bluuebunny/crossref_metadata_2025 huggingface dataset:
Oxidation of Carbon Monoxide over Transition Metal Ion-Zeolite Catalysts
Authors: Kubo Toshihiko , Tominaga Hiroo , Kunugi Taiseki
Published: July 2006

Adsorption of oxygen and oxidation of carbon monoxide was investigated on several X and Y type zeolites, their Na+ being replaced by transition metal ions. Oxygen adsorption was observed on Cr(II), Cu(I), and Fe(II) ions whose oxidation potentials are high, giving an oxygen atom to metal ion ratio of 0.43–0.62 or nearly 0.5. A small amount of oxygen was adsorbed on Tl(I), Co(II), and Mn(II), as expected from their standard oxidation potentials. No oxygen was adsorbed on Cu(II) and Ni(II), their valences being difficult to increase. The activities of these transition metal ions for oxidation of carbon monoxide increased exponentially with the increase of their standard oxidation potential. Kinetic studies on CO oxidation over Fe(II)–X and –Y zeolites have been made, and a Rideal mechanism is suggested where CO molecules in the gas phase attack the oxygen atoms dissociatively adsorbed in the bridged form of Fe3+–O2–Fe3+. The difference in the activities of Fe(II)–X and –Y catalysts is discussed.
Studies on Fragment Ion Distribution and Reaction with a Charge Spectrometer. V. Applicability of the MO Theory to the Fragmentation of Alkanes by Charge Exchange
Authors: Ikuta Shigeru , Yoshihara Kenji , Shiokawa Takanobu
Published: July 2006

The relation between the fragment ion distribution and recombination energy of the incident positive ions was studied by means of charge exchange reactions. The energy range which is consistent with the molecular orbital (MO) theory proposed by Hirota to account for the mass spectra by electron impact was also investigated, and the usefulness of the theory was discussed. The energy range to which the MO theory is applicable is very limited, the fragment ions produced at the high recombination energy to which it is apparently applicable, being the C2, C3 and C1 ion groups. It is probable that these species are not produced directly from the parent but by degradation mechanisms via intermediate steps, thus causing disagreement with the MO theory. Its applicability to alkanes is open to question. The dissociation schemes on n-alkanes are presented from the expreimental results.
Transport Properties of Multi-component Polar Gas Mixtures Containing Mono-, Di-, and Trimethylamines
Authors: Naser P
Published: July 2006

The viscosity and thermal conductivity coefficients of monomethylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA), and their binary mixtures have been measured in the temperature range 25–250 °C. In addition, determinations of thermal conductivity of ternary mixtures at 33 and 88 °C and of several quaternary mixtures (with ammonia) at 33 °C have been made. The results are discussed in the light of modern kinetic theory of gases. Finally, the coefficients of self-diffusion and mutual diffusion in binary mixtures of these gases are estimated from the experimental viscosity results.
An Optical Absorption Study of the Reaction of Bis(O,O′-diethyldithiophosphato)oxovanadium(IV) with Pyridine
Authors: Sato Mitsuo , Kwan Takao
Published: July 2006

The interaction of bis(O,O′-diethyldithiophosphato)oxovanadium(IV), VOdtp2, with pyridine has been studied in toluene by means of the optical absorptions. It has been found that the visible absorption band characteristic of VOdtp2 was shifted toward longer wavelengths upon the formation of the complex species identified as VOdtp2·Py and VOdtp2·Py2. The equilibrium constants and enthalpy and entropy changes for the formation of VOdtp2·Py were determined from the spectral characteristics, measured as a function of the solvent composition and the temperature. The results obtained were then discussed in comparison with those for the base addition of other oxovanadium complexes.
Spectrophotometric Study on the Extraction of Magnesium(II)–8-Hydroxyquinoline-5-sulfonic Acid Chelate Anion with Zephiramine
Authors: Sugawara Masao , Kambara Tomihito
Published: July 2006

The ion-pair of magnesium(II)–8-hydroxyquinoline-5-sulfonic acid chelate anion with zephiramine (Z+Cl−) was extracted into chloroform. The ternary complex has an absorption maximum at 390 nm in the organic layer. The optimum pH range for the extraction is 10.1–11.4. For the first extract, Beer’s law holds for 4.6–20.6 μg of magnesium(II) in 10-ml organic layer, the molar absorptivity being 6.73×103 cm−1 mol−11. The composition of the ternary complex is estimated to be [Mg2+(QS2−Z+)2(HQS−Z+)]o. The extraction equilibrium is given by

Mg^2++3[(HQS^-Z^+)]_o+2OH^-\ightleftharpoons[Mg^2+(QS^2-Z^+)_2(HQS^-Z^+)]_o+2H_2O

where QS denotes 8-hydroxyquinoline-5-sulfonic acid and o the organic phase. The equilibrium constant K is given by logK=16.95±0.13.
Studies of Nitrogen-Phosphorus Compounds. XXV. The Synthesis of Guanidium Condensed Phosphates
Authors: Kobayashi Etsuro
Published: July 2006

In order to develop fireproof materials, an attempt was made to prepare guanidium condensed phosphates ((H5CN3)n·Hn+2PnO3n+1, n=1–10) by means of a reaction between dicyandiamide (H4C2N4) and ammonium dihydrogen phosphate (NH4H2PO4) in an autoclave; then the conditions of the synthesis were investigated, and the components of the product were also identified. In the synthesis of gaunidium salt by means of a reaction between dicyandiamide and ammonium salt, generally only ammonium salts of strong acid have been used; also, high yields of guanidium salt could not be obtained with the (NH4)2H2PO4 used previously. In the present study, a mixture of 1 mol of H4C2N4 and 2 mol of NH4H2PO4 was heated in an autoclave at 130–300°C; 70–80% of the dicyandiamide was then converted into guanidium salt under the most suitable conditions. The majority of the product is soluble in water (the insoluble part is less than 3.5% at 150–220°C), and the solution is almost neutral. The components of the soluble part were 25–26% N and 20–24% P, the mole ratio of N to P being 2.8–2.5; this ratio decreased with an increase in the reaction temperature. On the other hand, the phosphates in the product consist of ortho-, pyro-, tri-, and middlepoly phosphates (n=4–10). The guanidium condensed phosphates thus obtained can be utilized as useful flame retarders for paper and wood, as guanidium orthophosphate can be.
Polarographic Studies of the Anodic Oxidation of Mercury. III. The Adsorption of the Mercury(II) Complexes of Ammonia and Alkylamines on the Mercury Electrode Surface
Authors: Matsui Yoshihisa , Takaya Hitoshi , Date Yoshio
Published: July 2006

