bluuebunny/crossref_metadata_2025 huggingface dataset:
Reactions of Metal Chelates. III. The Reactions of Bis(salicylaldehydato)copper(II) with Amides and Esters of Glycine and Glycylglycine
Authors: Hamada Kazuko , Ueda Hideo , Nakao Yasuo , Nakahara Akitsugu
Published: July 2006

The reactions of bis(salicylaldehydato)copper(II) in acidic, neutral and basic media with glycinamide, glycinester, glycylglycinamide and glycylglycinester have been systematically investigated. The reaction products have, in all cases, been isolated as crystals and characterized. As a result of this investigation, six new copper(II) chelates of Schiff bases derived from salicylaldehyde and glycine- or glycylglycine-amide have been obtained. The interrelation between those chelates has also been disclosed.
The Mixed Chromium(III) Complexes containing Acetylacetone and the Halogenations Thereof
Authors: Fujii Yuki , Kyuno Eishin , Tsuchiya Ryokichi
Published: July 2006

The following three mixed chromium(III) complexes containing acetylacetone, which had a charge of from −1 to +1, were prepared: NH4[Cr(acac)(ata)]·H2O, [Cr(acac)(edda)]·2H2O and [Cr(acac)(edma)(H2O)]Cl·H2O. The halogenations at γ-position of the acetylacetonate ring were attempted in these three mixed complexes with NCS, NBS and ICl respectively in methanol and in acetic acid solutions, where NCS, NBS and ICl are abbreviated forms of N-chlorosuccinimide, N-bromosuccinimide and iodine monochloride, respectively. From an inspection of UV-spectra of the above halogenation reaction mixtures, all the three mixed complexes were confirmed to be halogenated at the γ-position of the acetylacetonate ring. Of these complexes, NH4[Cr(acac-Cl)(ata)]·\frac12H2O and [Cr(acac-Br)(edda)] were isolated as crystals from the reaction mixtures. IR-spectra measurement was also used to certify the halogen-substitution at γ-position in the above two compounds.
Synthesis of Vitamin B12 Model Compounds
Authors: Sasaki Tadashi , Matsunaga Fujinao
Published: July 2006

Bis(dimethylglyoximato)cobalt(III) complexes with the general formula: [CoX(DH)2BA] (X: CN−, NO2−, SeCN−, SCN−, Br−. D: dianion of dimethylglyoxime. BA: such biologically interesting bases as imidazole, benzimidazole, 5,6-dimethylbenzimidazole, pyridine, γ-picoline, 4-vinylpyridine, nicotinic acid, isoquinoline, 5-amino-4-imidazolecarboxamide, and 6-aminopurine) were prepared from dimethylglyoxime, the base, and an adequate cobalt (III) salt. The treatment of [CoCN(DH)2Imd] (Imd: imidazole) with boron trifluoride etherate afforded [Co(CNBF3)(DBF2)2Imd] in an 86% yield. The reduction of [CoCl(DH2)Imd] with sodium borohydride gave a labile [Co(I)H(DH)2Imd], which was directly converted with phenylacetylene into a stable [Co(III)(C6H5CH=CH)(DH2)Imd] in a 60% yield and into [Co(DH)2Imd]·H2O in a 30% yield. These products were structurally elucidated on the basis of their spectral data.
A Mechanistic Approach to the Electrolytic Reductive Dimerization of Acrylonitrile
Authors: Asahara Teruzo , Sen\={o} Manabu , Arai Takeshi
Published: July 2006

The electrolytic reductive dimerization of acrylonitrile was investigated extensively especially in order to obtain some mechanistic information. The essential point of this reaction exists in the selective formation of adiponitrile under relatively wide conditions and this cannot be explained by a normal kinetic treatment based on the reaction scheme which has been accepted as probable. The heterogenuity in acrylonitrile concentration in the reaction system is assumed and the kinetic formulas are modified. This treatment explains the experimental results very satisfactorily. In order to confirm this mechanistic scheme, the effects of temperature, pH and solvents on the yield of reaction products were examined. All the results are consistent with the proposed mechanism.
Studies of Acetothiolacetate
Authors: Motoki Shinichi , Sato Tadao
Published: July 2006

Ketene dimer reacted with mercaptan to give acetothiolacetate (I) in the presence of triethylamine. The ester I underwent a thermal condensation to give dehydroacetic acid (III), with the liberation of mercaptan, merely upon heating, and the reaction was effectively promoted in the presence of triethylamine. The ester I reacted with alkyl halide and acyl halide in dioxane to give α-alkyl and α-acylacetothiolacetate (II) respectively. Ethyl acetothiolacetate, ethyl α-methyl-acetothiolacetate, and ethyl α-acetylacetothiolacetate reacted with mercuric oxide at a low temperature to give diacetylacetone (VI), methyl ethyl ketone, and dehydroacetic acid (III) respectively.
The Structure of Copolymers of l-Proline with l-Glutamic Acid in Aqueous Solutions
Authors: Sakai Rume , Isemura Toshizo
Published: July 2006

Three copolymers of l-proline and l-glutamic acid were synthesized, and their equilibrium conformation in an aqueous solution was studied in relation to their composition. The molar ratios of the proline to the glutamic acid residues in the copolymers were about 1:3, 1:1, and 8:1. All the copolymers were soluble in water, as were poly-α,l-glutamic acid and poly-l-proline II. The conformational change was caused by the pH effect on proline-poor copolymers. Evidence was obtained for the possibility of the absence of such a helix as a right-handed poly-l-proline-I-helix in the copolymers examined. The conformation of Copoly-8:1 was not affected by the pH and was identified as the poly-l-proline-II-helix.
The Photoreaction of β-Benzoylacrylic Acid
Authors: Sugiyama Noboru , Kataoka Hiroshi , Kashima Choji , Yamada Kazutoshi
Published: July 2006

The product of the irradiation of trans-β-benzoylacrylic acid (1) in methanol was proved to be α-methoxy-β-benzoylpropionic acid (2), whose methyl ester was identified with an authentic material. On the other hand, the product of the irradiation of methyl trans-β-benzoylacrylate (5) was the cis-isomer. The photoreaction of 1 in various solvents, including EtOH, iso-PrOH, t-BuOH, ether, and AcOH, was examined from the standpoints of the cis-trans isomerization and alcohol addition. The rate of the photoreaction of 1 in methanol was determined, and a reasonable mechanism for the over-all reaction was proposed.
A Novel Method for the Synthesis of 1-Phenyl-2,3-dihydro-4-pyridones
Authors: Sugiyama Noboru , Yamamoto Makoto , Kashima Choji
Published: July 2006

