bluuebunny/crossref_metadata_2025 huggingface dataset:
The Solubility of Elemental Mercury Vapor in Water
Authors: Sanemasa Isao
Published: July 2006

The solubility of mercury vapor in water has been measured by means of atomic absorption spectrophotometry over the temperature range of 5–60°C under atmospheric pressure. The aqueous solubility obeys Henry’s law at each temperature. The solubilities and the Henry coefficients are reported. From the solubility data, the heat of the solution of mercury vapor in water is found to be −5.3 kcal/mol. The relationship between the Henry coefficient, k, and the solution temperature, T, is expressed by logk=−1078×1⁄T+6.250. From this equation, the solubilities at 70–100°C are estimated. The solubility of the mercury vapor in sea water has also been measured over the temperature range of 5–30°C. A salting-out effect on the solubility is observed. The practical application of the aqueous solubility of the mercury vapor is discussed from the analytical point of view.
The Chemical Behavior of Low Valence Sulfur Compounds. IX. Photometric Determination of Thiosulfate, Trithionate and Tetrathionate in Mixture
Authors: Mizoguchi Tadaaki , Okabe Taijiro
Published: July 2006

The cyanolysis and photometric determination of thiosulfate, trithionate and tetrathionate have been investigated under the various conditions. The cyanolysis of thiosulfate catalyzed by cupric ions proceeded quantitatively in the presence of acetate buffer solution of pH 4.5, while the degree of cyanolysis of trithionate and that of tetrathionate were 0.3 and 0.6%, respectively. The degree of cyanolysis of trithionate was not so depressed as to a negligible extent by the methods previously proposed, but was depressed to 0.7% or less by the addition of such organic solvents as acetone, methanol, etc. The determination of thiosulfate, trithionate and tetrathionate in the concomitant presence of them could be made with a high accuracy.
NH2 Radicals Trapped on the Surface of Porous Vycor Glass at 77 K
Authors: Shimamoto Norio , Hatano Keiichiro , Katsu Takashi , Fujita Yuzaburo
Published: July 2006

The results of ESR studies of the amino radicals produced by the photolysis of ammonia adsorbed on the surface of porous Vycor glass at 77 K are described. The observed ESR signal patterns of the amino radicals were remarkably affected by the amount of ammonia on the surface. The isotropic and anisotropic spectra were analyzed by the use of isotopically-substituted amino radicals.
Studies of Polyphenyls and Polyphenylenes. I. The Syntheses and Infrared and Electronic Spectra of Several Sexiphenyls
Authors: Ibuki Eiichi , Ozasa Shigeru , Murai Kazue
Published: July 2006

Seven linear sexiphenyls were synthesized by the Ullmann reaction of iodobiphenyl and diiodobiphenyl. Infrared studies indicated that the fine structure in the 780–810 cm−1 region suggests the presence of consecutive m-phenylene units, and that the positions of the strong or medium bands in the 820–840 cm−1 region indicate approximately the number of continuous p-phenylene units. The electronic spectra commonly displayed a prominent E-band in the narrow region of 192–207 nm. The intense K-band above 260 nm was considered to be an indication of the presence of one or more p-phenylene units.
The High Resolution Mass Spectra of Shionane and Friedelane Derivatives
Authors: Hirota Hiroshi , Moriyama Yoshihiko , Tsuyuki Takahiko , Tanahashi Yoshiaki , Takahashi Takeyoshi , Katoh Yoshiaki , Satoh Hiroshi
Published: July 2006

High resolution mass spectra of shionane and friedelane derivatives were measured and characteristic fragmentation patterns were described.
Electric Properties of 1-Tetradecanol-Tetradecanoic Acid (Myristyl Alcohol-Myristic Acid) Mixed Bimolecular Films
Authors: Okuyama Masataka , Yoshida Tadayoshi , Tanii Tadaaki , Kunugi Masahito , Ishizaki Isao
Published: July 2006