A solution of ammonia, methylamine, n-propylamine, isopropylamine, or n-butylamine in N,N′-dimethyl-formamide gives an anodic prewave due to the adsorption of the oxidation product, Hg(amine)22+, on the dropping mercury electrode. The shape of the prewave of each amine can be well interpreted by an equation derived on the basis of the assumptions that the adsorption follows the Langmuir isotherm and that the adsorption coefficient of the adsorbate complex decreases exponentially as the electrode potential becomes more positive. Some physicochemical properties of the mercury(II) complexes, such as the overall stability constants and the adsorption coefficients at 0.0 V vs. SCE, were determined by analyses of the polarographic waves.
Kinetic Studies of the Nickel Maleate Complex Formation in Solution by the Pressure-jump Method
Authors: Harada Shoji , Yasunaga Tatsuya
Published: July 2006

Nickel maleate complex formation reaction in an aqueous solution, Ni2++Mal2−\oversetkf\undersetkd\ightleftharpoons NiMal, where Mal2− represents the maleate ion, was studied by the pressure-jump method. The rate constants and the stability constant were obtained; kf=8.4×105 M−1s−1, kd=2.1×103 s1, and K=4×102M−1 at 25°C and at μ→0. The thermodynamic parameters of this reaction were obtained from studies at various temperatures between 10 and 30°C. The results indicate that the nickel maleate is stable as a monodentated complex rather than as a chelate complex. Moreover, the nickel dicarboxylate complex formation reactions and the rate equations were discussed.
Aldol Condensations of Aldehydes over Disodium Phthalocyanine
Authors: Inoue Hiroo , Kunikawa Kenzo , Imoto Eiji
Published: July 2006

Disodium phthalocyanine (Pc–Na2) acts as a base for the aldol condensations of aldehydes, although it shows no effect upon those of ketones. In the aldol condensation of isobutyl aldehyde by Pc–Na2 in n-hexane, 2,6-diisopropyl-5,5-dimethyl-1,3-dioxane-4-ol (III) is produced through two processes with different rates; the reaction proceeds first by the slower rate, and then by a more rapid rate after a certain reaction period. The process is different from that of the catalysis by sodium ethoxide. During the reaction, Pc–Na2 is converted to sodium-free phthalocyanine (Pc–H2) via an intermediate. The formation of the intermediate results in the retardation of the aldol condensation with the product and phthalocyanine anions. Furthermore, the adsorption of water on Pc-Na2 brings about the retardation of the reaction.
Reaction of O,O-Dialkyl Dithiophosphoric Acid. III. Reductive Cleavage Reactions of Nitrogen-Nitrogen Bond by O,O-Diethyl Dithiophosphoric Acid
Authors: Oae Shigeru , Tsujimoto Nobuko , Nakanishi Akira
Published: July 2006

o-Nitroaniline was obtained when tri(o-nitrophenyl) triaziridine(I) was allowed to react with excess O,O-diethyl dithiophosphoric acid. It was found that azobenzene derivatives(IIa-e) are converted into the corresponding reduction products aniline derivatives (IVa-e) in the reaction with excess O,O-diethyl dithiophosphoric acid. Similarly, arylhydrazines (IIIa-c) were converted into the corresponding aniline derivatives (IVa,d,e) by the action of O,O-diethyl dithiophosphoric acid.
Synthetic Studies by the Use of Carbonates. III. The Condensation Reactions of Ethylene Carbonate with a Variety of Phenols Catalyzed by Lithium Hydride or Tetraethylammonium Halides
Authors: Yoshino Teruo , Inaba Shigeru , Ishido Yoshiharu
Published: July 2006

The condensation reactions of ethylene carbonate with a variety of phenols in the presence of tetraethylammonium halides were examined; they were found to give the corresponding aryl β-hydroxyethyl ethers in good yields. The reactions in the presence of lithium hydride in place of the tetraethylammonium halides were also examined for the sake of comparison, and these results were discussed.
The Carbon-13 Chemical Shift of n-Butane
Authors: Ando Isao , Nishioka Atsuo
Published: July 2006

The temperature dependence of the carbon-13 chemical shift of n-butane was calculated using the CNDO/2 method, taking into account the rotational isomers and assuming the Boltzmann distribution among them. The observed results could be well interpreted by assuming ca. 11.15 eV as the average excitation energy.
Photochemistry of Acridines. XIX. Photoreduction of Acridine in Mixed Solvents
Authors: Hoshino Mikio , Koizumi Masao
Published: July 2006

The photoreduction of acridine has been investigated in three kinds of mixed solvents, benzene-isopropanol, benzene-methanol and benzene-cyclohexane, all in aerated and deaerated conditions. The following general tendensies have been found for the plot Φrel  vs. mole fraction. It is approximately linear or slightly concave upward for molecular mechanism, while convex upward for radical mechanism. This indicates that for molecular mechanism a cage model trapping two radicals (e.g. C-radical and alcohol radical) is unsuitable while one act process involving two reactive sites is suitable.
Photochromism of Thallium Chloride
Authors: Sakka Sumio , Mackenzie J D
Published: July 2006

The ultraviolet-induced darkening and subsequent bleaching of crystalline thallium chloride was investigated in order to study the processes occurring in a photochromic glass containing TlCl crystalline particles. Doping with a small amount of copper, silver or indium ion was found to be effective in promoting darkenability of TlCl crystals. Exposure to visible light causes bleaching of UV-induced coloring of TlCl crystals. Almost no fading occurs, however, when TlCl crystalline pieces are kept in darkness at room temperature or higher temperatures up to about 70°C, where very quick fading in color is observed in the case of TlCl crystals embedded in a glassy matrix.
Temperature Effect on Raman Intensity of Liquid Sample and Local Field Correction
Authors: Fujiyama Tsunetake
Published: July 2006

