bluuebunny/crossref_metadata_2025 huggingface dataset:
The Protonation of Aromatic Hydrocarbon Radical Anions. I. A Comparison of Methods and a Study of the Mechanism
Authors: Hayano Shigeo , Fujihira Masamichi
Published: July 2006

The protonation mechanism of the aromatic hydrocarbon radical anions, such as biphenyl, naphthalene, phenanthrene, anthracene, 1,2-benzanthracene, and pyrene, in dimethylformamide (DMF) and water mixtures was studied. Three methods of measuring the concentration of the radical anions, i.e. polarography and ESR and UV absorption spectroscopy, were compared with each other by making simultaneous measurements of the same anthraquinone radical anion solution. A good linear relation of the polarographic anodic diffusion current to the UV absorbance was found, while the ESR signal intensity had linear relations with neither of the others in the system which contained an excessive number of parent molecules, 2×10−3m. The change in the visible absorption spectra of the aromatic hydrocarbon radical anions as a function of the time suggested that all the aromatic hydrocarbon radical anions decay by a first-order reaction. As a result, the radical anions were considered to decay through the following sequence:

R\ewdot+H2O\oversetk→RH·+OH−, RH·+R\ewdot\ightleftharpoonsRH−+R, and RH−+H2O\oversetk′→RH2+OH−.
The Solubilization of Orange OT in Anionic Surfactant Solutions: A Polarographic Study
Authors: Hayano Shigeo , Shinozuka Noriko
Published: July 2006

Orange OT (1-o-tolyl-azo-β-naphthol) solubilized in sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (SDBS) solutions showed a well-defined irreversible polarographic wave. The proportionality of the limiting current to the square root of the mercury height and to the dye concentration indicates the wave to be diffusion-controlled. It is noted that the anionic surfactants showed the waves due to the adsorption-de-sorption and reorientation of the surfactant molecules on the electrode. The apparent diffusion coefficients of the solubilized dye calculated from the polarographic data were in good agreement with those of the anionic surfactant micelle with electrolyte. We may conclude that the polarographic diffusion coefficient of the solubilized dye is equal to that of the micelle of the solubilizer surfactant. The marked surfactant concentration dependence of the diffusion coefficient was observed with both surfactants and was attributed to the interaction of the micelles. The transfer coefficient of the electrode reaction of Orange OT increased with an increase in the concentration of the surfactant. This tendency is different from the effect of the surface-active agents on the transfer coefficient in the reduction of inorganic ions. From the experimental observations, it seems that the electrode reaction of the solubilized dye is little effected by the charged micelles.
Proton Spin-Lattice Relaxation Studies of Intermolecular Interactions in the Mixtures of Chloroform and Proton-Acceptor Solvents
Authors: Sato Kazuo , Nishioka Atsuo
Published: July 2006

Proton spin-lattice relaxation measurements were carried out on chloroform in carbon tetrachloride, benzene, pyridine, acetone, and dimethylsulfoxide (DMSO) in order to investigate the effect of the intermolecular interaction on the spin-lattice relaxation time, T1 of chloroform. It was found that the order of the effects of solvents on T1 is as follows: DMSO>acetone, pyridine>benzene, carbon tetrachloride; this order corresponds to that of the association constant of chloroform with these solvents. The T1 values of benzene and acetone were also determined on chloroform-benzene and chloroform-acetone mixtures. On the basis of the results obtained on these solutions together with the results on the T1 of chloroform in various solvents, we estimated the lifetimes of the chloroform-benzene complex and of the chloroform-acetone hydrogen-bonding complex. We tried to keep the proton-density constant throughout the solutions, in order to avoid an ambiguity arising from its change, by adopting the corresponding deuterated compounds.
Studies of Seven-Membered Heterocyclic Compounds Containing Nitrogen. X. Syntheses of 5,6,8,9-Tetrahydro-7H-pyrimido[4,5-d]azepines
Authors: Yamamoto Hiroshi , Nakata Masaru , Morosawa Shiro , Yokoo Akira
Published: July 2006

5,6,8,9-Tetrahydro-7H-pyrimido[4,5-d]azepine and some of its derivatives were synthesized. 6-Acetyl-3-hydroxy-4,5,7,8-tetrahydro-6H-pyrazolo[3,4-d]azepine was also synthesized.
The Reactions of Photogenerated Solvated Electrons in Methanolic Solutions of Potassium Iodide
Authors: Seki Hiroshi , Imamura Masashi
Published: July 2006

Hydrogen formation from UV-irradiated potassium iodide solutions was studied using CH3OH and CH3OD as the solvents and nitrous oxide and acids as the solvated-electron scavengers. The maximum quantum yield of the solvated electron in CH3OH was found to be 0.6 both in nitrous oxide and in acid solutions. It was concluded that the solvated electron produces hydrogen in pure methanol through Reaction (1), e−solv→H+CH3O−, with a quantum yield of 0.35 at 25°. The rate constant of this reaction is 5.4×105sec−1, corresponding to a half-life of 1.3 μsec. From the results obtained with acid solutions, it was also concluded that nitrous oxide reacts with a solvated electron to produce one molecule of nitrogen in neutral methanol.
Preparation of Chromium(III) and Cobalt(III) Complexes with d,l-α-Phenylalanine-N,N-diacetic Acid
Authors: Uehara Akira , Kyuno Eishin , Tsuchiya Ryokichi
Published: July 2006

The following chromium(III) and cobalt(III) complexes with PADA (d,l-α-phenylalanine-N,N-diacetic acid) were prepared: K[Cr(OH)pada(H2O)]·5H2O (violet) (I), K[Cr(OH)pada(H2O)2]·3H2O (green)(II), (enH2)1⁄2[Cr(OH)pada(H2O)2] (green) (III), [Cr pada(o-phen)]·H2O (brown) (IV), K2[Cr(ox)pada]·2H2O (violet) (V), K[Co(OH)pada(H2O)]·5H2O (blue-violet) (VI), and K2[Co2(OH)2(pada)2] (brown-pink) (VII). On the basis of electronic spectra in both aqueous solution and solid state, it was found that PADA behaves toward central metal as a quadridentate ligand in complexes I, IV, V, VI, and VII; in other words, unlike the case of nitrilotriacetic acid (NTA), nitriloisopropionicdiacetic acid (NIPDA) and l-leucine-N,N-diacetic acid (LDA), PADA did not give different coordinating structures to the respective complexes in solid state and aqueous solution. From thermal analysis with derivatograph in the reaction processes of complex VI, it was found that the complex liberates one mole of coordinating water at about 170–180°C, resulting in the formation of the diol complex VII.
Studies on Cobaloxime Compounds. IV. The Polarography of Cobaloximes
Authors: Hohokabe Yorikatsu , Yamazaki Noboru
Published: July 2006