Stable bimolecular films (bilayers) were found to be formed in aqueous solutions from myristyl alcohol or from mixtures of myristyl alcohol and myristic acid. The electric capacitance and resistance of these bilayers were measured in solutions of pH 3–8. The capacitance of mixed bilayers was larger than that of myristyl alcohol bilayers (0.58 μF/cm2). When the bilayers were formed from sample solutions having mole ratios 1/1 and 2.3/1 (myristic acid to myristyl alcohol), the capacitance had minima at ca. pH 7. The resistance of mixed bilayers at ca. pH 5 was smaller than one tenth of that of the myristyl alcohol bilayer (ca. 7×108 Ω·cm2). The results are explained in terms of (i) van der Waals attraction between hydrocarbon chains, (ii) the tendency for myristic acid to form expanded layers, (iii) the head group attraction between the myristic acid ion and myristyl alcohol, and (iv) the tendency for myristic acid ions to dissolve in the aqueous phase.
Molecular Structure of 2-Fluoropropane as Determined By Gas Electron Diffraction
Authors: Kakubari Hironobu , Iijima Takao , Kimura Masao
Published: July 2006

The skeletal parameters, C–C, C–F, and C···F distances, of 2-fluoropropane have been determined by means of gas electron diffraction. The rg-values obtained are: C–C 1.514±0.004 Å, C–F 1.405±0.005 Å and C···F 2.366±0.006 Å. By a joint analysis of the diffraction data and the spectroscopic moments of inertia, determination of the remaining structural parameters has also been attempted, and the φz value of the CCC angle being found to be 114.6±1.5°.
Core-electron Spectra of Mono-substituted Benzenes Obtained by the Gas-phase X-Ray Photoelectron Spectroscopy
Authors: Ohta Toshiaki , Fujikawa Takashi , Kuroda Haruo
Published: July 2006

The gas-phase X-ray photoelectron spectra were observed on benzene and its eight mono-substituted derivatives; C6H5X, X=H, CH3, NH2, OH, F, Cl, Br, NO2 and CN. Binding energies of core levels were determined from the observed spectra by using the spectrum simulation technique, and they were compared with the chemical shift predicted from the CNDO/2 charge densities on the basis of the electrostatic potential model. It is shown that the Cls binding energies of benzene derivatives can be generally correlated with atomic charges, qj, by the following equation;

E_i(Cls)=290.2+22.67q_i+\undersetj\eweqi∑(q_j/R_ij) eV.

By using this relation and the observed Cls binding energies, the atomic charge analysis is carried out. Satellite bands were observed in the Cls spectra as well as in some other core-electron spectra of benzene derivatives. Theoretical calculations are carried out on the energies and probabilities of shake-up transitions. It is concluded that the observed satellites are mainly due to the shake-up processes associated with the excitations of π electrons.
The Facile Synthesis of 5′-Nucleotides by the Selective Phosphorylation of a Primary Hydroxyl Group of Nucleosides with Phosphoryl Chloride
Authors: Sowa Tsuneo , Ouchi Shunji
Published: July 2006

5′-Nucleotides were directly prepared by selective phosphorylation with phosphoryl chloride in the presence of water and pyridine in acetonitrile. The rate of phosphorylation with phosphoryl chloride was markedly improved by the addition of suitable amounts of water and pyridine; the maximal formation of 5′-nucleotides was obtained by mixing these three reactants phosphoryl chloride, water, and pyridine in a molar ratio of 2 : 1 : 2 at a low temperature, followed by adding nucleosides corresponding to a one-fourth or one-fifth of the phosphoryl chloride. By mixing phosphoryl chloride, water, and pyridine in acetonitrile under controlled conditions, a hygroscopic complex (Complex 1), an active phosphorylating agent in the present phosphorylation of nucleosides, was isolated. It was identified as an adduct composed of tetrachloropyrophosphate and pyridinium chloride by means of its infrared spectra and by its chromatographic behavior. One of the proposed structures of the adduct is trichloropyrophosphopyridinium chloride. Both the selectivity in the 5′-hydroxyl group of the nucleosides and the yield of 5′-nucleotides increase upon the addition of pyridinium chloride in the phosphorylation of the unprotected nucleosides with tetrachloropyrophosphate. In the phosphorylation with tetrachloropyrophosphate, the H+ derived from pyridinium chloride in acetonitrile is considered to increase the selectivity for the 5′-hydroxyl group by decreasing the reactivity of the hydroxyl groups in the ribose moiety of the nucleosides with the adduct. Similar results were obtained in the phosphorylation with phosphoryl chloride in the presence of pyridinium chloride in acetonitrile. Thus, several procedures for the selective phosphorylation of unprotected nucleosides to 5′-nucleotides are available.
Effect of Base on Palladium-Black Catalyzed Carbonylation of Iodobenzene
Authors: Ito Takeshi , Mori Kunio , Mizoroki Tsutomu , Ozaki Atsumu
Published: July 2006