The relative intensities of the 996 cm−1 line of liquid benzene and the 367 cm−1 line of liquid chloroform were observed at various temperatures with a high accuracy. The apparent intensity change due to the temperature was explained completely in terms of the local field effect, the density change, and the statistical distribution. The validity of Eckardt’s correction factor was strongly supported. In the case of liquid chloroform, an intensity change due to intermolecular interaction was observed after the elimination of the above three factors. The reliability of the relative intensity measurements of Raman lines was discussed.
Synthetic Photochemistry. I. The Cycloaddition Reaction of Methyl Acetopyruvate with Olefins
Authors: Takeshita Hitoshi , Tanno Shimaho
Published: July 2006

The photochemical cycloaddition reaction of methyl acetopyruvate, an unsymmetrical β-diketone, with olefins afforded the single 1 : 1 molar adducts in good yields. A ready method of the cyclization of the adducts to the β-methoxycarbonyl-Δα,β-cyclohexenones has preparative values.
Cyclization Reactions of 1,2-Bis(2-cyanophenyl)propionitriles. I. Structure of the “Red Pigment” formed by the Base-catalyzed Cyclization of 1,2-Bis(2-cyano-3-methoxyphenyl)propionitrile in the Presence of Diethyl Carbonate
Authors: Ando Kazuo , Tokoro Yama Takashi , Kubota Takashi
Published: July 2006

The reaction of 1,2-bis(2-cyano-3-methoxyphenyl)propionitrile (1) with diethyl carbonate and sodium ethoxide gave a red pigment 2, C22H19N3O4 in 79% yield. It afforded 5-amino-4,7-dimethoxy-11H-indeno[1,2-c]isoquinolin-11-one (4) on treatment with alkaline hydrogen peroxide. The “red pigment” has been confirmed to have a novel 5H-indeno[1,2-c]isoquinoline structure which transforms into colorless 11H-indeno-[1,2-c]isoquinoline form in an acidic medium. The mechanism of the formation of 2 from 1 imparts an interesting problem as regards carbanion reactivity.
Aromatic Substitution of Olefins. XXI. Reaction of o-Alkylstyrenes with Benzene in the Presence of Palladium(II) Acetate
Authors: Watanabe Morio , Yamamura Masaaki , Moritani Ichiro , Fujiwara Yuzo , Sonoda Akio
Published: July 2006

In aromatic substitution of olefins, steric factor of o-alkyl substituents of styrene was investigated. The formation of arylated products was found to be decreased by introduction of alkyl groups to ortho position of styrene.
Substituent Effects in the Benzofuran System. III. Cationic Polymerization
Authors: Okuyama Tadashi , Kunugiza Kiyomitsu , Fueno Takayuki
Published: July 2006

Cationic copolymerizations of various pairs of benzofuran derivatives have been carried out in CH2Cl2 using SnCl4–CCl3CO2H (2: 1) as catalyst at 0 °C. Effects of 2- and 3-methyl substitutions on the monomer reactivity ratio suggested that the polymeric cation adds at the 2-carbon of benzofuran. Analysis of the effects of 5- and 6-substituents on the reactivity revealed that the transmission efficiency of electronic effects through the two paths, the bonds 8–3 and 9–1–2, is comparable in magnitude. It was concluded that the transition state of the propagation step closely resembles a bridged carbonium ion intermediate.
Chemical Behavior of Intermediates Produced in Sulfuric Acid Glass by Gamma Irradiation. II. Yield of Trapped Hydrogen Atoms in the System Containing Metallic Ions
Authors: Sasaki Teikichi
Published: July 2006

The yield of trapped hydrogen atoms, Ht, in gamma-irradiated sulfuric acid glass is remarkably increased by adding a small amount, 10−2 M, of metallic ions. The increase is followed with a slow decrease at the higher solute concentrations. The efficiency of the formation depends on the kind of cationic solute. The largest G(Ht) is observed in a system containing Co2+ ions; it amounts to 8.7. These findings can be explained by a mechanism in which not only mobile electrons produced by the initial ionic processes, but also excited states of the matrix molecule, contribute to the Ht formation. The excitation energy is transferred from the matrix molecule to the solute, which consequently undergoes ionization; the resulting electron causes the Ht formation. This mechanism seems to be supported by the observation that the yield of Ht increases with a decrease in the charge-transfer energy of the solute in the rigid matrix.
Solvent Effects on the Formation of Aromatic Hydrocarbon Ions and Mo5+ on the Surface of Al2O3–MoO3
Authors: Ueda Hisashi
Published: July 2006

The formation of two aromatic hydrocarbon ions on the surface of Al2O3–MoO3 has already been postulated. The concentrations of these paramagnetic species were measured for various solvents by using DPPH single crystals as the reference standard. The formation of two different aromatic ions on the surface of Al2O3–MoO3 could also be confirmed by the solvent dependence. The intensity of microwave magnetic field H1 and the modulation width were considered in this measurement. Without solvent molecules such as benzene on the oxide surface, an ESR signal without cation hyperfine structure was almost exclusively observed. The intensities and intensity ratio between the two components of the ESR absorption at g=2.00, with and without hyperfine structure, change with solvent. The results indicated that solvent molecules, when adsorbed on the oxide surface, form a surface structure or a surface system which makes the charge transfer from the oxide surface to the solute hydrocarbon easier.
The Crystal Structure of Pyrazinic Acid
Authors: Takusagawa Fusao , Higuchi Taiichi , Shimada Akira , Tamura Chihiro , Sasada Yoshio
Published: July 2006

The crystal structure of pyrazinic acid has been determined by X-ray diffraction method. The crystal is orthorhombic, space group Pna21, a=11.352, b=7.363, c=6.454Å, and Z=4. The structure was solved by inspecting the sharpened Patterson map. The final R value is 6.4% for all observed reflections. The molecule does not take a zwitter ion, but a neutral form. The dimensions of the pyrazine ring are close to those of pyrazine. Each molecule is joined, through the O–H···N hydrogen bond with distance of 2.669 Å, to two neighboring molecules forming the chain. These chains are linked by the weak C–H···O hydrogen bond to form the sheet parallel to the (0 0 1) plane. This hydrogen bonding scheme is quite similar to that of nicotinic acid. The hydrogen bonding type found in nicotinic acid is considered energetically favored more than that found in picolinic acid.
The Chlorobromination of Olefins with Antimony (III and V) Chlorides
Authors: Uemura Sakae , Onoe Akira , Okano Masaya
Published: July 2006

