated as well as a serious breakdown or complete loss in the effective functional groups involved.
The Radiation-induced Dehalogenation of Dichloromethane and Dibromomethane in Methanol Solutions
Authors: Ogura Hajime , Fujimura Takashi , Unnai Takaaki , Kondo Masaharu
Published: July 2006

The scheme of the radiation-induced dehalogenation of dichloromethane and dibromomethane was investigated in deaerated methanol. The relative rate constants of those solutes toward esol− were determined by competition kinetics, using a N2O scavenger.
ENDOR Studies on the Hindered Alkylbiphenyl Anion Radicals
Authors: Ishizu Kazuhiko , Nemoto Fujito , Mukai Kazuo , Kohno Masahiro , Hasegawa Hideo
Published: July 2006

ENDOR observations were carried out for the anion radicals of 2,2′-bitolyl, 2,2′-diethylbiphenyl, and 2,2′-diisopropylbiphenyl. The spin densities obtained from the ring protons at the ortho-positions showed a depression in the order of the spherical bulkiness of the substituents, and the degrees of the steric hindrance of the biphenyl ring were estimated based on McLachlan’s MO calculation. ENDOR experiments demonstrated that methyl groups undergo free rotation, but it is greatly hindered in each higher alkyl derivative.
A Gel-state Liquid-membrane Iodide-ion Electrode
Authors: Shijo Yoshio
Published: July 2006

A new liquid-membrane iodide-ion electrode has been developed. The liquid membrane of the electrode consists of poly vinyl chloride gel containing a nitrobenzene solution of tridodecylethylammonium iodide as an ion exchanger, a lead wire is inserted directly into the gel. The properties of the electrode, such as the response time, the effect of the temperature, the reproducibility of the preparation, and the selectivity, have been determined.
The Magnetic Susceptibility of Two Coupled Dimers Consisting of S=1/2 Spins
Authors: Emori Shuji , Tokii Tadashi , Muto Yoneichiro
Published: July 2006

Tetramers consisting of two coupled dimers were classified as (a) linear, (b) cyclic, (c) rhombic, or (d) tetrahedral. The magnetic susceptibility for each tetramer model consisting of S=1/2 spins was obtained as an analytical equation. For the linear tetramer, the susceptibility equation was calculated numerically and compared with the observed values.
Circular Dichroism Spectra of (Aminocarboxylato)ammine[1,1,1-tris(aminomethyl)ethane]cobalt(III) (2+) Complexes
Authors: Yamanari Kazuaki , Hidaka Jinsai , Shimura Yoichi
Published: July 2006

Five triple mixed Co(III) complexes with one 1,1,1-tris(aminomethyl)ethane and one aminocarboxylato and one ammine ligand were prepared. The glycinato complex was optically resolved and three l-aminocarboxylato complexes were chromatographically separated into their diastereomers. The circular dichroism spectra of the complexes were discussed.
Catalytic Activities of Pyridoxal Analogues. I. The Catalytic Effects of Pyridoxal, Pyridoxal Methochloride, and Pyridoxal N-Oxide on the Racemization of l-Glutamic Acid
Authors: Ando Makoto , Emoto Sakae
Published: July 2006

An improved method for the syntheses of pyridoxal methochloride (1) and pyridoxal N-oxide (5) was investigated. Further, the catalytic activities of pyridoxal, 1, and 5 on the racemization of l-glutamic acid in the presence of cupric ions were studied.
Pyrolysis of 1,2-EpithiocycIohexane
Authors: Inoue Shodo , Oae Shigeru
Published: July 2006

Dicyclohexyl sulfide, cyclohexyl phenyl sulfide, dicyclohexyl disulfide, 2,3,5,6-bis(tetramethylene)-1,4-dithiane, cyclohexanethiol and cyclohexyl cyclohexenyl sulfide were obtained by the pyrolysis of 1,2-epithiocyclohexane apparently via the attack of sulfur radical species, formed by the pyrolysis of 1,2-epithiocyclohexane, on the double bond of cyclohexene.
A New Synthesis of 2-Pyrones
Authors: Izumi Taeko , Kasahara Akira
Published: July 2006

The reaction of sodium salt of penta-2,4-dienoic acids with lithium chloropalladite in a polar solvent such as water led to the formation of 2-pyrone derivatives.
The Photocycloaddition of 2-Cyclohexenone and Maleic Anhydride to Δ9,10-Octalin
Authors: Kunai Atsutaka , Kimura Koji , Odaira Yoshinobu
Published: July 2006

