bluuebunny/crossref_metadata_2025_split huggingface dataset:
Studies of Nitrogen-Phosphorus Compounds. XXV. The Synthesis of Guanidium Condensed Phosphates
Authors: Kobayashi Etsuro 
Published: July 2006

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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.