By the reaction of olefins with equimolar mixtures of SbCl5 and Br2 or LiBr, and of SbCl3 and Br2, in carbon tetrachloride, various bromochloroalkanes were obtained in good yields. The mixtures of certain metal chlorides of the Lewis acid type (e.g., FeCl3, SnCl4, and TiCl4) and Br2 could also be used as chlorobrominating agents, but these mixtures were found to be inferior to the SbCl5–Br2 mixture in product selectivities.
The Cationic Oligomerization of 2-Methylfuran and the Characteristics of the Oligomers
Authors: Ishigaki Akira , Shono Toshiyuki
Published: July 2006

The treatment of 2-methylfuran with phosphoric acid yields the 2,4,4-tris(5′-methyl-2′-furyl)-1-pentanol (1) as a tetrameric product. This product gives its acetate (2) on acetylation with acetic anhydride, and forms a equimolar adduct (3) after treatment with maleic anhydride. The structural formula of 1 is supported by the IR, UV, NMR, and mass spectral data and by the other experimental facts. The other oligomers are separated as a product (4) which contains tetra-, penta-, hexa-, and heptamer. The structure of these oligomers discussed, and some possible reaction mechanisms for oligomerization are suggested.
The Base-induced Reactions of 2-Halogeno-1,3-diketones in a Variety of Solvents
Authors: Wakui Tadahiro , Otsuji Yoshio , Imoto Eiji
Published: July 2006

The reactions of 2-bromo-2-methyldimedone (1), 2,2-dibromodimedone (6), 2-bromo- and 2-chloro-2-methylcyclohexane-1,3-dione (10a and 10b) and 2-acetyl-2,6-dibromocyclohexanone (14) with an equivalent of sodium acetate in a variety of solvents were studied. The constitutions and proportions of the products obtained by these reactions depended strongly on the structure of 2-halogeno-1,3-diketones and the solvents employed. The results were discussed in terms of the mechanisms proposed.
Radiation Synthesis of Methylal from Methanol Solution of Ferric Chloride
Authors: Ikezoe Yasumasa , Sato Shoichi , Oshima Keichi
Published: July 2006

The gamma radiolysis of FeCl3–CH3OH solution was studied by measuring the G-values of the products. The mechanism of the selective formation of the main product methylal (G=8.3) was discussed.
Synthetic Photochemistry. III. The Addition Reaction of Methyl Acetopyruvate to Cycloheptatriene: An Ene Reaction and (4+2)π and (6+2)π Cycloadditions
Authors: Takeshita Hitoshi , Mori Akira , Itô Shô
Published: July 2006

The irradiation of methyl acetopyruvate with cycloheptatriene by means of a high-pressure mercury lamp has yielded (6+2)π and (4+2)π cycloadducts, together with tropylcarbinol derivatives formed by a formal abstraction of allylic hydrogen by the excited carbonyl group, this being the major process in this reaction.
Stereochemical Studies on the Nuclear Alkylation of Phenols with 1-Phenylethyl Chloride and the Acidic Rearrangement of the 1-Phenylethyl Ethers of Phenols in the Phenolic Solvents
Authors: Okamoto Kunio , Kinoshita Tomomi , Makino Osamu
Published: July 2006

Phenolyses of optically active 1-phenylethyl chloride were carried out in phenol (50°C), p-cresol (100°C), p-chlorophenol (100°C), and 2,6-xylenol (100°C in the presence of variable concentrations of the sodium salts of the respective phenols or triethylamine; the distributions (%) for the O- and C-alkylation products and the net steric courses (α%) for each product were examined. The distribution and the steric course which were graphically extrapolated to the zero base concentration indicated that, if the influence of the liberated hydrogen chloride was excluded, in the phenolyses without an added base the major products are the 1-phenylethyl ethers of the respective phenols with net retained configurations and the minor products are the o-and p-1-phenylethylated phenols with net inverted configurations. The hydrogen chloride rearrangement of the optically active 1-phenylethyl ethers of the respective phenols proceeded rapidly to give o-1-phenylethylated phenols with predominantly retained configurations (for phenol, p-cresol, and p-chlorophenol) and p-1-phenylethylated phenols with net inverted configurations (for phenol and 2,6-xylenol) in the respective phenol–benzene (1:1 by wt) solvents. The p-toluenesulfonic acid rearrangement of 1-phenylethyl phenyl ether-18O proceeded to give o- and p-1-phenylethylphenols with partial loss of the oxygen-18 atom in the phenol–benzene (1:1 by wt) solvent, indicating the coexistence of the intermolecular course for the acidic rearrangement in the phenolic solvents. From these findings, it is concluded that the formation of the ortho-alkylates with retention of configuration, experimentally observed in the respective phenolyses without an added base, is attributed not to the direct retentive alkylation of the phenols, but to the rapid rearrangement of the 1-phenylethyl ethers with net retention of configuration, caused by the hydrogen chloride liberated in the SN1-phenolysis of 1-phenylethyl chloride in the respective phenolic solvents.
The Back-extraction Behavior of Chelate Compounds. I. The Extraction and the Back-extraction of the Metal Oxinates
Authors: Honjo Takaharu , Ameno Kiyoshi , Horiuchi Masanobu , Kiba Toshiyasu
Published: July 2006

The behavior of trace amounts of silver, bismuth, cadmium, cerium, cobalt, europium, iron, mercury, indium, manganese, lead, scandium, and zinc in backextraction have been examined in order to ascertain the basic conditions for the mutual separation of metals as their oxinates by back-extraction.
Reductions of Cobalt(III) Complexes by Ferrous Chelates. II. The Reductions of Cobalt(III) Complex with Polymeric Ligands by Means of Some Ferrous Chelates
Authors: Kurimura Yoshimi , Sekine Ikuko , Tsuchida Eishun , Karino Yukio
Published: July 2006