The condensation of β-diketones, benzoylacetone (II), acetylacetone (III), or 6-phenyl-2,4-hexanedione (IV) with benzylidenaniline (I), in the presence of three moles of potassium amide in liquid ammonia, was found to give a dihydropyridone or an aminodiketone. Thus, the condensation of II with I afforded aminodiketone, 1-anilino-1,5-diphenyl-3,5-pentanedione (V), which cyclized to 2,3-dihydro-1,2,6-triphenyl-4-pyridone (IX) upon being treated with sulfuric acid. The condensation of III with I gave 2,3-dihydro-1,2-diphenyl-6-methyl-4-pyridone (X) without any treatment with sulfuric acid. IV and I gave 2,3-dihydro-1,2-diphenyl-6-phenethyl-4-pyridone (XI) as the main product, with 3-benzyl-2,3-dihydro-1,2-diphenyl-6-methyl-4-pyridone (XII) as a by-product.
An Improved Synthesis of N,β-Dimethylleucine and the Resolution Thereof
Authors: Kotake Hiroshi , Saito Tomoo , Okubo Kazuo
Published: July 2006

A diastereoisomeric mixture of racemic β-methylleucine was synthesized by the condensation of 2-benzyl-4(5H)-imidazolone with the methyl isopropyl ketone, followed by catalytic hydrogenation and hydrolysis. The separation of the mixture into threo-β-methyl-Dl-leucine and erythro-β-methyl-Dl-leucine was mainly achieved by fractional crystallization from water. The resolution of each diastereoisomer was also accomplished through salt-formation with (−)- and (+)-ephedrine alternately before or after the methylation of the amino group. The specific rotation and the NMR and IR spectra of one isomer, threo-N,β-dimethyl-l-leucine, corresponded closely with those reported for dimethylleucine isolated from nature.
Characteristic Chemical Constitution of Pitch Materials Suitable for the MP Carbon Fiber
Authors: Otani Sugio , Yokoyama Akira
Published: July 2006

Pitch materials suitable for the MP carbon fiber were prepared from petroleum asphalt, coal tar pitch, and polyvinylchloride. The present investigation was undertaken to clarify the characteristic chemical constitution of each suitable pitch material and to define the significance of the special treatment required to prepare the pitch materials. The suitable pitch materials are generally composed of several structural units with aromatic fused rings and more or less alkyl side chains. The suitable pitch material finally obtained from the petroleum asphalt is characterized by a relatively high molecular weight and many quite long alkyl side chains. Special treatment is required to increase the aromaticity and the removal of the low-molecular-weight component. The suitable pitch material from the coal tar pitch is characterized by aromatic fused rings of the condensed type and only a few alkyl side chains, such as, the methyl group. The most desirable effect of the treatment is to accelerate the condensation between molecules without increasing the insoluble matter and to remove the low-molecular-weight component. The results concerning the polyvinylchloride pitch lend some support to the scheme suggested before.
Mössbauer Effect of 119Sn in Molecular Complexes of Tin(IV) Chloride with Several Aromatic Compounds
Authors: Ichiba Sumio , Mishima Mitsuo , Negita Hisao
Published: July 2006

The Mössbauer spectra of molecular complexes of tin(IV) chloride with some oxygen-containing aromatic compounds, such as hydroxybenzaldehydes and cinnamic acid, were investigated. Most of these complexes show the quadrupole splitting resulting from the addition of aromatic molecules to tin(IV) chloride, although in some cases broad absorption curves are observed. The isomer shifts of these complexes are 0.25—0.45 mm/sec, much smaller than that of tin(IV) chloride itself. These values are almost the same as those of the complexes of tin(IV) chloride with aliphatic compounds. From these results, the bond nature and structures of these complexes, which had not previously been studied, were discussed in some detail.
The Heat of Immersion of Ferric Oxide in Water
Authors: Morimoto Tetsuo , Katayama Noriko , Naono Hiromitu , Nagao Mahiko
Published: July 2006

Four kinds of ferric oxide (α-Fe2O3) which differ in origin and history have been used for measurements of the surface area, the water content, and the heat of immersion in water. Two cases have been discovered; in one there appears a maximum in the plot of the heat of immersion against the pretreatment temperature according to the origin of the sample, but in the other a maximum does not appear. The heavy hydration treatment carried out prior to the immersion measurements raises the value of the heat of immersion in water, but it has no serious effect on the heat of surface hydration calculated therefrom, as in the case of TiO2. The average value of the latter was 11.3 kcal/mol H2O.
The Oxovanadium(IV) Complexes of Schiff Bases Obtained from Substituted Salicylaldehydes and Alkyl Amines
Authors: Yamada Shoichiro , Kuge Yoshio
Published: July 2006

Many new oxovanadium(IV) complexes (abbreviated as VO(X-sal.R)2) of Schiff bases obtained from substituted salicylaldehydes and alkylamines have been synthesized as crystals, where X=H and 3-CH3O and R=CH3, C2H5, n-C3H7, n-C4H9, iso-C3H7, CH(CH3)(C2H5), CH2CH-(CH3)2 and cyclohexyl. Since all these complexes show similar electronic spectra, it is considered that they take an essentially similar configuration, that is, a square-pyramidal one in the solid state and in chloroform, even for R=α-branched alkyls. This result is different from that of the copper (II) complexes. It is also concluded that these oxovanadium(IV) complexes, when dissolved in pyridine, take up one pyridine molecule to form a six-coordinated species. The configuration of the pyridine solvate depends upon R.
Determination of Traces of Constituents with Schiff Bases. III. Extraction-Spectrophotometric Determination of Nickel with Salicylidene-o-aminophenol
Authors: Ishii Hajime , Einaga Hisahiko
Published: July 2006