It was found that palladium-black is a highly active catalyst for the carbonylation of iodobenzene with carbon monoxide and methanol in the presence of potassium acetate, triethylamine, or tributylamine to give methyl benzoate. The kinetic study of the carbonylation showed that the oxidative addition of iodobenzene to a palladium(0) complex is rate-determining, and that the bases affect considerably the rate-determining step.
The Substituent Effect. V. NMR Chemical Shifts of Hydrogen-bonding Hydroxyl Proton of Phenols in DMSO
Authors: Fujio Mizue , Mishima Masaaki , Tsuno Yuho , Yukawa Yasuhide , Takai Yoshio
Published: July 2006

The chemical shifts of the hydrogen bonded OH proton of m- and p-substituted phenols, and 4-substituted 2-cresols, 3-cresols, and 2,6-xylenols were determined in DMSO. The effects of substituents on the hydroxyl chemical shift of these series were correlated linearly with each other (correlation coefficient>0.999), except for the bulky planar substituents in the 3-cresol series which may be subject to the steric loss of their coplanarity with the benzene ring. The substituent effects were treated successfully with the equation, Δδ=ρ(σ0+r−Δ\barσR−). The phenol series gave r−=0.673 and ρ=1.530. The same r− value appeared to be applicable to all the other series with negligible changes in the ρ value. Deviations from the correlation of particular substituents, in particular those having acidic hydrogen, were attributed to the modification of the electronic nature of substituents arising from the strong substituent-DMSO interaction.
The Calculation of the Primary Radiolysis Yield of Water Vapor Irradiated by 10-keV Electrons
Authors: Ohno Shin-ichi , Nagayama Hisashi , Okazaki Kiyoshi , Sato Shin
Published: July 2006

The yields for the ionization and excitation from each molecular orbital of a water molecule irradiated by 10 keV electrons were calculated using the classical binary-encounter approximation. On further assuming fragmentation processes of the excited or ionized states consistent with the photochemical and mass spectrometrical results in the literature, we obtained, as the radiolysis yields of water vapor: G(electron)=2.96; G(OH−)=0.04; G(H3O+)=3.00; G(H)=4.83–5.21, including G(‘hot’ H-atoms)≤0.87; G(H2)=0.28–1.15; G(O)=0.83–1.21; G(OH)=6.70–7.08, and G(–H2O)=G(ionized water)+G(excited water)=2.91+4.96=7.87.
The CD Spectra of (l-Aspartato) (l-2,4-diaminobutyrato) cobalt (III) Complexes
Authors: Watabe Masatoshi , Yoshikawa Sadao
Published: July 2006

Systematic correlations in CD spectra are found when the CD spectra of the isomers of the [Co(l-aspartato)(l-2,4-diaminobutyrato)] complex, the [Co(N)3(O)3] type, are compared with those of the isomers of the [Co(l-2,4-diaminobutyrato)2]+, the [Co(N)4(O)2] type, and those of the isomers of the [Co(l-aspartato)2]−, the [Co(N)2,(O)4] type.
Kinetics and Mechanisms of Hydrothermal Reaction of Granulated Blast Furnace Slag
Authors: Kondo Renichi , Abo-El-Enein Salah A , Daimon Masaki
Published: July 2006

Kinetics and mechanisms of hydrothermal reactions of the systems slag-lime-water (I) and slag-quartz-lime-water (II) have been studied. In the initial stage of reaction in system (I), nearly amorphous calcium silicate hydrate with low lime content was formed and continued to grow in strength. Formation of hydrogarnet (3CaO·Al2O3·SiO2·4H2O) accompanied by the crystallization of calcium silicate hydrate caused a reduction in strength. In the reaction in system (II), a product with high lime content was formed which was then changed into a low lime product after complete consumption of free lime. Slag was highly reactive but inhibited reaction of quartz, especially during the initial stage of the hydrothermal solidification process. The rate of hydrothermal reaction as well as the characteristics of the products change considerably with temperature.
The Electronic Structure of the Electron-donor-acceptor System in the Excited State. The Exciplex and the Fluorescent State of EDA Complex
Authors: Mimura Tsutomu , Itoh Michiya , Ohta Toshiaki , Okamoto Toshihiko
Published: July 2006