The photocycloaddition to Δ9,10-octalin (1) was investigated. Both 2-cyclohexenone and maleic anhydride reacted with 1 to afford the corresponding photocycloadducts, 2 and 3 respectively.
Base-catalyzed Oxygenation of 2,6-Di-t-butylphenols. A Convenient Method for Preparation of p-Quinols
Authors: Nishinaga Akira , Itahara Toshio , Matsuura Teruo
Published: July 2006

The oxygenation of 4-alkyl-2,6-di-t-butylphenols in diethylamine containing sodium, amide under mild conditions afforded the corresponding p-quinols in excellent yields.
Kinetic Studies of the Aggregation of Acridine Orange onto Poly-(α,l-glutamic acid)
Authors: Tsuda Motoyuki
Published: July 2006

The aggregation process of acridine orange (AO) onto the helical poly-α,l-glutamic acid (PLGA) was studied by means of a stopped-flow and rapid-scan spectrophotometer. After the flow stop, a rapid spectral change was observed in which the α-band and the β-band fell, and the γ-band and the polymer band rose. A mechanism of the process was proposed by which after a rapid nucleative process, AO molecules are cooperatively bound to form a dimer and that then the dimer grows to the oligomer and to the polymer of AO which has the form of a super-helix around the core of the α-helix of PLGA.
Solubility of Transition Metal Complexes in Aqueous Salt Solutions. I. Tris(1,10-phenanthroline)iron(II) Perchlorate
Authors: Miyoshi Katsuhiko , Taura Toshiaki , Shimada Chiyori , Yoneda Hayami
Published: July 2006

Solubility of tris(1,10-phenanthroline)iron(II) perchlorate was determined at 25°C by spectrophotometry in aqueous solutions of sodium halides, sulfate, acetate, and trichloroacetate up to ionic strength of 0.5. It was found that the solubility is higher in the presence of water-structure breaking anions but is lower in the presence of water-structure making anions than is expected from the change in activity coefficients with ionic strength. This was interpreted in terms of compatibility and incompatibility of the influence of the complex cation on the water structure with that of added anions, and the hydrophobic nature of the complex cation was noted.
The Solvent Extraction-Polarographic Determination of Cadmium(II) as the Tris(2,2′ -bipyridine)iron(II) Tetraiodocadmate(II) Complex
Authors: Hasebe Kiyoshi , Ohtsuki Tsukasa , Kambara Tomihito
Published: July 2006

A new method for the solvent extraction-polarographic determination of cadmium has been proposed. The quaternary complex formed by the tris(2,2′-bipyridine)iron(II) cation and the tetraiodocadmate(II) anion can be readily extracted into benzyl alcohol. The extracted complex shows a well-defined reduction wave in the ternary electrolyte-solvent mixture, composed of benzyl alcohol, an aqueous electrolyte solution, and methyl cellosolve. The available range of the present method covers from 5.7×10−6 to 91.4×10−6 M of cadmium(II) in the aqueous phase. The optimum pH range for extraction is 3–9, and the extracted species is stable in the ternary solvent mixture for 5hr. Zinc (II), bromide, and chloride ions do not interfere, but copper (II), mercury (II), and iron(III) do interfere.
Phase Equilibria in the Fe–Fe2O3–Eu2O3 System at 1200 °C
Authors: Sugihara Tadashi , Kimizuka Noboru , Katsura Takashi
Published: July 2006

The standard Gibbs energies of the reaction of EuFeO3 and Fu3Fe5O12 were determined to be −63300±200 cal and −297800±600 cal respectively at 1200°C by means of following reactions: Fe+1/2 Eu2O3+3/4 O2=EuFeO3 and 5 Fe+3/2 Eu2O3+15/4 O2=Eu3Fe5O12, based on the phase equilibria in the Fe–Fe2O3–Eu2O3 system.
The 13C Magnetic Resonance Study on the Effects of Divalent Paramagnetic Metal Acetylacetonates on Pyridine, Quinoline, and Isoquinoline. Specific Interactions with Mn(AA)2
Authors: Hayamizu Kikuko , Murata Makoto , Yamamoto Osamu
Published: July 2006

13C nuclear magnetic resonance studies of pyridine solutions containing paramagnetic Ni (II), Co(II), Cu(II), or Mn(II) acetylacetonate are made by observing the induced chemical shift, the line width, and the spin-lattice relaxation time due to the paramagnetism of these metals. The origin of the paramagnetic effects on the 13C spectra induced by Ni, Co, or Cu acetylacetonate is mainly the contact interaction, while the 13C spectra of the pyridine–Mn(AA)2 system can not be interpreted by the same interaction. The 13C spectra of quinoline and isoquinoline containing Mn(AA)2 are also studied; the results indicate that the predominant mechanism is the dipole-dipole interaction.
Thermal Bleaching of the Colored Form in the Photochromism of 2-Hydroxy-2′,4,4′-trimethoxytriphenylmethanol in Acetonitrile
Authors: Hamai Sanyo , Kokubun Hiroshi
Published: July 2006