A method was established for the spectrophotometric determination of microgram amounts of nickel after the extraction of nickel(II) as a salicylidene-o-aminophenol (SAP) complex from an alkaline aqueous solution into chloroform. Nickel(II) reacts with SAP to form a complex which can be extracted into organic solvents such as benzene, chloroform, methyl isobutyl ketone, etc., in the presence of ammonium ions. The extraction of nickel was almost quantitative, and a maximum and constant absorbance was obtained in the pH range from 8.5 to 9.8. The complex extracted was very stable and had an absorption maximum at 418 mμ. The composition of the complex was confirmed to be 1 to 1 (metal to ligand). A linear relationship was maintained between the concentration of nickel and the absorbance. The molar extinction coefficient and the sensitivity for log(I0⁄I)=0.001 at 418 mμ were 17000 and 3.5×10−3 μg Ni/cm2, respectively. Several ions such as cobalt(II), copper(I and II), chromium(III), lead(II), manganese-(II) and citrate interfered with the determination.
Spectrophotometric Study of Solution Equilibria between Ammonia and Copper(II) and Nickel(II) Chelates of Aminopolycarboxylic Acids
Authors: Kodama Mutsuo , Miyamoto Katsumi
Published: July 2006

The addition of ammonia produces a remarkable change in the visible absorption spectra of copper(II)- and nickel(II)-aminopolycarboxylate chelates. This can be ascribed to the formation of a mixed ligand chelate involving ammonia and the aminopolycarboxylate anion. On the basis of the change in the absorbance of copper(II)- and nickel(II)-aminopolycarboxylate chelates, the solution equilibria between ammonia and these aminopolycarboxylate chelates were investigated. Copper(II) and nickel(II) chelates of ethylenediaminetetraacetic acid (EDTA), N-(2-hydroxyethyl)-ethylenediamine-N,N′,N′-triacetic acid (EDTA-OH), ethylenediaminetetrapropionic acid (EDTP), cyclohexanediaminetetraacetic acid (CyDTA), and diethylenetriaminepentaacetic acid (DTPA) were found to form mixed ligand chelates with a composition of M(NH3)Z2−n. From the intercept of the linear relation between log(AY−A)⁄(A−AM) and log[NH3]f, the equilibrium constant, KNH3, defined as KNH3=[M(NH3)Z2−n]⁄[MZ2−n]·[NH3]f, was determined.
Epoxidation of Eight- and Twelve-Membered Cyclic Olefins with Hydrogen Peroxide in the Presence of Metal Oxide Catalysts
Authors: Itakura Jo , Tanaka Hisao , Ito Hiroo
Published: July 2006

The oxidation of eight- and twelve-membered cyclic olefins by H2O2 was carried out in various alcohols using some metal oxides as catalysts. In contrast to the case of cyclohexene and norbornene, which can be hydroxylated, the oxidation of 1,5,9-cyclododecatriene, cyclododecene, 1,3- and 1,5-cyclooctadiene and cyclooctene with H2O2 in the presence of selenium dioxide resulted in selective formation of the corresponding monoepoxides. The following rate equation was obtained with cyclooctene (COE) in isopropanol:

−d[H2O2]⁄dt=k3′[SeO2][H2O2]+k3″[SeO2][H2O2][COE].
A Study of the Solvent Effect in the Copolymerization of N-Phenylethylenimine with β-Propiolactone
Authors: Kagiya Tsutomu , Kondo Tomizo , Fukui Kenichi
Published: July 2006

The effect of the solvent on the copolymerization of N-phenylethylenimine with β-propiolactone has been studied quantitatively. The copolymerization rates for the various solvents used increase in the order: diethyl ether > toluene < carbon tetrachloride < methyl acetate < N,N-dimethylacetamide < anisole < dioxane < acetone < ethylene dichloride < acetonitrile < acetophenone < nitrobenzene < dimethyl sulfoxide < nitroethane. The rates in solvents with high dielectric constants are much larger than those in solvents with low dielectric constants. However, in the case of solvents with similar dielectric constants, the rates decrease with an increase in the nucleophilicity of the solvent; moreover, the dependency of the copolymerization rate on the nucleophilicity of the solvents is much larger in the solvents with high dielectric constants than in those with low dielectric constants. The rate of the consumption of N-phenylethylenimine is markedly affected by the nucleophilicity of the solvents in solvents with high dielectric constants, but it is little affected in solvents with low dielectric constants. Although there is no effect of the nucleophilicity of the solvents on the consumption rate of β-propiolactone, the rate of the consumption of β-propiolactone varies with the electrophilicity of the solvent in solvents with high dielectric constants. On the other hand, the β-propiolactone content in the copolymer increases in proportion to the nucleophilicity of the solvents with high dielectric constants, whereas the β-propiolactone content in solvents with low dielectric constants is almost constant regardless of the electric nature of the solvents.
Effect of the Binary Solvent System on the Copolymerization of N-Phenylethylenimine with β-Propiolactone
Authors: Kagiya Tsutomu , Kondo Tomizo , Fukui Kenichi
Published: July 2006

The effect of the binary solvent system on the copolymerization of N-phenylethylenimine with β-propiolactone has been studied quantitatively. The copolymerization was carried out in three kinds of binary solvent systems, each consisting of components with similar dielectric constants (ε) and with very different nucleophilicities: (1) the nitrobenzene - N,N-dimethylacetamide system, ε\fallingdotseq36, (2) the ethylene dichlorice - tetrahydrofuran system, ε\fallingdotseq10, (3) the toluene-anisole system, ε\fallingdotseq3. In the binary solvent system with the highest dielectric constant, the copolymerization rate decreased with an increase in the content of the nucleophilic solvent. In the nitrobenzene -N,N-dimethylacetamide system, the copolymerization rate markedly decreased upon the addition of a small amount of N,N-dimethylacetamide in nitrobenzene. On the other hand, in the ethylene dichloride - tetrahydrofuran binary solvent system, with a lower dielectric constant than the nitrobenzene and N,N-dimethylacetamide system, the rates decreased in proportion to the tetrahydrofuran content. The β-propiolactone content in the copolymer increased with the amount of the larger nucleophilic solvents, and the dependency of the copolymer composition on the nucleophilicity of the solvents was much larger in the binary solvents with high dielectric constants than in the binary solvents with low dielectric constants. In the toluene - anisole system, which has a very low dielectric constant, the copolymerization rate and the composition of the copolymer were almost constant, independent of the composition of the solvents.
The Addition Reactions of Dialkyl Phosphites to Polyfluorocyclobutenes
Authors: Ueda Teruo , Inukai Kan , Muramatsu Hiroshige
Published: July 2006