Various types of cobaloximes, e.g., Co-alkyl derivatives with different bases as an axial ligand and polymeric cobaloximes with the general formula of Co(OH)(DH)2(Copoly—AM-VPy) (DH: dimethylglyoximato monoanion) in which Copoly—AM-VPy is a low-molecular-weight copolymer of acrylamide and 4-vinylpyridine, were prepared, and their half-wave potentials in cathodic reduction were compared to each other and to those of a few vitamin B12 compounds. All of them showed a single irreversible cathodic wave. Methyl- and cyano-cobaloximes were reduced at more negative potentials than the corresponding methylcobalamin and cyanocobal-amin(vitamin B12). The half-wave potential of methylcobaloxime shifted in the direction of the more negative potentials as the donating strength of the axial base increased. This was correlated with the charge-transfer transition energies of those cobaloximes as determined from their electronic spectra. The polymeric cobaloximes were reduced at less negative potentials than the others.
Several Novel Ru(VI) and Ru(IV) Complexes Derived from [RuO4bipy] and [RuO3phen]2O
Authors: Ishiyama Toshio
Published: July 2006

Five novel neutral complexes of ruthenium(VI) and ruthenium(IV) with 2,2′-bipyridine and 1,10-phenanthroline, [RuO2(OH)2bipy]·3H2O, [Ru(OH)3phen]2O, [RuO2bipy2]·3H2O, [RuO2bipy·phen]·3H2O and [RuO2phen2], were prepared and characterized by a study of their infrared, visible and ultraviolet absorption spectra, and by polarographic measurements. [RuO2(OH)2bipy] and [Ru(OH)3phen]2O were obtained by the reduction of previously-reported complexes, [RuO4bipy] and [RuO3phen]2O respectively, with methanol, and [RuO2bipy2], [RuO2bipy·phen] and [RuO2phen2], by the reactions of [RuO4bipy] and [RuO3phen]2O in methanol with 2,2′-bipyridine and 1,10-phenanthroline respectively. [RuO2bipy·phen] and [RuO2phen2] were also obtained in methanol by the substitution reactions of [RuO2bipy2] and [RuO2bipy·phen] with 1,10-phenanthroline respectively. The five complexes were all diamagnetic. [RuO2(OH)2bipy] was assumed to be a “ruthenyl” complex with two oxide ions coordinated at the trans positions, like such well-known trans-dioxoruthenyl analogues as Cs2[RuO2Cl4] and [RuO2(OH)2(NH3)2], and [Ru(OH)3phen]2O was assumed to be a binuclear complex with an oxygen-bridge between ruthenium atoms. [RuO2bipy2], [RuO2bipy·phen], and [RuO2phen2] were assumed to be mononuclear complexes with two oxide ions coordinated at the trans positions, and their oxidation numbers were found polarographically, to be 4.
The Chemical-transport Reaction of Spinel-type Oxides
Authors: Nagasawa Koichi , Bando Yoshichika , Takada Toshio
Published: July 2006

Single crystals and thin films of spinel-type oxides were prepared by a chemical-transport reaction in a closed system, using HCl gas as the transport agent. This paper will report on the preparation conditions and the reaction process of the chemical-transport reaction. The reaction process of Co3O4 was found to be different from that of other oxides, since Co3O4 was dissociated into CoO and O2 in the closed tube. The reaction process was explained by the difference in the dissociated oxygen pressure between the source zone and the crystallization zone in the system. The chemical-transport reaction of NiFe2O4 was applied to the preparation of thin film. The single-crystal thin films were epitaxially grown on the (110) and (111) surfaces of MgO.
The Effect of Axial Pyridine Ligands on the Charge Transfer Bands of trans-Bis(dimethylglyoximato)Cobalt(III) and -Iron(II) Complexes
Authors: Yamano Yukio , Masuda Isao , Shinra Koichiro
Published: July 2006

The electronic absorption spectra of [CoIII(dmgH)2B2]+ and [FeII(dmgH)2B2] (dmgH=dimethylglyoximate monoanion and B=pyridine derivatives) are inspected with respect to the effect of the axial pyridine ligands on the charge-transfer bands of the complexes. The characteristic bands observed in the 275–305 mμ region for the Co(III) complexes and in the 485–555 mμ region for the Fe(II) complexes, which have been assigned to a metal→oxime charge-transfer band, are shifted to shorter wavelengths with a decrease in the basicity of the pyridine derivatives. The results have been discussed by taking into account the π-interaction of the dπ(dxz, dyz) orbital of the central metal ion with the empty π-orbitals of both the dimethylglyoximate and the pyridine derivatives. It is suggested that the π-interaction is stronger in the Fe(II) complexes than in the Co(III) complexes, while the σ-bond is stronger in the latter. The infrared spectral evidence that the C=N stretching frequency is dependent on the axial pyridine derivatives, and that it is observed at a lower frequency in the Fe(II) than in the Co(III) complexes, is consistent with the above results.
Kinetics and Mechanism of the Ligand Substitution Reaction of the Mercury(II)-4-(2-pyridylazo)resorcinol Complex with 1,2-Cyclohexanediamine-N,N,N′,N′-tetraacetic Acid
Authors: Funahashi Shigenobu , Tabata Masaaki , Tanaka Motoharu
Published: July 2006

Kinetics and mechanism of the ligand substitution reaction of the mercury(II)-PAR complex with CyDTA were studied at 25°C in the presence of halogenide ion at an ionic strength of 0.1. The rate law can be written as