The photochromism of 2-hydroxy-2′,4,4′-trimethoxytriphenylmethanol (HTMM) in acetonitrile differs from that of other 2-hydroxytriphenylmethanol derivatives in some aspects. The colored form, 2′,4,4′-trimethoxy-o-fuchsone (TMF), of HTMM partly converts to 2-hydroxy-2′,4,4′-trimethoxytriphenylmethyl cation (Cat) at an early stage of the bleaching reaction. At a later stage a slow bleaching of TMF to HTMM becomes the main decay process. Bleaching of the produced Cat is so slow that Cat remains even after complete disappearance of TMF. The formation of Cat was concluded to be a reaction between adsorbed TMF and water on the cell surface. The rate determining step is not a diffusion process since the activation energy found is much larger than that of viscosity. Cat decays by the reaction with water, not with hydroxide ion.
The Birch Reduction of Heterocyclic Carboxylic Acids. I. The Birch Reduction of 3-Furoic Acid
Authors: Kinoshita Takamasa , Miyano Kouichi , Miwa Toshio
Published: July 2006

The reduction of 3-furoic acid with sodium and 2-propanol in liquid ammonia gave 2,3-dihydro-3-furoic acid, which was isolated as a methyl ester (1) in 85% yield. The acid-catalyzed addition of methanol, ethanol, or 2-propanol to the ester 1 yielded 5-alkoxytetrahydro-3-furoate ester, 2, 3, or 4, respectively, in a quantitative yield. When methanol or ethanol was used as a proton source in the reduction, work-up of the reaction mixture gave 5-alkoxytetrahydro-3-furoic acid, which was isolated as the methyl ester, 2 or 3, in 87 or 92% yield, respectively. A mechanism for the Birch reduction of aromatic carboxylic acids is proposed.
Absolute Configurations and Chiroptical Properties of Optically Active Derivatives of Tricyclo[4.3.0.03,8]nonane (“Twist-brendane”)
Authors: Nakazaki Masao , Naemura Koichiro , Harita Sigeyuki
Published: July 2006

(+)-Tricyclo[4.3.0.03,8]nonane (“twist-brendane”) was synthesized via (+)-tricyclo[4.3.0.03,8]nonan-9-one from (+)-endo-2-carboxybicyclo[2.2.2]oct-5-ene. Optically active derivatives of twist-brendane with two functional groups such as (−)-2,9-twist-brendanedione and (−)-9-methylenetwist-brendan-2-one were synthesized from (−)-endo-2-carboxybicyclo[2.2.2]oct-5-ene. Absolute configurations of the compounds were established and their chiroptical properties were discussed.
Coenzyme Models. III. Enhanced Charge Transfer Interaction between the Oxidized and Reduced Forms of Nicotinamide in Micellar and Polymeric Systems. NAD Coenzyme Model
Authors: Shinkai Seiji , Tamaki Kiyoshi , Kunitake Toyoki
Published: July 2006

The micelle of 1-lauryl-3-carbamoylpyridinium bromide(NLaN) and poly-1-(p-vinylbenzyl)-3-carbamoylpyridinium chloride (PVCG) were shown to form charge transfer complexes with dihydronicotinamides and several aromatic compounds in aqueous media. A broad charge transfer absorption at longer wavelengths was easily detected, and the association constant of 1 : 1 complexes which was estimated from the CT band was enhanced by 6.2–220 times in the NLaN micelle and by 14–66 times in the polymeric system, compared with non-micellar, monomeric system. The enhancement of the interaction between NLaN and its reduced from (NLaNH) was similar in the CTAB micelle and in a nonionic micelle. The increased electron-acceptabilities of the pyridinium group in micellar and polymeric systems were discussed in reference to NAD coenzyme.
Changes in the Catalytic Activity of Cold-worked Platinum during the Oxidation of Carbon Monoxide
Authors: Kishimoto Shozo
Published: July 2006

The rate of the oxidation of carbon monoxide was measured on cold-worked platinum to study the influence of annealing on the catalytic behavior. It was found that the presence of lattice defects (dislocations) in the crystal plays a role in initiating the reaction and serves to create new active sites during an acceleration period of the reaction.