The radiation-induced addition reactions of dialkyl phosphites to polyfluorocyclobutenes, such as perfluoro-, 1,2-dichlorotetrafluoro-, 1-chloro-2,3,3,4,4-pentafluoro-, 1,3,3,4,4-pentafluoro- and 1-chloro-3,3,4,4-tetrafluorocyclobutenes were carried out. In general, the corresponding dehydrohalogenated 1 : 1 adducts, polyfluorocyclobutenylphosphonates, were obtained as the main products instead of the expected 1 : 1 adducts. The direction of attack of the phosphonyl radical on the unsymmetrical double bond and reaction mechanism were discussed.
A New σ-Bonded Complex Formation between 2-Vinylpyridine and Palladium(II) or Platinum(II) Chloride
Authors: Kasahara Akira , Tanaka Keiko , Izumi Taeko
Published: July 2006

Sodium tetrachloropalladate(II) reacts with 2-vinylpyridine in methanol, ethanol, or isopropyl alcohol, to give, respectively, di-μ-chloro-bis[2-methoxy-2-(α-pyridyl)ethyl]dipalladium(II), di-μ-chloro-bis[2-ethoxy-2-(α-pyridyl)-ethyl]dipalladium(II), and di-μ-chloro-bis[2-isopropoxy-2-(α-pyridyl)ethyl]-dipalladium(II). The reaction of potassium tetrachloroplatinate(II) with 2-vinylpyridine in methanol or ethanol affords, respectively, di-μ-chloro-bis[2-methoxy-2-(α-pyridyl)ethyl]diplatinum(II) and di-μ-chloro-bis[2-ethoxy-2-(α-pyridyl)ethyl]diplatinum(II). The structures of these complexes containing the covalent metal - carbon bonding have been confirmed by a study of their absorptions and of the NMR spectra.
The Synthesis of Cyclic α-Amino Acids. III. The Synthesis of Methyl (+)- and (−)-3-Amino-3-C-carboxy-3-deoxypentopyranosides
Authors: Yanagisawa Hiroaki , Kinoshita Mitsuhiro , Umezawa Sumio
Published: July 2006

Cyclization of D′-methoxy-diglycolaldehyde, prepared by periodate cleavage of methyl β-l-arabinopyranoside, with ethyl nitroacetate gave a mixture of stereoisomers of cyclic α-nitro ester, i.e. methyl (+)-3-deoxy-3-C-ethoxycarbonyl-3-nitropentopyranoside. Catalytic reduction of the cyclic α-nitro ester afforded an isomeric mixture of cyclic α-amino esters, from which, on column chromatography, there could be isolated four diastereoisomers of methyl (+)-3-amino-3-deoxy-3-C-ethoxycarbonylpentopyranoside. Hydrolysis of each diastereoisomer gave the corresponding cyclic (+)-α-amino acid having a skeleton of pentopyranoside. The stereochemistry of the isomeric amino acids was studied by NMR spectroscopy and chemical degradation. On the other hand, three enantiomeric cyclic (−)-α-amino acids were also obtained from methyl β-d-xylopyranoside by the analogous route as that from methyl β-l-arabinopyranoside.
The Alkaline Hydrolysis of Halophenols
Authors: Oae Shigeru , Furukawa Naomichi , Asari Takashi
Published: July 2006

The mechanism of both the alkaline fusion and the alkaline hydrolysis of halophenols has been investigated. In case of alkaline fusion, the product identified is resorcinol, the formation of which has been found to proceed through the benzyne intermediate. While the alkaline hydrolysis of halophenols gives different ratio of dihydroxyphenol and phenol by changing the mole ratio of halophenol to alkali, by utilizing 14C tracer experiment and substituted halophenol, the mechanism of the formation of both products has been revealed to proceed by way of the direct substitution of halide with hydroxide. Copper compounds are found to be effective in this reaction.
The Yield of Hydrogen Atoms in the Vapor Phase Radiolysis of Ammonia
Authors: Nishikawa Masaru , Kuroda Kazufumi , Matsuura Niro
Published: July 2006

γ-Radiolysis of NH3+C3H8 mixtures was investigated at 22±1°C and total pressure ∼50cmHg. From the observed yield of hydrogen, H atom yield of ammonia radiolysis of GH=5.1–5.8 was obtained after subtraction of contribution from the propane fraction. The value is significantly lower than that determined from the study of NH3+D2 and NH3+N2H4 systems, and also that from the study of NH3+C3H8 system reported previously. A variety of possibilities is discussed with respect to the cause of the disagreement. The effect of addition of N2O or SF6, which acts as an electron scavenger, was also studied. The yield of hydrogen from NH3+C3H8 mixtures decreased appreciably, and ΔG(H2) in the absence and presence of electron scavengers was related to the change in the neutralization process.
The Electronic Spectra and the Intermolecular Interaction of Würster’s Ions in Crystals
Authors: Tanaka Jiro , Mizuno Masagi
Published: July 2006

The electronic spectra and the intermolecular interaction of Würster’s radical have been studied for the dimer state and for the crystalline states. The polarization properties of the excited states have been investigated in detail, and the longest wavelength absorption band of the dimer has been established as having a charge-transfer character. The strength of the charge-transfer band and the shift of the monomer band in the dimer or in the crystalline states are shown to be intimately correlated with the strength of the intermolecular interactions between the stacked radicals. A theoretical analysis of the excited state of the dimer and the crystals is presented; the results are in good agreement with the experimental findings.
Solution Properties of Poly-m-chlorostyrene
Authors: Matsumura Kimiyoshi
Published: July 2006

The solution properties of poly-m-chlorostyrene in toluene and butanone were measured by the light-scattering and viscosity methods. The dependencies of the second virial coefficients, the end-to-end distances, and the intrinsic viscosities on the molecular weights were not very different from those of the other polystyrene derivatives. It was made clear that the unperturbed dimension of poly-m-chlorostyrene was larger than that of poly-p-chlorostyrene, and similar to that of poly-o-chlorostyrene. The relationships between poly-m-chlorostyrene and solvents (toluene and butanone) were similar to those between polystyrene and poly-o-chlorostyrene and the solvents, but the reverse of that between poly-p-chlorostyrene and the latter; that is, compared with butanone, toluene was a “good” solvent for poly-m-chlorostyrene.
Synthetic Hydrogen-containing Ultramarine Phases
Authors: Kubo Yasushi , Yamaguchi Goro
Published: July 2006