−\fracd[Hg(par)22−]dt=(k1′[H+]+k2′+k3,X′[H+][X−])\frac[Hg(par)22−][Hpar−][Hcydta3−]

where X− refers to a halogenide ion (chloride, bromide, iodide). The rate constants k1′, k2′, and k3,X′ were determined as: k1′=(2.4±0.1)×107  m−1 sec−1, k2′=(1.9±0.1)×10−2 sec−1, k3,Cl′=(4.5±0.2)×109  m−2 sec−1, k3,Br′=(3.2±0.1)×1011  m−2 sec−1, k3,I′=(5.6±0.2)×1014  m−2 sec−1. The rate constants for the paths involving mixed hydroxo and halogeno complexes (k2′ and k3,X′) are quantitatively accounted for in terms of electron donation of ligands OH− and X−.
The Crystal Structure of 2,2′-Bipyridinium Tetrabromocobaltate(II)
Authors: Koda Shigetaka , Ooi Shun’ichiro , Kuroya Hisao
Published: July 2006

The crystal structure of 2,2′-bipyridinium tetrabromocobaltate(II) has been established by successive Fourier analyses. The atomic parameters were refined by least-squares techniques, using the three-dimensional X-ray data, to an R factor of 0.127 for 1461 non-zero reflections. The complex crystallizes in the space group P21/c with four formula units in the unit cell with dimensions of a=8.42, b=14.00, c=12.88 Å, and β=98.7°. The crystal consists of slightly distorted tetrahedral [CoBr4]2− anions and 2,2′-bipyridinium cations, in which two pyridinium ring planes are inclined toward one another at an angle of 39°. The two N+–H groups in the cation participate in N+–H···Br− type hydrogen bonds (N···Br=3.23 Å and 3.31 Å). The mean value of the four Co–Br bond lengths is 2.42 Å.
Sound Velocity in Aqueous Solutions of Lead Nitrate and Ammonium Iodide
Authors: Nomoto Otohiko , Endo Harumi
Published: July 2006

The sound velocity in aqueous solutions of NH4I and Pb(NO3)2 is investigated in relation to the temperature and the concentration. In both solutions the V(T) curves show maxima Vp at the peak temperature Tp the Tp shifting to a lower temperature with an increase in the concentration. While the shift of Tp is sensibly linear with the concentration for Pb(NO3)2, the curve for NH4I is almost constant up to 25 wt%, though it decreases linearly above this concentration. This corresponds to the rather abrupt change in the degree of dissociation obtained from the conductivity data. The constancy of Tp below 25wt% is tentatively explained on the basis of Danford and Levy’s X-ray diffraction study which concluded that NH3 is included in cavities of the water framework and that the framework molecules are partially replaced by NH3.
Studies of the Pyrolysis of Triglycerides
Authors: Kitamura Kazuo
Published: July 2006

The pyrolysis of triglycerides (trilaurin and tripalmitin) in an atmosphere of nitrogen at 300–700°C has been attempted. Fatty acids, acrolein, ketones, and olefins have been identified as pyrolysis products. As intermediates of the pyrolysis, unsaturated glycol difatty acid esters and acid anhydrides were also detected. These results suggest a reaction mechanism of the pyrolysis involving the above compounds.
A Novel Synthesis of 4H-1,3-Thiazin-4-one Derivatives
Authors: Yokoyama Masataka
Published: July 2006

4H-2,5,6-Substituted-2,3-dihydro-1,3-thiazin-4-ones were synthesized by the condensation reaction of β-alkylthio-β-mercapto-α-cyanoacrylamide with a variety of ketones and aldehydes in an acidic medium.
The Radical Polymerization and Copolymerization of Triallylidene Sorbitol with Styrene or Acrylonitrile
Authors: Oughi Tatsuro , Yagughi Yoshikazu , Oiwa Masayoshi
Published: July 2006

The polymerization of triallylidene sorbitol (TAS) and the copolymerization of TAS with styrene (St) or acrylonitrile (AN) have been carried out, using benzoyl peroxide as an initiator at 80°C. They were kinetically investigated in relation to the degradative or effective chain transfer by the allylidene group, and by the cyclization by three double bonds. The results can be summarized as follows: 1) the relation among the rate of polymerization, Rp, the initiator concentration, (I), and the monomer concentration, (M), can be expressed by the following equation: ((I)/Rp–a)−1=A(M)+B, where a, A, and B are constant; 2) the ratio of the rate of unimolecular cyclization to the total rate of bimolecular propagation and the chain transfer of uncyclized radical was estimated to be 0.291; 3) the degree of polymerization depends on the monomer concentration, but not on the initiator concentration; 4) the rates of copolymerization decrease markedly with an increase in the TAS or tricrotylidene sorbitol (TCS) mole fraction in monomer mixtures; and 5) the following monomer reactivity ratios were ascertained: St(M1)-TAS(M2)r1=4.60, r2=0.13, AN(M1)-TAS(M2) r1=0.70, r2=0.26, St(M1)-TCS(M2) r=2.31, r2=0.39, AN(M1)-TCS(M2) r1=0.30, r2=0.36. The Q and e values for the functional group were calculated from the above values as 0.05 and −0.08 (TAS), and 0.10 and −0.25 (TCS) respectively.
The Hofmann Rearrangement. I. Kinetic Substituent Effects of ortho-, meta-, and para-Substituted N-Bromobenzamides
Authors: Imamoto Tsuneo , Tsuno Yuho , Yukawa Yasuhide
Published: July 2006

The kinetic substituent effects on the Hofmann rearrangements of ortho-, meta-, and para-substituted N-bromobenzamides were studied in an aqueous sodium hydroxide solution. The rate constants of the meta- and para-derivatives were correlated by means of our equation:

logk⁄k0=−2.39(σ0+0.41Δ\barσR+)+0.002

The reaction rates of ortho-derivatives were found to be 2–20 times faster than those of the corresponding para-derivatives. The reaction mechanism of this rearrangement was discussed in terms of LFER, the ortho/para rate ratios, and the activation parameters; as a result, the concerted mechanism (the participation of the phenyl group in electron-deficient nitrogen at the transition state) was favored rather than the two-step mechanism. The similarity of the reaction mechanism of the Hofmann to the Lossen rearrangement was also shown on the basis of LFER.
Photochemical Reaction of 3,4-DiphenyIsydnone
Authors: Huseya Yoshiharu , Chinone Akiko , Ohta Masaki
Published: July 2006