The effects of polymeric ligands on the electron-transfer reaction of the cobalt(III) complex have been studied for the reductions of the complex ions of cis-Co(en)2ACl2+ (A=poly-4-vinylpyridine, PVP, or pyridine, py) by the aquo ferrous ion and some Fe(II)-nitrilopolycarboxylate chelates. The specific rate of the Fe2+ reduction of the Co(en)2PVPCl2+ is smaller than that of the Co(en)2PyCl2+. The specific rate of the Fe(II)-chelate reduction increases considerable when the pyridine ligand in the Co(en)2-PyCl2+ is replaced by PVP. The effects of the chelating agents, the degree of coordination, the ionic strength, and the concentration of the reductant on the reduction rate of the Co(en)2ACl2+ by the Fe(II)-nitrilopolycarboxylate were also examined. The resulting reactivity patterns of the polymer complex ions could mainly explained by the effect of the higher electrostatic field caused by the positively-charged polymer structure.
The Electronic Spectra of Diphenylacetylene and 1,3-Butadiyne
Authors: Takabe Tetsuko , Tanaka Masashi , Tanaka Jiro
Published: July 2006

The electronic absorption spectra of 2,4-hexadiyne-1,6-diol, diphenylacetylene, and diphenyldiacetylene were measured in a single crystalline state with a polarized light. The results of the polarization measurement and the theoretical calculations gave confirmative assignments of the electronic transitions of these molecules.
The Photochemical Reaction of 1,4-Naphthoquinone Derivatives with Hydrogen Donors
Authors: Maruyama Kazuhiro , Arakawa Seiichi
Published: July 2006

The reaction products of the photochemical reactions of 1,4-naphthoquinone and its methyl- or halogenoderivatives with xanthene were investigated. Methyl-substituted 1,4-naphthoquinones produce the corresponding 1,4-naphthohydroquinones, but naphthoquinone and its halogeno-derivatives react to give substituted or added products by the xanthyl group in addition to the hydroquinone derivatives. Stable free radicals, which remain unchanged under atmospheric pressure, are also obtained in the latter reactions. The courses of the photochemical reactions were investigated by means of the CIDNP technique, and the reaction mechanism was discussed.
Resonace Raman Spectra of Acid-Base Indicators. II. Hydroxyarylazobenzene Derivatives
Authors: Saito Yutaka , Kim Bak-Kwang , Machida Katsunosuke , Uno Toyozo
Published: July 2006

The effects of pH on resonance Raman spectra of several hydroxyarylazobenzene-type acid-base indicators have been investigated. All the compounds examined show the azo-type spectra in basic solutions, while the neutral solution spectra are the azo-type for p-hydroxyphenyl compounds and the quinoid-type for α- and β-hydroxynaphthyl compounds. The spectrum of Tropaeoline O changes complicatedly along with the protonation and deprotonation on the pH change.
p-(3,4-Diphenyl-1,3-cyclopentadien-1-yl)phenyltropylium Perchlorate. An Intermediate in the Synthesis of [5.6.7]Quinarene System
Authors: Takahashi Kazuko , Takenaka Shunsuke , Kikuchi Yoriko , Takase Kahei , Nozoe Tetsuo
Published: July 2006

Attempt was made to dehydrogenate p-(3,4-diphenyl-1,3-cyclopentadien-1-yl)phenyltropilidene, prepared by treating p-tropylphenyllithium or p-tropylphenylmagnesium bromide with 3,4-diphenylcyclopent-2-enone, to 3″, 4″-diphenyl-1- cycIoheptatrienylidene-4-cyclopentadienylidene-2,5-cyclohexadiene, 10,11-diphenyl [5.6.7]quinarene. The resulting blue pigment showed spectral properties in line with those of p-(3,4-diphenyl-1,3-cyclopentadien-1-yl)phenyltropylium ion, [5.6.7]quinarenium ion, carrying a delocalized positive charge (VII’) but not those of expected cross-conjugated hydrocarbon.
Dye Sensitized Photo-oxidation of Diphenylamine
Authors: Bansal W R , Puri S , Sidhu K S
Published: July 2006

Evidence is presented to show that excited O2(1∑g+, 1Δg) is an intermediate in the dye (methylene blue, rose bengal, eosin) sensitized oxidation of diphenylamine which yeilds N-phenyl-p-benzoquinonimine. The relative rates in different solvents are reported and a mechanism is suggested.
The Decomposition of Nitrous Oxide in the Radiolysis of n-Hexane Solutions
Authors: Hatano Yoshihiko , Abboud José-Luis
Published: July 2006

The effect of the addition of N2O (10−2−10−4 mole fraction) in the radiolysis of liquid n-hexane has been examined. The oxygen-contaning products such as water and alcohols have been detected. The number of nitrogen molecules products per an electrons scavenged by N2O exceeds unity even at the lowest concentration.
Reactivity of exo- and endo-Tricyclo[3.2.1.02,4]octan-8-ylidenes and 7-Norbornenylidene
Authors: Murahashi Shun-ichi , Okumura Kazuo , Maeda Yusuke , Sonoda Akio , Moritani Ichiro
Published: July 2006

endo-Tricyclo[3.2.1.02,4]octan-8-ylidene (2) generated by the thermolysis of sodium salt of endo-tricyclo[3.2.1.02,4]octan-8-one tosylhydrazone (5) gave toluene (3.9%), cyclohepta-1,4-diene(6, 14%), cyclohepta-1,3-diene(7, 3.5%), bicyclo[3.3.0]octa-1,6-diene(8, 4.8%), bicyclo[3.3.0]octa-1,7-diene(9, 9.0%), and endo-tricyclo[3.2.1.02,4]octane (10, 21%). In sharp contrast, exo-tricyclo[3.2.1.02,4]oct-8-ylidene (1) gave toluene (1.5%) and tricyclo[5.1.01,7]oct-5-ene (14, 57%). The results indicate significant homoconjugative interaction between the p-orbital of the divalent carbon and the symmetric Walsh orbital of the cyclopropane. This is in line with the results of 7-norbornenylidene (3) in which the interaction between the divalent carbon and the carbon-carbon double bond stabilizes the nonclassical methylene. Thermolysis of sodium salt of 7-norbornenone tosylhydrazone (18) gave rise to cyclohexa-1,3-diene (3%), norbornene (6%), toluene (5%), spiro[2.4]hepta-4,6-diene (19, 10%), and bicyclo[3.2.0]hepta-1,6-diene (21, 56%).
An Inversion of Configuration of Threonine and Allothreonine in the N,O-Acyl Migration Reaction with Concentrated Sulfuric Acid
Authors: Wakamiya Tateaki , Tarumi Yuzo , Shiba Tetsuo
Published: July 2006