Hydrogen was analyzed on synthetic sulfur-containing sodalite-type sodium aluminosilicates. Specimens synthesized from the NaAlSiO4-Na2S system in a H2 or N2 atomsphere or in a N2-S2 atmosphere contained hydrogens which were introduced by ion-exchange during water-washing. Specimens synthesized from the same system in H2S-containing atmospheres also contained hydrogens introduced from the synthetic atmosphere. The latter specimens had the formula: Na8Al6-Si6O24S·xH2S·yS, which was characterized by a constant number of sodium ions (eight per unit cell), whereas the former contained variable numbers of sodium ions according to the duration of water-washing. A difference in correlation between the sulfur content and the lattice constant was observed between these two series of specimens, indicating different manners of existence of the hydrogen.
Polarographic Reduction of Cobalt(II) in Acetonitrile in the Presence of Acetate Ions
Authors: Itabashi Eiki , Ikeda Shigero
Published: July 2006

The effect of the nature and the concentration of the supporting electrolyte on the polarographic reduction of cobalt(II) acetate in acetonitrile has been investigated. An acetonitrile solution of cobalt(II) acetate yields a two-step and a three-step reduction wave in 0.05m LiClO4 and in 0.05m NaClO4 solution, respectively. The same solution gives ill-defined reduction waves in the presence of quaternary ammonium perchlorates, such as (CH3)4NClO4, (C2H5)4NClO4, or (n-C4H9)4NClO4. The Co(CH3CN)n2+, Co(OAc)+, and Co(OAc)3−species are present in a solution containing alkali metal perchlorate electrolyte. Co(OAc)+ and Co(OAc)3− are the predominant species in a quaternary ammonium perchlorate solution. The reduction potential becomes more negative with increase in the number of acetate ions coordinated to cobalt(II). The reduction potential of cobalt(II) acetate becomes less negative upon the addition of alkali metal perchlorate to the quaternary ammonium perchlorate supporting electrolyte. This effect is caused by the dissociation reaction of cobalt(II) acetate, in which an acetate ligand is transferred to the alkali metal ion.
The Kinetic Studies of the Acid-catalyzed Etherification of the Tautomers of p-Nitrosophenol and p-Benzoquinoneoxime with Ethanol in Dioxane
Authors: Furuya Yoshiaki , Urasaki Iwao , Itoho Kazuo , Takashima Akiyoshi
Published: July 2006

The rates of the acid-catalyzed reversible etherification of the allelotrope of p-nitrosophenol and p-benzoquinoneoxime with ethanol in dioxane-forming p-nitrosophenetole have been measured by ultraviolet spectrophotometry. The rate of the forward reaction was expressed as the sum of the second- and the third-orders over a fairly large concentration region of the allelotrope and of ethanol. The plots of the logarithm of the apparent forward second-order rate constant against −log(CBH+⁄CB) gave a straight line with a slope of −0.95. A probable mechanism involving the rate-determining formation of a σ-complex by the nucleophilic attack of the hydroxyl O-atom of ethanol on the α-carbon of the hydroxyl group of protonated p-nitrosophenol, and also the rate-determining deprotonation from the oxime group of the σ-complex by the allelotrope of p-nitrosophenol, was postulated.
Macro Chelate Rings. I. Synthesis of 2,7-Dimethyl-4,5-bis-(salicylideneaminomethyl)acridone as a Quadridentate Chelating Agent and Its Metal Complexes
Authors: Okawa Hisashi , Yoshino Tamotsu
Published: July 2006

2,7-Dimethyl-4,5-bis(salicylideneaminomethyl)acridone, which may form a quadridentate metal complex involving a ten-membered chelate ring, was synthesized by a sequence of steps and characterized. A monomeric cobalt(II) complex of the ligand was isolated and examined.
The Basicities of Substituted Diphenyl Sulfoxides
Authors: Oae Shigeru , Sakai Kazuo , Kunieda Norio
Published: July 2006

The basicities of nine meta- and para-substituted diphenyl sulfoxides have been determined spectrophotometrically in sulfuric acid media. The pKBH+ values thus obtained indicate that these sulfoxides possess rather weak basicities (pKBH+; −3.67–−5.74). and these pKBH+ values gave a good correlation with Brown-Okamoto’s σ+ values, (ρ=−2.00), instead of σ-values. These observations seem to suggest a considerable conjugative interaction between phenyl groups and sulfoxide group of these diphenyl sulfoxides.
Synthetic Studies of Sesamol Derivatives. XI. Synthesis of 5,6-Methylenedioxy-2-isopropenylbenzo[b]furan
Authors: Fukui Kenji , Nakayama Mitsuru , Tanaka Sachihiko
Published: July 2006

5,6-Methylenedioxy-2-isopropenylbenzo[b]furan, an analogue of the naturally-occurring 5,6-dimethoxy compound, has been synthesized by the dehydration of the corresponding 2-(1’-hydroxy)isopropyl derivative, which was obtained from 2-hydroxy-4,5-methylenedioxybenz-aldehyde. By the catalytic hydrogenation of the benzofuran, its 2-isopropyl derivative and its 2-isopropyl-2,3-dihydrofurano-compound were prepared. The NMR spectra of these compounds have been compared.
A New Synthesis of Tephrosic Acid
Authors: Fukui Kenji , Nakayama Mitsuru , Harano Teruo
Published: July 2006

2′-Carboethoxymethoxy-4′,5′-dimethoxy-7-hydroxyisoflavone was prepared from 7-benzyloxy-4′,5′-dimethoxy-2′-hydroxyisoflavone via the corresponding 2′-carboethoxymethoxyisoflavone. The hydrolysis of the 7-hydroxyisoflavone with dilute alkali gave tephrosic acid (2,4-dihydroxyphenyl 2-carboxymethoxy-4,5-dimethoxybenzyl ketone) in a good yield.
Ring Expansion of Bicyclic gem-Dihalo- and Monohalocyclopropanes
Authors: Ando Teiichi , Hosaka Hirokazu , Yamanaka Hiroki , Funasaka Wataru
Published: July 2006