In a recent communication, we proposed 1H-1,3-diphenyldiazirine for the photolysis product of 3,4-diphenylsydnone. However, it was found later that the product was identical with the already known 2,4,5-triphenyl-1,2,3-triazole. In this paper, details of the photolysis of 3,4-diphenylsydnone and identification of the product are described. The formation of triazole derivative by the photolysis of 3,4-diphenylsydnone seems to be interesting. The reaction mechanisms are discussed.
Aroyloxy-Radikal. Die Aktivierungsenergien bei der Kohlendioxyd-Abspaltung und bei der Anlagerung an Benzol-Doppelbindung
Authors: Suehiro Tadashi , Ishida Mototoshi
Published: July 2006

Bei der Einwirkung von Trityl-Radikal auf Benzoylperoxyd-carbonyl-14C,p-Chlorbenzoylperoxyd-carbonyl-14C bzw. auf p-Methoxybenzoylperoxyd-carbonyl-14C in Benzol bei 25°C und 45°C wurde die Ausbeute an Kohlendioxyd, Tetraphenylmethan und an Benzoesäure-trityl-ester nach der Isotopen-Verdünnungsmethode bestimmt. Aus der Abhängigkeit der Ausbeute von Temperatur wurden die relativen Aktivierungsenergien der Aroyloxy-Radikale bei der Kohlendioxyd-Abspaltung (E1,r) und bei der Anlagerung an die Benzol-Doppelbindung (E4,r) im Vergleich zu der bei der Kombination mit Trityl-Radikal (E5) errechnet. Die relativen Aktivierungsenergien waren wie folgt: Bei Benzoyloxy-Radikal E1,r=12.9 Kcal/Mol und E4,r=6.3 Kcal/Mol; bei p-Chlorbenzoyloxy-Radikal E1,r=13.5 Kcal/Mol und E4,r=6.2 Kcal/Mol; bei p-Methoxybenzoyloxy-Radikal E1,r=14.7 Kcal/ Mol und E4,r=6.1 Kcal/Mol.
Configuration Interaction Studies on Contact Shift and Contact Nuclear Spin-Spin Coupling in Paramagnetic Transition Metal Complexes
Authors: Katô Hajime , Kato Hiroshi
Published: July 2006

The magnitude of the contact shift for hydrogen nuclei is directly related to the unpaired electron density, ρH, on the proton. The mechanism by which the unpaired electrons transfer from the transition metal d-orbitals to the ligand orbitals is studied on the basis of the method of intergroup (ligand and metal) configuration interaction. The ρH is given as a sum of two terms, ρHP and ρHD, due to the spin-polarization mechanism and the spin-delocalization mechanism respectively. When the interaction between metal and ligand is restricted to a localized bond N–M, such as nickel(II)-benzylamine, ρHP\simeq−(CMm)2|χH(0)|2πHN⁄3\simeq0.001–0.0001 (Here πHN is the mutual atom(H)-atom(N) polarizability.). When the interaction between metal and ligand is not restricted to a special localized bond, as in metalocene, ρHP\simeq−(CMm)2|χH(0)|2πHH⁄3\simeq0.01–0.001. The spin delocalization term has the order of magnitude of: ρHP\simeq−(CMm)2(βMN)2|χH(0)|2(PHN)2⁄2(δE)2 (Here PHN is the bond order between the H and N atomic orbitals.). If the proton H is not directly bonded to the atom N, ρHD\simeq0.0001. If the proton H is directly bonded to the atom N, ρHD\simeq0.001. By disregarding the contributions smaller than the order of magnitude O(S2), the formulation of the contact nuclear spin-spin coupling constant is derived. The most dominant term is identical with the formula which was derived by Pople and Santry for singlet free-ligand molecules.
Studies of the Surface of Titanium Dioxide. I. The Effect of Reduction by Hydrogen on the Heat of Immersion in Water
Authors: Iwaki Toru , Miura Masaji
Published: July 2006

The reduced state of the surface of titanium dioxide was studied by the measurement of the heat of immersion in water. When the titanium dioxide was reduced by hydrogen at 500°C, the heat value decreased appreciably with an increase in the pressure of hydrogen, in contrast to the increase in the heat value due to the reduction by an organic contaminant. The heat value was not restored to the original state even after oxygen had been introduced at 500°C to the reduced sample, while the color of the sample returned to white from bluish gray. These phenomena were interpreted by examining the adsorption of water, the reduced amount, and the reflectance spectrum.
Positron-lifetime Measurements in Polymerizing Organic Solids
Authors: Ito Yasuo , Okuda Kouji , Tabata Yoneho
Published: July 2006

The measurement of the e+ lifetime in solid monomers during polymerization has been carried out. The mechanism of solid-state polymerization can be analyzed by the measurement of the lifetime of positrons and the amounts of positronium formed. This method was applied to the solid-state polylmerization of acrylamide. It was found from the experiments that the lifetime spectrum changes remarkably in the induction period of polymerization. The decrease in the annihilation rate λ2 was interpreted in terms of the formation of a larger free volume during polymerization. The intensity of the slow component was also observed to decrease in the induction period of polymerization. The accumulation of active species which capture positrons and the decrease in the number of free volumes were suggested as explanations of the phenomena.
Radiotracer Studies on Adsorption of Surface Active Substance at Aqueous Surface. III. The Effects of Salt on the Adsorption of Sodium Dodecylsulfate
Authors: Tajima Kazuo
Published: July 2006

The adsorbed amounts were measured on the surface of aqueous solutions containing tritiated sodium dodecylsulfate (TSDS) and varying amounts of NaCl by the direct radiotracer method. The surface tensions were also measured for the same solutions by the drop-volume method. The Gibbs adsorption isotherm, derived without assuming the adsorption of the chloride ion, was applied, and the amounts of adsorption were calculated for both dodecylsulfate and chloride ions. The observed amounts of dodecylsulfate adsorption were confirmed to be in good agreement with those calculated, and the calculated amounts of chloride adsorption turned out to be nearly zero or slightly negative, which is usually theoretically assumed because of the ionic repulsion due to the adsorbed dodecylsulfate. Further, the adsorption of the dodecylsulfate ion attained a constant and saturate value beyond a certain concentration (SAC) below the critical micelle concentration (CMC). The logarithms of SAC were found to vary linearly with the logarithms of CMC for the range of salt concentration studied. The value of SAC being in a close relation with the surface phenomena is considered to be another measure of the surface activity of surfactants.
Effects of Pressure on the Chemical Properties of Solid Surfaces. V. The Surface Acidity of the Compressed Aluminum Sulfate
Authors: Kawakami Takeshi , Konno Akihiro , Ogino Yoshisada
Published: July 2006