On the N,O-acyl migration reaction of β-hydroxy-α-amino acids with concentrated sulfuric acid, a configuration of the carbon atom carrying hydroxyl group was found to be inverted through the reaction. Thus, threonine residue in peptide was converted to allothreonine residue and vice versa in the selective chemical cleavage of threonine peptide employing the N,O-migration with concentrated sulfuric acid. The reaction mechanism involving SNi elimination of O-sulfate formed as an intermediate was suggested. The inversion did not occur in the N,O-acyl migration reaction with other mineral acids than sulfuric acid.
Studies of the Reactions of Amines with Sulfur Trioxide. IV. One-step Synthesis of N-substituted Imidobissulfates from Amines
Authors: Kanetani Fujio , Yamaguchi Hachiro
Published: July 2006

The scope and limitations of a one-step synthesis of N-substituted imidobissulfates, RN(SO3K)2 (R=Me, Et, n-Pr, iso-Pr, n-Bu, iso-Bu, sec-Bu, tert-Bu, n-C6H13, cyclo-C6H11, PhCH2–, PhCH2CH2–, PhCH(CH3)–, or Ph), starting from amines and the sulfur trioxide-triethylamine complex are described. The yields are generally good (55–90%). However, with aniline only a poor (13%) yield was obtained. With tert-butylamine, tert-butylamidosulfate was obtained quantitatively instead of the expected tert-butylimidobissulfate. Bis(cyclohexylammonium) salts of the imidobis(sulfuric) acids are prepared, and their properties are briefly recorded.
The Reactions of β-Hydroxychalcones and 2-Acetoxy-1,3-diarylpropan-1,3-diones with Lead Tetraacetate
Authors: Kurosawa Kazu , Moriyama Akira
Published: July 2006

The reaction of β-hydroxychalcone with lead tetraacetate gave benzil. The reaction of 4,4′-dimethoxy-β-hydroxychalcone gave 2-acetoxy-1,3-di(p-methoxyphenyl)propan-1,3-dione and 4,4′-dimethoxybenzil. The reactions of 2-acetoxy-1,3-diarylpropan-1,3-diones yielded 2,2-diacetoxy-1,3-diarylpropan-1,3-diones and benzils respectively. The formation of the benzils from β-hydroxychalcones and 2-acetoxy-1,3-diarylpropan-1,3-diones has been shown to involve 1,2-aryl and 1,2-aroyl migration respectively by studies of the oxidations of 14C-labelled compounds.
Photochemistry in Micellar System. I. Stabilization of the Radical Anions of Anthraquinonesulfonates
Authors: Kano Koji , Matsuo Taku
Published: July 2006

Micellar effects on the photochemical reactions of sodium 9,10-anthraquinone-2-sulfonate and disodium 9,10-anthraquinone-2,6-disulfonate were studied by means of ESR and electronic spectroscopy. In the presence of anionic and non-ionic surfactants, irradiation of the quinones in aerobic phosphate buffer (pH 8.0) gave the corresponding radical anions, which were incredibly long-living (over several weeks) as compared with irradiation without surfactant. Plausible mechanisms of the micellar effects on the stabilization of the radical anions are discussed.
Charge-transfer and Proton-transfer in the Formation of Molecular Complexes. X. Picric Acid Complexes with 2,5-Dichloroaniline
Authors: Matsunaga Yoshio , Saito Gunzi , Sakai Naoto
Published: July 2006

Yellow 2,5-dichloroanilinium picrate was found to isomerize into a red complex of the charge-transfer type at 74 °C with a heat of transition of 4.2 kcal/mol. In addition, a charge-transfer complex with a 1 : 3 mole ratio was isolated.
Experimental Determination of Ionization Potentials of Organic Amines, β-Carotene and Chlorophyll a
Authors: Nakato Yoshihiro , Chiyoda Takeshi , Tsubomura Hiroshi
Published: July 2006

Ionization potentials (Ip’s) of several organic compounds have been determined by the method of photocurrent measurements in gas and organic solvents. It has been found that the vapor-phase Ip’s, calculated from those determined from the onsets of the photo-currents in solutions by using Born equation for the solvation energies of the cations and a common term for the energy of the electron in solution, agree well with those measured in the vapor phase. Based on this result, the Ip’s of molecules in the gas phase can be derived from those measured in the solution. This method is useful for the determination of Ip’s of large molecules which cannot be obtained in the gas phase. Some of the Ip’s obtained are: 5.6 for 1,1,4,4-tetrakis(dimethylamino)butadiene, 5.7 for 3,3′-dimethyl-2,2′-bibenzothiazolinylidene, 6.4 for β-carotene, 6.1 for chlorophyll a, 6.3 for dihydridobis(π-cyclopentadienyl)tungsten (eV unit). The conditions of lowering the Ip’s of organic molecules are discussed.
Derivatives of l,2-Dithiole-3-thiones. VII. Study of Reaction of Thiocarbonyl S-Imide with Amines
Authors: Tamagaki Seizo , Sakaki Keishi , Oae Shigeru
Published: July 2006

Thiocarbonyl S-imide of 4,5-benzo-1,2-dithiole-3-thione reacted with primary and secondary amines of various types to give both rearranged and amine-exchanged imines. By kinetical studies a plausible mechanism involving the addition and elimination of amine on the tetravalent sulfur atom was proposed.
Restricted Rotation Involving the Tetrahedral Carbon. XI. Barriers to Rotation and Conformational Preferences of Substituted 9-Isopropyltriptycenes
Authors: Suzuki Fumio , Oki Michinori , Nakanishi Hiroshi
Published: July 2006