Some bicyclic gem-dichlorocyclopropanes (Ia through Id) and gem-chlorofluorocyclopropanes (IIa through IId) were prepared by the addition of dichloro- and chlorofluorocarbene, respectively, to the appropriate cyclic olefins. The reduction of these dihalocyclopropanes with tri-n-butyltin hydride gave the corresponding monochloro- (IIIa through IIId) or monofluorocyclopropanes (IVa through IVd) in fairly good yields. When treated with an excess of hot quinoline, the endo-chloro isomers of IIa, IIb, IId, IIIa, IIIb, and IIId were converted to their ring expansion products, whereas their exo-chloro isomers were recovered unchanged. In contrast, the exo-chloro isomers of IIe and IIIc decomposed more readily than their endo-chloro isomers under similar conditions. These results were discussed on the concept of a concerted disrotatory process.
1,3-O-Benzylidene-l-sorbose
Authors: Maeda Takashi , Kimoto Mitsuru , Wakahara Shigeru , Tokuyama Kanji
Published: July 2006

It has been proposed that 1,3-O-benzylidene-l-sorbose (III) exists as an equilibrium mixture of a pyranose form (IIIp), a keto-form (IIIk) and a furanose form (IIIf) in solutions. The acetylation of III in pyridine afforded the acetates of IIIf; one of them (IV) is in a keto-form (IVk) in a crystalline state, and at a low temperature, while the acetates of IIIf and IIIp at higher temperatures. When a pyridine solution of III was allowed to stand for some time before acetylation, the yield of the acetate of IIIp increased. The recrystallization of III usually gave crystals of IIIf, however, while the addition of petroleum ether to the concentrated pyridine solution of III afforded a powder which was consisted mainly of IIIp. These results suggest that III exists as IIIf in a crystalline state and as an equilibrium mixture of IIIf, IIIk, and IIIp in solution; the existence of this equilibrium was also confirmed by proton magnetic resonance spectroscopy.
The Nucleophilic Substitution Reactions of 2-Aminotropone Derivatives
Authors: Toda Takashi , Ryu Shôji , Nozoe Tetsuo
Published: July 2006

The nucleophilic substitution reactions of 2-aminotropone (I), 2-methylaminotropone (II), 2-dimethylaminotropone (III), and 2-troponyl trimethylammonium iodide (IV), and their alkyl derivatives were investigated. It was found that the properties of I and II are similar to those of tropolones. On the other hand, those of III are analogous to those of tropolone methyl ethers, while those of IV are, rather, comparable to those of 2-halotropones or tropolone tosylates.
The Mechanism of ESR Relaxation in Peroxylamine Disulfonate Ion ·ON(SO3)22−
Authors: Fujiwara Shizuo , Sakioka Kayoko
Published: July 2006

The mechanism of ESR relaxation in ·ON(SO3)22− is discussed. As the line width in an aqueous solution is plotted against the concentration, it is almost concentration independent in the range lower than 7×10−3 mol/l, but the dependence increases in the higher range. Powles and Moseley showed that the anisotropy of the g-value contributes to the line width in the lower concentration range, but the line width in the higher-concentration range, which is investigated in the present investigation, can not be accounted for by the g-tensor anisotropy. Hence, it is supposed that electron spin exchange or nuclear quadrupole interaction contributes in the higher-concentration range. The latter can, however, be eliminated by the line width measurement in a deuterium measurement in a deuterium oxide solution, and so it may be concluded that electron spin exchange is the main contribution to the line width in the higher-concentration range. This is in accordance with the proposal of Jones. Furthermore, we could show that, by calculation of the line shape for Bloch’s equation, including exchange interactions, the exchange frequency of 5.4×107 sec−1 can give a line fitting the observed line shape for the 7.8×10−2 mol/l solution. This result can be taken as another evidence showing that the electron spin exchange is the main source of the line width in the higher-concentration range.
The Effects of Organic Additives on the Solubilities and CMC’s of Potassium Alkyl Sulfates in Water. II. Effects of Some Nonhydroxy Compounds
Authors: Shirahama Keishiro , Hayashi Makoto , Matuura Ryohei
Published: July 2006

Solubilities and critical micelle concentrations (CMC) of potassium dodecyl sulfate (KDS) and hexadecyl sulfate (KHS) were measured in aqueous solutions to which dioxane, acetone, urea, or dimethyl sulfoxide had been added over the temperature range of 5–40°C. It was found that all additives mentioned above raised solubility and CMC with an exception for dioxane which showed a slight minimum on a CMC-additive concentration curve. Solvent effects on the alkyl and ionic groups of a surfactant molecule were separated by considering the difference of the standard free energy change for the solution process of KHS and that of KDS. It was deduced that a primary effect on the alkyl group is the one that a strongly cohesive solvent, water, is replaced by a less cohesive organic solvent and other mechamisms, such as an effect on the water structure, follow as the secondary. In terms of the above considerations, effects on the Krafft point were also referred to.
Reactions of Ions in the Radiolysis of Liquid Propane
Authors: Tanno Kuniyasu , Shida Shoji
Published: July 2006

The reactions of ions, especially fragmentation of excited ions and the subsequent reactions of fragment ions in the radiolysis of liquid propane have been investigated by the use of charge scavengers such as sulfur hexafluoride (SF6) and ammonia (NH3). It has been confirmed that the fragment ions are produced by the dissociation of the excited parent ion prior to the parent ion-electron recombination. The yields of C2H5+ and C3H7+ have been measured by the use of the reaction, RH++ NH3→R+ NH4, with the results G≥0.28 and ∼1.1 respectively. These ions neutralize with electrons to form ethylene or propylene. The hydride ion transfer reaction between C2H5+ and propane may be competing with the neutralization of C2H5+ by electron in the absence of an additive. The yields of fragment ions are compared in the radiolysis of several saturated hydrocarbons.
Electron Diffraction Studies of Formaldehyde, Acetaldehyde and Acetone
Authors: Kato Chuichi , Konaka Shigehiro , Iijima Takao , Kimura Masao
Published: July 2006