In order to clarify the mechanism of the acidity change due to compression, aluminum sulfate was compressed under various pressures ranging from 0 to 4200 kg/cm2 and at a temperature of 20, 65, or 80°C, and the surface acidity and the structure of these samples were measured. It was found that the acidity change due to compression was proportionate to the protonic acid. Lewis acid was made to appear only by heating the sample at temperatures higher than 90°C. Further, for the purpose of increasing the surface acidity, the compression of the sample at lower temperatures was found to be more effective than the compression at higher temperatures. In addition to the spectroscopic data, the results of DTA and TGA experiments supported the idea that the observed acidity change resulted from the distortion of the structural unit of aluminum sulfate.
Ionization of Some Quinones by the Interaction with Aliphatic Amines
Authors: Yamaoka Tsuguo , Nagakura Saburo
Published: July 2006

The interactions of alkylamines with p-benzoquinone and its chloro-derivatives in ethanol and ethyl ether were studied by the rapid scan spectrophotometric method. The formation of anion radicals was found spectroscopically for the n-butylamine-p-benzoquinone, n-butylamine-chloranil, dimethylamine-p-benzoquinone, and tri-n-butylamine-chloranil systems. The rates of ionization reactions were determined to be 0.30 sec−1 mol−1 (at 253.7°K), 0.89 sec−1mol−1 (at 222.7°K), and 1.39 sec−1mol−1 (223.2°K) for the tri-n-butylamine-chloranil, n-butylamine-chloranil, and n-butylamine-p-benzoquinone systems, respectively. The activation energy for ionization of the tri-n-butylamine-chloranil system in ethanol was estimated to be 0.57 kcal/mol.
Structures of Bicyclo[2.2.2]octene and Bicyclo[2.2.2]octadiene as Studied by Gas Electron Diffraction
Authors: Yokozeki Akimichi , Kuchitsu Kozo
Published: July 2006

Bicyclo[2.2.2]oct-2-ene and bicyclo[2.2.2]octa-2,5-diene have been investigated by gas electron diffraction. They are found to have C2v symmetry in respect of the thermal-average nuclear positions. The structural parameters with estimated limits of error (the γg bond lengths and the angles difined in the γα structure) determined by a leastsquares analysis on the molecular intensities are as follows for octene and octadiene, respectively: C(sp3)–C(sp3) (weighted average of the C1–C7, and C7–C8 bonds)=1.549±0.008 and 1.553±0.017 Å, C(sp2)–C(sp3)=1.509±0.015 and 1.521±0.008 Å, C(sp2)–C(sp2)=1.341±0.008 and 1.339±0.005 Å, C(sp3)–H (average)=1.112±0.008 and 1.105±0.012 Å, ∠C–C=C=114.2±0.6° and 113.5±0.5°, The dihedral angle θ between the C1–C2–C3 C4 and C1–C6–C5–C4 planes=121.2±2.1° and 123.4±2.2°, ∠C=C–H=122.4±6.0° and 125.5±4.0°, ∠H–C–H=109.2±4.0° and 111.3±7.0°. A conformational analysis based on an empirical prescription of strain energies, similar to that of Jacob et al., and a molecular-orbital analysis (CNDO/2) have accounted for the observed bond angles given above to within 1.5°.
Some New Oxygenated Cobalt Complexes
Authors: Munakata Megumu
Published: July 2006

Cobalt(II) complexes with ornithine, 2,4-diaminobutyric acid and 2,3-diaminopropionic acid were studied as new oxygen complexes. The former complex was reversibly, while the latter two complexes were irreversibly oxygenated at room temperature. These oxygenated complexes were diamagnetic and showed electronic absorption spectra similar to that of oxygenated cobalt histidine complex, and they were assumed to be O2-bridged binuclear complexes, L2Co–O2–CoL2 (L: ligand). Cobalt and O2 of the binuclear complexes existed in the state of Co(III) and O22−, respectively. Thermodynamic measurements showed that oxygenation was an exothermal process, and deoxygenation an endothermal one. The reversibility correlated with the reduction potential of the central cobalt(III) ion and the enthalpy change of the oxygenation. Easier deoxygenation corresponded to more positive reduction potential and to smaller enthalpy change.
The Photonuclear Reactions Leading to 24Na and 28Mg
Authors: Saito Tatsuya
Published: July 2006

The photonuclear reaction yields of 24Na and 28Mg in magnesium, aluminum, silicon, phosphorus, and sulfur were obtained at energies between 20 MeV and 250 MeV by the induced radioactivity method. The 12C(γ,n)11C yield was used as a standard for the beam monitor. The excitation curves of the 27Al→24Na, 28Si→24Na, Si30→28Mg, 31P→24Na, 31P→28Mg, 32S→24Na, and 32S→28Mg reactions were obtained from the yields by the photon-difference method. Each of these excitation functions indicates a peak in the 50–70 MeV energy range, except in the case of the sulfur target, in which the peak is due to the contribution from the compound-nucleus process. The interaction of photons with nuclei at photon energies exceeding the peak energy region probably does not lead to the formation of the compound nucleus. In the energy range from 70 MeV up to 150 MeV, the cross sections are due to the contribution from the quasi-deuteron process. At energies above 150 MeV and up to 250 MeV, the quasi-deuteron and pion production processes compete. In the high-energy photonuclear reaction mechanisms, the quasi-deuteron and pion production processes must be considered at the initial cascade process, but the evaporation process may be considered after the cascade process.
Conductometric Determination of Ion-pair Formation Constants of Tris(ethylenediamine)cobalt(III) Ion with Maleate and Fumarate Ions in Aqueous Solutions
Authors: Katayama Shunzo , Tamamushi Reita
Published: July 2006