The semiempirical SCF-MO-CI calculation was applied to the electron donor-acceptor (EDA) interaction in 9,10-dicyanoanthracene and naphthalene system which exhibits the exciplex fluorescence and also the fluorescence due to the EDA complex stable in the ground state. On the basis of energy contour maps of the ground and excited states and of electronic transitions in the EDA system, the relaxation process from the F.G. excited state of the EDA complex to an identical fluorescent state with the exciplex was discussed on the intermolecular interaction, and also on the intramolecular interaction in (9,10-dicyanoanthracene)-(CH2)3- (naphthalene) systems.
ESR Studies of Phenoxyl Radicals Produced by the PbO2 Oxidation of Hindered Polyphenols. III. p- and m-Phenylenebisgalvinoxyls, Stable Triplets
Authors: Mukai Kazuo
Published: July 2006

PbO2 oxidation of two hindered polyphenols produced, in turn, primary, secondary, and ternary radicals. The ternary radicals are π-conjugated biradicals; the structures of the radicals were assigned to be p- and m-phenylenebisgalvinoxyls. Both zero field splitting parameters and hyperfine splitting constants were determined from ESR spectra.
C–S Stretching Vibrations and Molecular Conformations of Isobutyl Methyl Sulfide and Related Alkyl Sulfides
Authors: Nogami Norimasa , Sugeta Hiromu , Miyazawa Tatsuo
Published: July 2006

The Raman and infrared spectra of isobutyl methyl sulfide and related alkyl sulfides were measured. The Raman spectra of the liquid, unannealed solid, and annealed solid of isobutyl methyl sulfide were compared and skeletal normal vibrations of possible rotational isomers were treated. Three rotational isomers were found to coexist in the liquid state whereas only one isomer was observed in the annealed solid. The energy differences among the three rotational isomers were measured. The correlations between the CH2–S stretching frequencies and molecular conformations were established, in common, for the molecules of isobutyl methyl sulfide, methyl propyl sulfide and ethyl methyl sulfide.
The Role of Solvents in the Dimerization of the 2,3-Dichloro-5,6-dicyano-p-benzoquinone Anion Radical
Authors: Yamagishi Akihiko
Published: July 2006

The reversible dimerization of the anion radical of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) has been studied in water, acetonitrile (MeCN), and other organic solvents. The analysis of the thermodynamic parameters of dimerization equilibria reveals that a large negative entropy term plays a primary role in determining the equilibrium constants. The temperature-jump measurement shows that the forward rate constant in water containing 5.8 M urea is nearly a diffusion controlled one, (1±0.5)×108 M−1 s−1 at −6°C. In MeCN-water mixtures, the backward reaction rate increases with the square of the MeCN concentration. This result suggests that a dimer is effectively decomposed by the successive attacks of the two MeCN molecules.
Metal Phosphinylides and Phosphinothioylides. IV. Reactions with Tetrahydrofuran
Authors: Goda Koshiro , Yoshifuji Masaaki , Okazaki Renji , Inamoto Naoki
Published: July 2006

Diphenylphosphinic (1) and diphenylphosphinothioic chlorides (2) were allowed to react in tetrahydrofuran (THF) in the presence of metal or metal salts at 120–150°C. In the cases of lithium and magnesium, [Ph2PX]–(X=O, S) thus formed attacked the α-carbon of THF to give ring-opening products, which were produced by deoxygenation, sulfurization, and reaction with 1 and 2. In the cases of iron, copper, and their salts, O-4-chlorobutyl diphenylphosphinate (12) and diphenylphosphinothioate (13) were obtained in a homolytic fashion. The formation mechanisms have been discussed.
Some Mixed-Ligand Manganese(III) Complexes Produced by the Reactions of Tris(acetylacetonato)manganese(III) with Hydrogen Halides in Organic Solvents
Authors: Isobe Kiyoshi , Kawaguchi Shinichi
Published: July 2006