The molecular structures of formaldehyde, acetaldehyde, and acetone have been investigated by the sector-microphotometer method of electron diffraction. Certain of the bonded interatomic distances, rg, were determined to be as follows: for formaldehyde, r(C–O)=1.2093±0.0033 Å and r(C-H)=1.0967±0.0535 Å; for acetaldehyde, r(C=O)=1.2085±0.0033 Å and r(C–C)=1.5142±0.0051 Å; for acetone, r(C=O)=1.2110±0.0041 Å and r(C–C)=1.5167±0.0048 Å. The value of rg(C=O) for formaldehyde was perfectly consistent wth the zero-point average distance, rz(C=O), determined by microwave spectroscopy.
The Crystal and Molecular Structure of Carbazole
Authors: Kurahashi Masayasu , Fukuyo Makoto , Shimada Akira , Furusaki Akio , Nitta Isamu
Published: July 2006

The crystal structure of carbazole has been refined with three-dimensional X-ray data. Single crystals obtained from the melt are orthorhombic with four molecules in a unit cell of the dimensions a=7.772, b=19.182 and c=5.725 Å; space group is Pnma. Positional and thermal parameters were obtained by the least-squares method. The final discrepancy index R is 10.9% excluding zero intensity data. The e.s.d.’s in bond lengths not involving hydrogen atoms are 0.006–0.010 Å, and the corresponding errors in bond angles are about 0.5°. The molecule is planar within the deviation of 0.03 Å. A crystallographic mirror plane normal to the b-axis passes through the nitrogen atom and is perpendicular to the molecular plane. Comparison of the observed and theoretical bond lengths is made with discussion thereof. Some physical properties related to the crystal structure are also discussed by comparing its structure with that of fluorene. With the help of thermodynamical data, it has been argued that the hydrogen bond of N–H···N between molecules is not formed not only in the crystalline state but also in the liquid state.
Theory of Photoselection for Zeeman Split Phosphorescence
Authors: Azumi Tohru , Nagakura Saburo
Published: July 2006

General equations applicable to photoselection experiments for Zeeman split phosphorescence are derived. The general equations are also extended to the cases where excitation and observation are effected with unpolarized light, and expressions for the ratio of phosphorescence intensities of the three split subcomponents are obtained. Some comments on experimentation are made.
The Mechanism of the Scintillation from a Benzene Solution of p-Terphenyl
Authors: Saito Tsunenari , Sato Shin
Published: July 2006

The luminescence from a benzene solution containing p-terphenyl induced by γ-ray irradiation has been compared with that induced by UV irradiation at 2500 Å in the presence of various quenchers. The quenching efficiencies of electron and positive ion scavengers (SF6, N2O, CO2 and NH3) were found to be greater for the γ-ray excitation than for the UV excitation, while 1,3-butadiene, which is known as a quencher for excited benzene, (1B2u), showed almost the same efficiency for both modes of excitation. These results suggest that, even in a benzene solution, a series of ionic reactions is partly responsible for the formation of the scintillating state of p-terphenyl, and that the apparent quenching effect of ion scavengers is mainly due to their interference in the formation of the excited state of the benzene which is produced by the recombination reaction between the benzene cation and an electron. It was estimated that more than 30% of the excited state of benzene is formed by the recombination reaction.
ESR Studies of Bis-(N,N-diethylethylenediamine)copper(II) Perchlorate
Authors: Yokoi Hiroshi , Sai Mitsuru , Isobe Taro
Published: July 2006

The ESR of bis-(N,N-diethylethylenediamine)copper(II) perchlorate has been examined in the polycrystalline state at three temperatures corresponding to the color change in the copper (II) complex due to thermochromism, in the glassy state of an aqueous solution at the temperature of liquid nitrogen, and in the magnetically-diluted state in diamagnetic bis-(N,N-diethylethylenediamine)nickel(II) perchlorate powder at three temperatures corresponding to the color change of the diluent due to thermochromism. The g and A values for square planar copper(II) complexes have been discussed in connection with the strength of the axial ligand field. The ESR results indicate that the structure of bis-(N,N-diethylethylenediamine)copper(II) perchlorate changes remarkably according to its circumstances, and possible mechanisms for the thermochromism have been suggested.
The Kinetics of the Autoxidation of Ferrous Ions in Aqueous Tripolyphosphate Solutions
Authors: Kurimura Yoshimi , Kuriyama Hideo
Published: July 2006

The kinetics of the autoxidation of ferrous ions in tripolyphosphate solutions (pH 2–8) at an ionic strength of 0.20 m NaClO4 was studied using a spectrophotometric technique. The rate expression for the oxidation reaction is given by:

d[Fe(III)]⁄dt=4kI[FeII(Htpp4−)][O2]+4kII[FeII(Htpp4−)2][O2],

and 4kII found is to be 1.0×102  m−1 sec−1 at 15°C. The simultaneous reaction paths of

FeII(Htpp4−)+O2\xrightarrowkIFeIII(Htpp4−)+O2- and FeII(Htpp4−)2+O2\xrightarrowkIIFeIII(Htpp4−)2+O2-

are consistent with the results obtained. When there is an excess of the triphosphate solution in the pH range from 6 to 8, the latter may be the rate-determining step. The acceleration of the oxidation of the ferrous ions in the triphosphate solution may be due to the fact that the stabilization of the oxidation products, FeIII(Htpp4−) and FeIII(Htpp4−)2, is greater than that of the corresponding ferrous triphosphate complexes. As the activation parameters for the latter reaction, the experiments gave the values of ΔH\eweq∼10 kcal mol−1 and ΔS\eweq∼−25 cal mol−1. deg−1. The negative and relatively small value of the entropy of activation suggests that the activated complex is more extensively hydrated than is the ferrous complex of FeII(Htpp4−)2.
Syntheses and Reactions of N-(Phenylpyruvoyl) Amino Acids
Authors: Chigira Yasuhiro , Masaki Mitsuo , Ohta Masaki
Published: July 2006