The conductance behavior of mixtures was investigated for the systems tris(ethylenediamine)cobalt(III)chloride-sodium maleate and tris(ethylenediamine)cobalt(III)chloride-sodium fumarate in aqueous solutions of various ionic strengths at 25°C. Appreciable deviation of the measured conductivity from additivity was attributed to the ion-pair formation of tris(ethylenediamine)cobalt(III) ion with maleate Ma2− and fumarate Fu2− ions. The concentration formation constants Kc at various ionic strengths were determined by means of computer analysis of the deviation. The thermodynamic ion-pair formation constants K at 25°C were as follows: logK=3.60 for [Co(en)3]3+·Ma2− and logK=2.95 for [Co(en)3]3+·Fu−2.
Hydrolysis of Nickel(II) Ion in Aqueous 3m Sodium Chloride Medium
Authors: Ohtaki Hitoshi , Biedermann Georg
Published: July 2006

The hydrolytic reaction of nickel ion was studied at 25°C in an aqueous 3m sodium chloride medium. In the range of the total nickel concentration of 0.0145–1.000m, the emf data obtained could be explained in terms of the formation of the complex Ni4(OH)4 (the charge is omitted), the formation constant of the species being found to be log*β4,4=−28.55±0.10, together with some minor species NiOH (log*β1,1≤−10.5) and Ni2OH(log*β1,2≤−10.5).
Studies of the Solvent Extraction of Potassium by Nitrobenzene in the Presence of Organic or Inorganic Acids
Authors: Iwachido Tadashi
Published: July 2006

Aromatic compounds with an acidic group, such as –OH, –SH, –COOH, –SO3H, >NH, (Remark: Graphics omitted.)CH, and (Remark: Graphics omitted.)B− (tetraphenylborate) were tested as extracting agents for potassium. The first four acids showed an extractability lower by far than that of the last three. Most inorganic acids exhibited no signs of extraction. Bulky and electronattracting substituents, such as nitro or halogen group, were proved to be effective in enhancing the extractability. The addition of iodine was also effective. A few kinds of surfactants showed considerably high extractability. Some factors influencing the extraction were speculated upon.
The Fluorine, Chlorine, Bromine, and Iodine Contents of Volcanic Rocks in Japan
Authors: Yoshida Minoru , Takahashi Kazuyoshi , Yonehara Norinobu , Ozawa Takejiro , Iwasaki Iwaji
Published: July 2006

The halogen contents of 49 Japanese volcanic rocks are; F: 50–1700 (average 410), Cl: 17–1220 (av. 270), Br: 0.09–8.10 (av. 0.85), I: 0.011–0.32 (av. 0.088) μg/g. The fluorine and chlorine were determined by usual photometric methods, and the bromine and iodine, by photometric methods based on their catalytic action, after decomposition and separation procedures suitable for each case. The bromine and iodine contents are appreciably lower than the values generally accepted for igneous rocks. The bromine content agrees with Sugiura’s value. The frequency distribution of each halogen content shows an approximate lognormality. The chlorine and bromine contents are strongly correlated, and the Br/Cl atomic ratio is in a narrow range (0.66–3.7)×10−3 (av. 1.5×10−3). No other correlation is observed among the halogen contents at all. Each halogen content has no marked relation to the type of rock. A regional difference is seen in the F/Cl and I/Br ratios. Three ultrabasic rocks have very low fluorine (≤20) and chlorine contents (≤50 μg/g). On the other hand, they have a slightly lower bromine content (0.15–0.34 μg/g) than, and almost the same iodine content (0.07–0.13 μg/g) as, the volcanic rocks.
The Synthesis of Phosphonophenylazochromotropic Acids and the Stability Constants of Its Alkaline Earth Metal Chelates
Authors: Kina Kenyu , Miyata Haruo , Tôei Kyoji
Published: July 2006

The acid dissociation constants of the three isomeric phosphonophenylazochromotropic acids and their chelate stability constants with alkaline earth metals have been measured by the pH titration method at an ionic strength of 0.10 and at 25.0±0.1°C. The stability order with respect to the ligands is as follows: ortho->meta->para-, and the stability constant of each ligand decreases in the order: Mg>Ca>Sr>Ba; this order is parallel to the reciprocal of the ionic radii of the metal ions. From a comparison between the chelate stability of o-phosphonophenylazochromotropic acid and that of Neo-Thorin, it has been concluded that the magnesium ion forms a more stable chelate bond with the phosphonic group than with the arsonic group.
Intramolecular Hydrogen Bonds. XVII. Intramolecular Hydrogen Bonding Involving the Mercapto Group as a Hydrogen Donor
Authors: Mori Nobuo , Kaido Shinichi , Suzuki Koichi , Nakamura Mikio , Tsuzuki Yojiro
Published: July 2006

The SH stretching absorption spectra of some mercapto compounds in dilute carbon tetrachloride solutions and also in acetonitrile solutions have been measured at 20°C. Alkyl mercaptans show absorption bands which are suggestive of the rotational isomerism around the C–S bond. The spectral data indicate that benzyl mercaptan, ω-ethoxyalkyl mercaptans, and ethyl α- and β-mercaptoalkanoates form practically no intramolecular hydrogen bond between the SH group and the hydrogen-acceptor group. In thiosalicylic acid and its ethyl ester, the hydrogen-bonding to the carbonyl group is partially possible even in acetonitrile. On the other hand, the corresponding free carboxylic acids are not hydrogen-bonded between the S atom and the carboxyl group.
The Preparation and Properties of Mesoionic 5-Iminothiazole Derivatives
Authors: Shiba Toshie , Kato Hiroshi
Published: July 2006

Mesoionic 5-iminothiazoles were prepared by the cyclization of N-thiobenzoyl-methylaminoacetonitriles with hydrogen chloride or acyl chlorides. The reaction between a 5-aminothiazolium chloride and acyl chlorides, isocyanate, sulfonyl chloride, and nitrous acid gave the corresponding N-substituted mesoionic 5-iminothiazole derivatives. The spectral data of these compounds as well as the ready bromination of the ring support the view that this ring system is aromatic.
Isolation and Characterization of Pteridines from Pseudomonas ovalis
Authors: Suzuki Akira , Goto Miki
Published: July 2006