Although tris(acetylacetonato) manganese(III) is reduced by hydrogen halides in organic solvents, ultimately resulting in manganese(II) chloride, bromide or bis(acetylacetonato)manganese(II), the equimolar reactions afforded the intermediary manganese(III) products MnX(acac)2, where X is Cl, Br, or I. These mixed-ligand complexes were characterized by measurements of electronic and infrared spectra, molecular weight, electric conductivity and magnetic susceptibility, and concluded to exist as a five-coordinate molecule in non-coordinating solvents, but behave as a uni-uni valent electrolyte in methanol. Six-coordinate complexes [Mn(acac)2(H2O)2]Br·2H2O and MnX(acac)2B were also derived therefrom, where B is 4-methylpyridine, pyridine oxide or dioxahe. Further reaction of MnCl(acac)2 with equimolar hydrogen chloride in methylene chloride at −78 °C produced MnCl2(acac)(O-py)2 or MnCl2(acac)H2O in the presence or absence of pyridine oxide (O-py), respectively, but the corresponding dibromo and diiodo complexes could not be obtained in similar reactions with hydrogen bromide or iodide.
Ion-exchange Chromatographic Studies of the [Co(N)4(O)2]+-type Complexes
Authors: Kobayashi Kazuhiro , Shibata Muraji
Published: July 2006

The following complexes of the [Co(N)4(O)2]+ type have been prepared: [Coox(tn)2]+, u-fac-, s-fac-, and mer-[Coox(NH3)(dien)]+, cis- and trans-[Coox(NH3)2(en)]+, u-fac- and s-fac-[Co(ida)(NH3)(en)]+, fac-[Co(ida)(NH3)3]+, and cis(O)trans(N)cis(NH3)-, cis(O)cis(N)cis(NH3)-, and cis(O)cis(N)trans(NH3)-[Co(gly)2(NH3)2]+. The geometrical structures have been determined on the basis of the PMR spectra, the absorption spectra, etc. Including these new complex species, twenty-six species of the [Co(N)4(O)2]+ type have been investigated through ion-exchange chromatographic separation. The elution orders obtained have been discussed in connection with the geometrical configurations.
Mixed Ligand Copper(II) Complexes of Amino Acids and Related Compounds with Possible Ligand-Ligand Interactions
Authors: Yamauchi Osamu , Nakao Yasuo , Nakahara Akitsugu
Published: July 2006

Ternary systems composed of copper(II) and two ligands, each with an oppositely charged uncoordinated group in the side chain, have been investigated by synthetic and spectral methods. The absorption and circular dichroism(CD) spectra in the d-d region were measured at various pH values for the binary and ternary systems, Cu(B)2 and Cu(A)(B), where A refers to ethylenediamine-N-monoacetic acid(EDMA), glycylglycine(Gly·Gly), glycyl-β-alanine(Gly·β-Ala), ethylenediamine(en), or glycine(Gly), and B to d- and l-arginine (d- and l-Arg), l-ornithine(l-Orn), l-lysine(l-Lys), l-alanine(l-Ala), or l-valine(l-Val), and the following complexes containing ligands with polar side chains were isolated as crystals: [Cu(EDMA)(l-Arg)]C1O4·H2O; [Cu(EDMA)(l-Orn)]ClO4·1/2H2O; [Cu(EDMA)(l-Lys)]ClO4; [Cu(Gly·Gly) (l-Arg)]·3/2H2O. From comparison of the CD magnitudes expressed in terms of the relative magnitude which assumes half the value for Cu(B)2 as unity, the magnitude enhancements observed for the systems Cu(EDMA)(d- and l-Arg), Cu(EDMA)(l-Orn), Cu(EDMA)-(l-Lys), and Cu(Gly·β-Ala)(d- and l-Arg) in water and in 50% aqueous ethanol have been inferred to be due to the intramolecular electrostatic interactions between the charged groups in the side chains of ligands A and B.
Friedel-Crafts Reaction of 1,3,5-Trialkylbenzenes with Sulfur Monochloride and N-Chlorodimethylamine
Authors: Yoshifuji Masaaki , Tanaka Susumu , Inamoto Naoki
Published: July 2006

The reaction of sulfur monochloride gave 2,4,6-tri-t-butylchlorobenzene (3) from 1,3,5-tri-t-butylbenzene (1), but gave the corresponding sulfide and disulfide from mesitylene (2). The reaction of N-chlorodimethylamine gave 3, 2-chloro-3,5-di-t-butyltoluene and 2,4,6-trimethylchlorobenzene from 1, 3,5-di-t-butyltoluene and 2, respectively. The reaction of N-chlorodimethylamine with benzene gave chlorobenzene or N,N-dimethylaniline in 1-nitropropane or nitromethane.
Mössbauer Spectroscopic Studies of the Effect of Anions in the Second Coordination Sphere in the EC-decay
Authors: Sano Hirotoshi , Ohnuma Toshiaki
Published: July 2006