α-Ethoxy- and α-acetoxycinnamoyl chlorides were synthesized by treatments of α-ethoxy-and α-acetoxycinnamic acid with thionyl chloride and oxalyl chloride, respectively, and reactions of ammo acid esters with the cinnamoyl chlorides were investigated in order to seek for a synthetic method of N-(phenylpyruvoyl) amino acids. N-Hydroxy- or N-benzyloxy-Dl-alanine esters prepared from 2-bromopropionic esters and hydroxylamine or benzyloxyamine were treated with α-ethoxycinnamoyl chloride to give the corresponding N-(α-ethoxycinnamoyl) derivatives. Treatment of l-leucine ethyl ester with α-acetoxycinnamoyl chloride afforded N-(α-acetoxycinnamoyl)-l-leucine ethyl ester, the removal of the acetyl group from which was readily accomplished under mild, basic conditions, and N-(phenylpyruvoyl)-l-leucine ester was obtained. Treatment of the ester with ammonia yielded 3-benzylidene-6-isobutyl-2,5-piperazinedione.
Oscillopolarographic Behaviour of Lanthanide Ions at the Dropping and Hanging-drop Mercury Electrodes
Authors: Iwase Akio , Yokoyama Chieko
Published: July 2006

The oscillopolarographic behaviour of lanthanide ions at the dropping mercury electrode and hanging-drop mercury electrode was discussed. The variations of incision depth on the oscillopolarograms with a dropping mercury electrode in KSGN, KCl, KBr and NaClO4 at pH 3.65 and 4.65 were found to depend on the first ionization potentials and the basicity of the lanthanide. On the basis of the results obtained it can therefore be presumed that the electrode reaction rate increases with the increase of the first ionization potentials.
Syntheses and Properties of Some Metal Bromo-Dithiolium Complexes
Authors: Ouchi Akira , Eguchi Hiroshi , Takeuchi Toshio , Furuhashi Akiko
Published: July 2006

The bromo-3-methyl-5-phenyl-1,2-dithiol-1-ium complexes were obtained from metal benzoylacetonate, using hydrogen sulfide and bromine with a catalyst of hydrogen bromide. These complexes resemble bromo-bis(3,5-dimethyl-1,2-dithiol-1-ium) complexes and many of them are of the high-spin type. The Zn(II) and Cd(II) complexes are of the ML2Br4 type (where M=metal and L=3-methyl-5-phenyl-1,2-dithiol-1-ium), like 3,5-dimethyl-1,2-dithiol-1-ium complexes, while Cu(I) is of the MLBr2 type. However the analytical results shows that the Mn(II), Fe(II) and Co(II) complexes are of the ML2Br3 type. Infrared spectra as well as electronic spectra are shown and discussed.
Methods of Preparing the 2,2′-Dipyridyl and 1,10-Phenanthroline Cobalt(III) Complexes of the [CoX2dip2]- and [CoX2phen2]-Type
Authors: Maki Nobufumi
Published: July 2006

The bis(2,2′-dipyridyl) and bis(1,10-phenanthroline) cobalt(III) complexes of the [CoX2N4]-type, including the following new compounds, have been prepared: [Co(CN)2dip2]NO3·7H2O, [Co-(CN)2dip2]2SO4·12H2O, Na[Co(SO3)2dip2]·5H2O, Na[Co(S2O3)2dip2]·7H2O [Co(N3)2dip2]N3·2H2O, [Co(N3)2dip2]ClO4, [Co(N3)2dip2]2SO4·5H2O, [Co(N3)2dip2]NO3·2H2O, [Co(N3)2dip2]Cl·3H2O, [Co(SCN)2dip2]NCS·\frac52H2O, [Co(SCN)2dip2]ClO4·2H2O, [Co(SCN)2dip2]Cl·3H2O, K[Co(SO3)2phen2]·5H2O, [Co(NO2)2phen2]Cl·4H2O, Na[Co(S2O3)2phen2], [Co(N3)2phen2]N3[Co(CN)2phen2]NO3·6H2O, [Co(CN)2phen2]Cl·4H2O. The known compounds, including the cobalt(II) and cobalt(III) complexes of the luteo type, have also been prepared by methods other than those described hitherto in the literature. The absorption spectra in the visible and ultraviolet regions have been measured and compared with those of the bis(ethylenediamine)cobalt-(III) complexes. The rhodanato-cobalt(III) complexes, [Co(SCN)2dip2]ClO4·2H2O and [Co-(SCN)2phen2]NCS, have been ascertained to be the sulfur-bonded thiocyanato complexes on the evidence of the absorption spectra in the visible and infrared regions.
Reaction of N-(α-Acetoxycinnamoyl)-N-hydroxy Derivatives of Dl-Alanine Esters. Formation of Imidazolidinone and Its Transformations into Pyrrolidinedione and Oxazolidinone
Authors: Chigira Yasuhiro , Masaki Mitsuo , Ohta Masaki
Published: July 2006

Treatment of N-benzyloxy-Dl-alanine ethyl ester (I) with α-acetoxycinnamoyl chloride (II) gave N-(α-acetoxycinnamoyl)-N-benzyloxy-Dl-alanine ethyl ester (III), which was treated with aqueous sodium bicarbonate, piperidine or hydroxylamine to afford N-benzyloxy-N-(phenyl-pyruvoyl)-Dl-alanine ethyl ester (IV). Reaction of III or IV with ammonia afforded 5-benzylidene-2-methyl-4-oxo-2-imidazolidinecarboxylic acid (V), which was transformed into 5-methyl-4-phenyl-2,3-pyrrolidinedione (VI) by treatment with aqueous sodium hydroxide and into methyl 5-benzylidene-2-methyl-4-oxo-2-oxazolidinecarboxylate (VII) by treatment with methanolic hydrogen chloride. VI was also derived from III or IV by treatment with sodium hydroxide. N-(α-Acetoxycinnamoyl)-N-hydroxy-Dl-alanine t-butyl ester prepared from N-hydroxy-Dl-alanine t-butyl ester and II, was treated with aqueous sodium hydroxide to give t-butyl 5-benzylidene-2-methyl-4-oxo-2-oxazolidinecarboxylate.
Spectrophotometric Determination of l-Ascorbic Acid
Authors: Ogata Yoshiro , Kosugi Yoshio
Published: July 2006

A novel quantitative determination of l-ascorbic acid by UV spectrophotometry in a HCl-KCl buffer has been developed. Ascorbic acid (λmax 244 mμ) of over 2×10−5  m can quantitatively be determined by this method. Several oxidizing, reducing, acidic or basic reagents and other organic compounds which may be present together with ascorbic acid in ordinary drugs and drinks do not interfere the determination.