Four ribityllumazine compounds were isolated from the cultured medium of Pseudomonas ovalis. Three of them were characterized as 6-methyl-8-(1-d-ribityl)-2,4,7-trioxohexahydropteridine, 6-(3-indolyl)-8-(1-d-ribityl)-2,4,7-trioxohexahydropteridine and 6-(p-hydroxyphenyl)-8-(1-d-ribityl)-2,4,7-trioxohexahydropteridine by comparison with synthetic samples. The fourth compound, named putidolumazine, was supposed to be a new compound (2-carboxyethyl)-8-(1-d-ribityl)-2,4,7-trioxohexahydropteridine from its chemical and spectroscopic properties. This was confirmed from the identity of both natural and synthetic products.
Studies on the Interaction of Isocyanides with Transition-metal Complexes. VII. Insertion Reactions of Isocyanide into Alkyl-platinum Sigma Bonds
Authors: Yamamoto Yasuhiro , Yamazaki Hiroshi
Published: July 2006

The reactions of trans-iodobis(phosphine)aklylplatinum(II) compounds with isocyanide were carried out. The reactions of isocyanide with the methyl and benzyl derivatives of platinum(II) with triphenylphosphine or dimethylphenylphosphine gave salt-like complexes [trans-Pt(PR3)2(CNR′)CH3]I (1) (PR3=PPh3, PPhMe2; R′=C6H11, C(CH3)3). When 1 was refluxed in benzene or toluene, an insertion of isocyanide took place, affording trans-iodobis(phosphine)(1-cyclohexylimino)alkylplatinum(II). Two P-CH3 proton resonances were observed in the NMR spectrum of trans-Pt(PPhMe2)2I[C(CH3)=NC6H11], indicating that the two methyl groups on the same phosphorus atom are magnetically nonequivalent. It was deduced from this NMR behavior that all the iminoacyl complexes prepared have a five-coordinate structure.
Reactions of Tosylhydrazide Derivatives Having Olefinic Groups
Authors: Sato Tadashi , Homma Itomi
Published: July 2006

When α,β-unsaturated ketone tosylhydrazones (5) were heated in 85% aqueous acetic acid, a smooth decomposition was induced and β-tosylketones (4) were obtained in fair yields. Tosylhydrazones, devoid of an olefinic group in the specified position, failed to undergo the present reaction. When allyl halides (17) were reacted with the anion of tosylhydrazide in DMSO, substitution occurred on the N-1 of tosylhydrazide, unlike as in the case of the reaction of chlorides with tosylhydrazide in pyridine, which effected the substitution on N-2. On warming in acetic acid, these 1-allyltosylhydrazides (18) afforded olefins (19) in fair yields, with a complete allylic rearrangement. A concerted cyclic mechanism was proposed for the 5→4 and 18→19 reactions.
Studies of N-Sulfinyl Compounds. IV. The Reactions of N-Sulfinylanilines and -phenylhydrazines with Styrene Oxide
Authors: Tsuge Otohiko , Mataka Shuntaro
Published: July 2006

The reaction of p-substituted N-sulfinylanilines with styrene oxide in the presence of tetraethylammonium bromide gave the corresponding 1,2,4,5- and 1,2,4,6-tetraarylpiperazines, whose configurations were established on the basis of the NMR spectral studies. On the other hand, while a similar reaction of p-substituted N-sulfinylphenylhydrazines with the oxide in benzene gave the corresponding diaryl disulfide, diaryl sulfide, and p-substituted biphenyl, the reaction in acetonitrile did not give the biphenyl. The pathways for these reactions are suggested.
Cyclic Acetylenes. XIII. The Syntheses and Properties of p,p′-Bridged Cyclic Diphenyldiacetylenes
Authors: Kataoka Mutsuo , Ando Takashi , Nakagawa Masazumi
Published: July 2006

Concerning the studies on the effect of ring strain on the electronic spectra of cylcic acetylenes, a series of polymethylene ether derivatives of p,p′-dihydroxydiphenyldiacetylene (VIn, n=13, 14, 15, and 18) has been prepared by the oxidative coupling of p-hydroxyphenylacetylene polymethylene ethers (Vn, n=13, 14, 15, and 18) under a high dilution condition. A slight bathochromic shift accompanied by hypochromism was observed in the electronic spectra of VIn resulting from the increase of the ring strain. The same trend has been observed in the p,p′-bridged cyclic tolans. However, the bathochromic shift observed in the p,p′-series makes a contrast with the hypsochromic shift in the strained o,o′-bridged cyclic diphenyldiacetylene (I) and o,p′-bridged cyclic tolans (II). The NMR and IR spectra of VIn were discussed.
Cyclic Acetylenes. XIV. The Effects of Ring Strain on the Electronic Spectra of Cyclic Tolans and Cyclic Diphenyldiacetylenes
Authors: Toda Fumio , Ando Takashi , Kataoka Mutsuo , Nakagawa Masazumi
Published: July 2006

Characteristic features of the electronic spectra of o,o′-bridged cyclic diphenyldiacetylenes (In), o,p′-bridged cyclic tolans (IIn), p,p′-bridged cyclic diphenyldiacetylenes (IIIn) and p,p′-bridged cyclic tolans (IVn) are compared. The hyperchromism observed in the longest-wavelength absorption maxima (λmax) in the higher homologues of In, IIIn, and IVn as compared with the absorption intensities of the respective open-chain analogues is explained in terms of the coplanarity of the chromophore system, and the marked hypochromism observed in the lower homologues of these cyclic acetylenes is attributed to ring strain. The hypochromism observed in the series of IIn is ascribed to the superposition of the effects of ring strain and the twisting of phenyl groups. The bathochromic shifts of λmax with the increase of ring strain in the p,p′-bridged series (IIIn and IVn) are explained by the pronounced increase of the energy of the ground state of the strained molecule of this series. On the other hand, the hypsochromic shifts of λmax of o,o′-bridged series (In) are regarded as the result of the minor increase of energy of the ground state along with the increase of the ring strain.
The Preparation of 4′,6′-Di- and 2′,4′,6′-Tri-O-acetates of Theophylline Nucleosides of 3′-Deoxy-3′-nitro-β-d-galacto-, gluco- and mannopyranose
Authors: Nakagawa Toshio , Takamoto Tetsuyoshi
Published: July 2006