The 57Fe-Mössbauer emission spectra of 57Co-labelled [Co(NH3)6](NO3)3, [Co(en)3](NO3)3, K3[Co(CN)6], K3[Co(NO2)6], [Co(NH3)6]2(C2O4)34H2O, [Co(en)3]2(C2O4)3·9H2O, [Co(NH3)6][Fe(CN)6], [Co(NH3)6][Cr-(C2O4)3]·3H2O, and [Co(NH3)6][Fe(C2O4)3]·3H2O sources have been determined. It has been demonstrated that oxalate anions and trisoxalatochromate and trisoxalatoferrate complex anions located outside the first coordination sphere of the decayed atom are still involved in the local radiolytic processes initiated by the EC-decay. The yields of 57Fe species found in the ferrous-charge state were interpreted by using the data of γ-radiolysis and hot-atom chemistry of the 59Co(n,γ)60Co reaction.
Photochemistry in the Adsorbed Layer. V. Effects of Surface Pretreatments upon the Photolysis of Adsorbed 2-Pentanone
Authors: Anpo Masakazu , Wada Toshiaki , Kubokawa Yutaka
Published: July 2006

The effects of surface pretreatment upon the photolysis as well as the absorption and phosphorescence spectra of 2-pentanone adsorbed on porous Vycor glass have been investigated. The rate of propane formation (Norrish type I reaction) passes through a maximum and then decreases at higher degassing temperatures, while that of ethylene formation (Norrish type II reaction) decreases with increasing degassing temperature. Simultaneously, the phosphorescence intensity increases while the blue shift of the (n,π*) band decreases. This suggests that with a rise in degassing temperature the triplet lifetime increases while the surface polarity decreases. Thus, the decrease in the rate of ethylene formation is attributed to destabilization of the 1,4-biradicals formed by the intramolecular hydrogen abstraction, and the decrease in the rate of propane formation to the decrease in the lifetime of the n-propyl radicals, the hydrogen abstraction efficiency, and the probability of α-cleavage.
The Extraction Spectrophotometric Determination of Iron(III) with Eriochrome Cyanine R and Tridodecylethylammonium Bromide
Authors: Shijo Yoshio
Published: July 2006

A sensitive spectrophotometric procedure for the determination of iron(III) has been developed, utilising the ternary complex system of iron–Eriochrome Cyanin R–Tridodecylethylammonium. The iron–Eriochrome Cyanin R chelate anion was extracted with tridodecylethylammonium bromide in xylene. The extracted species had an absorption maximum at 613 nm in the organic layer. The optimum pH range for the extraction was 5.8–6.5. Beer’s law held for 0.2–2 μg of iron(III) in 5 ml of the organic layer. The molar absorptivity of the extracted species was 1.73×105 cm−1·l mol−1·1 at 613 nm. The composition of the ternary complex was assumed to be (Remark: Graphics omitted.) Lead, mercury, tin, chromium, beryllium, thorium, uranium, nitrate, iodide, thiocyanate, and perchlorate interfered with the determination of iron(III).
The Decomposition of the Oxalato Complex of Manganese(IV) in Oxalate Buffer Solutions
Authors: Uehiro Takashi , Taminaga Iwao , Yoshino Yukichi
Published: July 2006

The spontaneous decomposition of the oxalato complex of manganese(IV), [Mn2IVO2(C2O4)4]4−, in oxalate buffer solutions is investigated photometrically. It is found that the reaction proceeds in two steps, the first step being [Mn2IVO2(C2O4)4]4−→[MnIII(C2O4)3]3− and the second, [MnIII(C2O4)3]3−→manganese(II) complexes. The experimental rate at pH 3.9 is written as:

rate & =-d[Mn_2^IV]/dt

 & =α[Mn^III]+β[Mn_2^IV]^1/2[Mn^III]+γ[Mn_2^IV]^1/2,

where Mn2IV and MnIII denote [Mn2IVO2(C2O4)4]−4 and [MnIII(C2O4)3]3− respectively. Compared with α and β terms, the contribution of the γ term is much smaller. A mechanism involving the CO2− radical is postulated for the reaction.
Aromatic Solvent-induced Shift(ASIS). I. An Interpretation Based on the Dipole-Quadrupole Interaction
Authors: Nikki Kunio , Nakagawa Naoya , Takeuchi Yoshito
Published: July 2006