Several 9-isopropyltriptycene derivatives were prepared by addition of benzynes to 9-isopropylanthracenes. Rotation about the C9-Cpr bond of these compounds is found to be frozen at room temperature on the NMR time scale. Those compounds which carry a substituent at 1-position exist as dl-isomers, at least overwhelmingly. No sign of existence of meso-isomer is found. On the other hand, 9-isopropyl-2,4-dimethyltriptycene exists as a mixture of d, l, and meso isomers, composition of which is almost 1 : 1 : 1. Repulsive nonbonding interaction is a decisive factor to determine the conformational preference. Approximate methods for line shape analysis of two methyl groups in an isopropyl group are discussed. Activation energies for rotation about the C9-Cpr bond increase with the increase in the size of 1-substituent except for the methyl group. The smaller effective size of the methyl group than that expected from the van der Waals radius is attributed to cogwheeling arrangement of methyl and isopropyl groups at the transition state of rotation and/or the higher energy level of the ground state due to the severe interaction between methyl and isopropyl groups.
Reaction of 1-Methyl-4-phenylquinazolinium Salts with Diazomethane
Authors: Yamada Yoshihisa , Oine Toyonari , Inoue Ichizo
Published: July 2006

For the synthesis of 5-phenyl-1,4-benzodiazepines, reaction of quinazolinium salts with diazomethane was studied. In the course of the study, it was found by NMR spectroscopy that the starting materials (2) reacted even with a slight amount of water present in the solvent to give hydrates 5. Treatment of 2c with diazomethane at 10 °C under absolute anhydrous conditions gave quinazoline 8c and benzodiazepines 9 and 10c in about the same ratio. In the reactions at lower temperatures, the distribution of the products varied markedly, and the ring expansion product 10c was obtained in an improved yield. The mechanism for the formation of 8, 9, and 10 was discussed.
Chemical Behavior of Intermediates Produced in Sulfuric Acid Glass by Gamma Irradiation. I. Reactivities of Mobile Electrons with Inorganic Ions
Authors: Sasaki Teikichi
Published: July 2006

The yield of the trapped hydrogen atom, Ht, produced in the 6 M sulfuric acid matrix at 77 K was decreased by the presence of an electron scavenger. Based on the competition reaction kinetics, the reactivities of mobile electrons, em−, with metallic and oxygen-containing ions were determined from the decrease in the Ht yield. It was found that em− is scavenged most efficiently with the TeO42− ion. The relative reaction rates of em− with oxyanions were generally larger than those of the corresponding eaq− reactions. On the other hand, a good accordance in the reaction rates for both forms of electrons was observed in the cases of the reactions with metallic ions. An interpretation was given to the discrepancy in the observed reaction rates that em− in the epithermal energy region goes over the Coulomb barrier, which is too high for eaq− to pass through, and thus reacts more efficiently with anionic species than does eaq−. Some unstable intermediates produced at 77 K polymerized with the solute during the thermal annealing. The ESR and optical spectra of the polymerized cadmium and molybdenum are shown, together with those of the primarily-produced species.
Proton Nuclear Magnetic Resonance Spectroscopy of Partially-deuterated n-Pentanes
Authors: Kondo Masahiro , Ando Isao , Chûjô Riichirô , Nishioka Atsuo
Published: July 2006

The proton NMR spectra of some partially deuterated n-pentanes were observed under both proton-deuteron (H–D) spin-coupled and -decoupled conditions. With using the spectrum-simulation method, it was confirmed experimentally that the chemical shift of the CH2(3) protons appears at a higher field than that of the CH2(2) protons.
Phase Equilibria of the Systems Containing Silver Iodide and Alkali Iodide. II. AgI–NaI–H2O System
Authors: Nishimura Norio , Higashiyama Tatsuo
Published: July 2006

Phase diagrams were constructed for the equilibria of the AgI–NaI–H2O system at temperatures 0–70 °C. A compound AgI·NaI·3H2O was isolated, and the compound was found by means of X-ray analysis to belong to the orthorhombic system with cell constants a=8.78, b=33.5, and c=6.48 Å.
The Cyclopolymerization of Triallyl Citrate
Authors: Matsumoto Akira , Ohata Tetsuji , Oiwa Masayoshi
Published: July 2006

The radical polymerization of triallyl citrate was carried out at 60 °C, benzoyl peroxide being used as the initiator and benzene as the solvent; here it has been considered kinetically in terms of cyclopolymerization. Thus, the kinetic equations for the polymerization of the triallyl ester were first derived by an extension of the kinetic treatment for the cyclopolymerization of the diallyl ester. Next, they were applied to the polymerization of triallyl citrate. In consequence, the following results were obtained: (i) the rate of polymerization, Rp, was not proportional to either the square root or first power of the initiator concentration, [I]; rather, Rp/[I]1⁄2 and [I]1⁄2had a linear relationship, (ii) the relation between the rate of polymerization over the degree of polymerization, Rp/\barPn,o, and the monomer concentration, [M], was also linear, and (iii) the ratio of the unimolecular cyclization reaction to the bimolecular propagation reaction of the uncyclized radical, Kc, was estimated to be 4.5 mol/1 from the dependence of the residual unsaturation on the monomer concentration.
Bromine Addition to Chloronorbornene Derivatives
Authors: Yanagida Y\={u}ji , Shigesato Hideo , Nomura Masakatsu , Kikkawa Sh\={o}ichi
Published: July 2006

The reaction of bromine with both trans-5,6-dichloro-2-norbornene (I) and exo-cis-5,6-dichloro-2-norbornene (III) in an acetic acid solution gave trans-adducts in a 100% yield, while the bromination of endo-cisr-5,6-dichloronorbornene (II) afforded the endo-cis adduct in a ca. 100% yield. The latter observation was explained in terms of a sterical inhibition of the bromide ion’s attack in the endo-direction by the two endo-chloro substituents. In the CCl4 solution, however the reaction of I with bromine afforded the exo-cis adduct in a 64% yield, together with the trans-adduct (36% yield). Then, the reaction of I with bromine was carried out in several other solvents (CH3OH, Cl(CH2)2Cl, CH3CO2C2H5, and CCl4). As the polarity of the solvents (the ET values are used here as a measure of the solvents’ polarity) decreased, the formation of the exo-cis adduct became progressively more predominant, while the addition of bromide salt retarded the formation of the exo-cis adduct. Such results and the kinetic studies suggested that the exo-cis adduct was formed through the carbonium bromide ion-pair mechanism. The stereoisomers obtained in this study were assigned on the basis of the NMR spectra.
The Magnetic Circular Dichroism of Some Copper(II) β-Diketone Chelate Complexes in Various Media
Authors: Katô Hajime , Kimura Takahide
Published: July 2006