7-(3′-Deoxy-3′-nitro-β-d-glucopyranosyl)theophylline (1) was treated with acetic anhydride in the presence of boron trifluoride, perchloric or phosphoric acid as a catalyst to afford the corresponding 2′,4′,6′-tri-O-acetate (4) in 87, 60 and 48% yields, respectively. With galacto-isomer (2), tri-O-acetate (6) was obtained in a high yield by the use of phosphoric acid or a large excess of perchloric acid as a catalyst, while 4′,6′-di-O-acetate (5) was selectively prepared in 82% yield when a trace of perchloric acid was used. The similar preparation of 4′,6′-di- and 2′,4′,6′-tri-O-acetates (7 and 8) of manno-isomer (3) was also carried out in the presence of boron trifluoride and phosphoric acid, respectively. The positions of the acetyl groups in the diacetates 5 and 7 were unequivocally deduced from NMR data.
Studies of the Synthesis of Furan Compounds. XXIV. The Synthesis of 5-[2-(5-Nitro-2-furyl)-1-(4-nitrophenyl)vinyl]-1,3,4-oxadiazole and Its Related Compounds
Authors: Hirao Ichiro , Kato Yasuhiko , Hirota Toshiyuki
Published: July 2006

5-[2-(5-Nitro-2-furyl)-1-(4-nitrophenyl)vinyl]-1,3,4-oxadiazoles and -1,3,4-thiadiazoles have been prepared from 3-(5-nitro-2-furyl)-2-(4-nitrophenyl)acrylic acid. All of these compounds exhibited strong antibacterial activities against Staphylococcus aureus.
Electrochemical Reduction of Aza-heteroaromatic Compounds. IV. Stabilities of Neutral Free Radicals Electrolytically Derived from 1-Methylcyanoquinolinium Perchlorates
Authors: Kato Shozo , Nakaya Jun′ichi , Imoto Eiji
Published: July 2006

Three isomers of 1-methylcyanoquinolinium perchlorates were reduced by controlled potential electrolysis for one-electron transfer, and the reduction products were identified in order to clarify their reduction mechanisms and the effect of the cyano group on the stabilities of cyanoquinolinyl radicals. The 1-methyl-4-cyanoquinolinyl radical was stable enough to survive at room temperature under anaerobic conditions. The 1-methyl-2- and 1-methyl-3-cyanoquinolinyl radicals were short-lived and were subsequently dimerized to the 1,4-dihydrotype. The 1-methyl-4-cyanoquinolinyl radical was autoxidized to 1-methyl-4-cyanoquinolinium salts in an electrolyte solution and to 1-methyl-4-cyano-2-quinolone in an ethanol solution.
Iminodithiocarbonates. III. Reactions with Some Electrophiles and the Structural Effect on Nucleophilic Reactivities and Basicities
Authors: Ueno Yoshio , Nakai Takeshi , Okawara Makoto
Published: July 2006

With a view toward demonstrating the structural effect on the reactivity of iminodithiocarbonates, the reactions of some electrophilic reagents with the following four iminodithiocarbonates have been studied; 2-methylimino-(IVa) and 2-phenylimino-1,3-dithiolane (IVb) and S,S′-dimethyl-N-methyl-(Va) and S,S′-dimethyl-N-phenyliminodithiocarbonate (Vb). Cyclic IVa and its N-ethyl homologue reacted with an equimolar amount of phenyl isocyanate at room temperature giving 1:2 cycloadducts. However, the other imino compounds (IVb, Va, and Vb) did not react at all even at elevated temperature. All these imino compounds reacted with acid chlorides to afford the corresponding N-acyliminium salts which could, in some cases, be isolated; however the rate of formation of the salts varied significantly with the structure of the imino compound. Some reactions with alkyl halides and phenyl isothiocyanate were also attempted. From the present results and those previously obtained on their reactions with epoxides and with ketenes, it has been concluded that the nucleophilic reactivity of the imino compounds increases in the order Vb<Va<IVb<IVa. Furthermore, it was found that the basicity of the imino compounds increased in the order Vb<IVb<Va<IVa. The observed ring effect and N-substituent effect on the reactivity and basicity of the imino compounds are discussed in connection with similar effects on the stability of closely related tri(hetero)carbonium ions, i.e., bis(alkyl thio)-dialkylaminocarbonium ion (I).
Relative Reactivities in the Addition of Free Trichloromethyl Radicals to Substituted Styrenes. An Attempt to Separate Polar and Resonance Effects
Authors: Sakurai Hideki , Hayashi Shun-ichi , Hosomi Akira
Published: July 2006

Relative reactivities in dibenzoyl peroxide-catalyzed addition of bromotrichloromethane to nine nuclearsubstituted styrenes have been investigated with unsubstituted styrene. The effect of meta substituents upon the relative rates was correlated with the simple Hammett equation using either σ or σ+ constants. The relative rates of para-substituted styrenes, however, did not obey the simple Hammett relation, with the results best explained on the basis of polar (ρσ+) and resonance (ED) terms. All para substituents examined increase the reactivity.

log(k⁄kH)=ρσ++ED

The ED term shows a striking correlation with logQ, of the corresponding para styrene in Alfrey-Price′s Q-e scheme of free-radical copolymerization. That the polar term originates in charge-transfer interactions between the olefin and the electrophilic trichloromethyl radical and can be expressed by ρσ+ is further supported by the evidence that charge-transfer energies of substituted styrenes showed good correlation with σ+. Factors influencing the reactivity have been discussed.
Some Oxidation and Reduction Products of 4-Acetyltropolone and Its Methyl Ethers
Authors: Nozoe Tetsuo , Takase Kahei , Shimizu Kohei , Yasunami Masafumi
Published: July 2006

The chemical properties of the acetyl side-chain of 4-acetyltropolone and its methyl ethers in relation to some oxidizing and reducing reagents were examined. The selenium-dioxide oxidation of one of the methyl ethers afforded a glyoxyloyl derivative in its hydrate form. The catalytic reduction of 4-acetyltropolone gave a mixture of 4-(1-hydroxyethyl)- and 4-ethyltropolones. The reduction of two isomeric methyl ethers with sodium borohydride gave 4-(1-hydroxyethyl)-2-methoxy- and 6-(1-hydroxyethyl)-2-methoxytropones respectively, from which two isomeric methyl ethers of 4-ethyltropolone were prepared in pure states.