The magnetic circular dichroism (MCD) and absorption spectra of Cu(acac)2, Cu(bzac)2, Cu(TFacac)2, and Cu(TFacac)2 in benzene, chloroform, methylene chloride, 1,4-dioxane, pyridine, and piperidine are observed. The behavior of these spectra can be well explained by proposing this order of energy levels: dxz, dyz<dx2−y2<dz2<dxy. The MCD spectra in pyridine do not show any dispersion in the neighbourhood of the absorption peak which seems to correspond to the dxz, dyz→dxy transition; this fact suggests that the B-term of the MCD parameters is dominant at room temperature. There is no serious difference between the MCD of Cu(acac)2 and Cu(bzac)2, or between Cu(HFacac)2 and Cu(TFacac)2. It appears that this lowering of symmetry is not important in interpreting the MCD spectra.
Crystal and Molecular Structure of (−)-erythro-1′-(2,5-Dimethoxyphenyl)-3′-diethylaminobutyl Acetate Hydrobromide
Authors: Masuda Yoshihiro , Iitaka Yoichi , Hamano Hiroaki
Published: July 2006

In order to determine the stereospecificity and absolute configuration of 1′-(2,5-dimethoxyphenyl)-3′-diethylamino-n-butanol, X-ray structure analysis of its acetate hydrobromide has been carried out. The crystal of the derivative belongs to the monoclinic space group C2, with lattice constants a=14.218, b=8.290, c=18.187Å, β=108.1°, containing four formula units of C18H29O4N·HBr in a unit cell. The structure was solved by the heavy atom method and refined by the block-matrix least squares method to an R value of 0.06. The absolute configuration was determined by the use of the anomalous dispersion method, the configuration at the two asymmetric carbon atoms being found to be S.
Novel Radical Salt Polymers as Hydrogenation Catalyst of α-Olefins
Authors: Kawazura Hiroshi , Yamamoto Yoshiro , Ohmori Toshio , Murano Kentaro , Inokuchi Hiroo
Published: July 2006

Novel polymeric radical salts prepared by inserting alkali-metals into semi-conductive polymers derived from poly(tetrahalophenylene sulfides) were found to be effective hydrogenation catalyst for α-olefins; their activity trends as to the sort of alkali-metal and halogen of the matrix polymer were Cs>K>Na and F>Cl>Br respectively. The catalyst also showed an activity for the cis-trans isomerization of hex-2-ene which was proportional to that for the hydrogenation. The activities of the catalyst were discussed in terms of its steric confinement.
The Structure of Ternstroemiaxanthin, a New Aldehydic C40-Carotenoid
Authors: Kikuchi Kiyoshi , Yamaguchi Masaru
Published: July 2006

A new carotenoid, ternstroemiaxanthin, was isolated as a main constituent from the red seeds of “Ternstroemia japonica,” and the structure of the pigment was determined to be 3-hydroxy-β,ψ-caroten-18′-al (I) by spectral and chemical methods.
Reactions of 2-Cyano-2-dimethylamino-1,3-dithiolane
Authors: Hiratani Kazuhisa , Nakai Takeshi , Okawara Makoto
Published: July 2006

The reactions of 2-cyano-2-dimethylamino-1,3-dithiolane (2) with electrophiles (organic halides and perchloric acid) and nucleophiles were investigated. It was found that 2 dissociated partially to 2-dimethylamino-1,3-dithiolan-2-ylium (1) and cyanide ions in polar solvents. In the reactions of 2 with electrophiles, nitriles were obtained along with the formation of salts of 1. The reactions of 2 with nucleophiles were studied since 2 was expected to be a precursor of the cation 1. In some cases, its reactivity differs from that of perchlorate of 1. A mechanism was discussed in which the cyanide ion might behave as a base to abstract a proton from the nucleophiles.
The Cyclocopolymerization of Triallyl Citrate with Several Vinyl Monomers
Authors: Ohata Tetsuji , Matsumoto Akira , Oiwa Masayoshi
Published: July 2006

Triallyl citrate (TAC) was copolymerized with allyl benzoate (ABz), vinyl acetate (VAc), vinyl chloride (VC), acrylonitrile (AN), and styrene (St) at 60°C with benzoyl peroxide or 2,2′,-azobisisobutyronitrile as the initiator; it was considered kinetically in terms of cyclocopolymerization. The following monomer reactivity ratios were obtained: VAc: r1=1.29, r2=0.76, rc=0.61; ABz: r1=1.63, r2=1.10, rc=0.47; VC: r1=0.40; r2=1.90, rc=0.31; AN: r1=0.01, r2=8.7; St: r1=0.03, r2=53.0, where r1, rc and r2 denote the monomer reactivity ratio of the uncyclized, cyclized, and monovinyl radicals respectively. In the copolymerization of TAC with AN, the penultimate effect was also observed: r1=r1′=0.01, r2=k122⁄k121=11, r2′=k222⁄k221=5.
Emission Spectra of Carbon Disulfide, Hydrogen Sulfide, and Thiols by Controlled Electron Impact
Authors: Toyoda Minoru , Ogawa Teiichiro , Ishibashi Nobuhiko
Published: July 2006

The emission spectra in the 200–600 nm region produced by the controlled electron impact method were investigated in the vapor phase on hydrogen sulfide, carbon disulfide, methanethiol, and ethanethiol at low pressures. The photoemissions were observed and assigned for an excited parent molecule, molecular ions, and fragments, such as CS2, CS2+, H2S+, H, CH, CS, and HS+. The intensities of the photoemission of most of the species were found to increase linearly with both the electron beam current and the gas pressure, and these species were concluded to be produced in some one-electron unimolecular processes.