Two general theoretical ways of estimating aromatic solvent-induced shifts(ASIS), which are based on the dipole (solute)-induced diple (solvent) interaction [(μ-μ′) interaction] or the dipole (solute)-quadrupole (solvent) interaction [(μ-Q) interaction], are proposed. Solvent shifts can occur by means of the magnetic anisotropy of solvent molecules, which take specific orientations due to those electro-static interactions. As an example, we calculate the ASIS of a hypothetical spherical molecule, a model for camphor, with a dipole near the center and covered with protons, immersed in benzene. The estimated ASIS based on (μ-μ′) interaction is much too small to account for the shifts normally observed, while those based on (μ-Q) interaction agree well with the observed ASIS in respect to both its magnitude and angular dependency (e.g., the carbonyl plane rule). More specifically, the theoretical and experimental ASIS for methyl protons of camphor are compared.
Oxidation of Cyclopropylamines and Aziridines with Lead Tetraacetate
Authors: Hiyama Tamejiro , Koide Hiroshi , Nozaki Hitosi
Published: July 2006

The title reaction of 2-phenylcyclopropylamine gives cinnamaldehyde, while that of the 1-phenyl isomer produces benzonitrile and ethylene. The similar treatment of 2-phenylaziridine provides benzaldehyde as the only isolable product. These reactions are explained by assuming the common intermediacy of nitrenium ions such as (Remark: Graphics omitted.) respectively. The assumption is confirmed by the oxidation of the corresponding amines with sodium hypochlorite. Entention of the reaction to 2,3-polymethyleneaziridines with R group on C-2 afforded R–CO–(CH2)n–C≡N type products (R=H, alkyl, phenyl) in preparative yields. This provides a novel method of C=C bond cleavage of cycloalkenes.
A Structure Analysis of a Bromo Derivative of Parasiticolide A by the X-Ray Diffraction Method
Authors: Fukuyama Keiichi , Kawai Hiromitsu , Tsukihara Tomitake , Tsukihara Kumiko , Katsube Yukiteru , Hamasaki Takashi , Hatsuda Yuichi , Kuwano Harumitsu
Published: July 2006

The structure of a bromo-derivative of parasiticolide A, C26H29O8Br, has been determined by singlecrystal X-ray analysis. The compound crystallized in the space group P212121, with a=14.658, b=15.323, and c=11.181 Å. The absolute configuration of the molecule was determined using the anomalous dispersion effect of the bromine atom for CuKα radiation.
Synthesis and NMR Spectra of para-Substituted Benzyl Hydrodisulfides and Related Compounds
Authors: Kawamura Shunichi , Horii Toyokazu , Nakabayashi Takeshige , Hamada Masayuki
Published: July 2006

The titled compounds were synthesized and their NMR spectra were measured. The chemical shifts of benzyl hydrodisulfides were not related to σ or σR, while those of the corresponding thiols were related to σ.
Pyrimidine-Fused 1,4-Benzodiazepines. Reaction of 1,4-Benzodiazepines with Formamide–POCl3
Authors: Kobayashi Shigeru
Published: July 2006

Synthesis of new pyrimidine-fused 1,4-benzodiazepines was achieved practically in a single step by heating 1,4-benzodiazepines with formamide and POCl3 in a sealed tube. A plausible mechanism of the reaction is proposed.
Synthetic Photochemistry. VI. The Cycloaddition of Methyl Acetopyruvate with Cyclopentadiene: A Concomitant Formation of (4+2)π and (2+2)π Adducts
Authors: Takeshita Hitoshi , Mori Akira , Toyonaga Yoshinori
Published: July 2006

The irradiation of methyl acetopyruvate in cyclopentadiene using a high-pressure mercury lamp yielded two (4+2)π and two (2+2)π adducts. These products were inert under the photochemical conditions.
Complex Formation of Indium(III) with Murexide and the Decomposition of Murexide in the Presence of Indium(III) in Acid Perchlorate Media
Authors: Kawai Yoichi , Imamura Taira , Fujimoto Masatoshi
Published: July 2006

Kinetic and equilibrium data on the complex formation between In(III) and murexide are derived using stopped-flow method and also from the rate of decomposition of the ligand in acid perchlorate media. The rate of complex formation is independent of the acid concentration over the wide range of [H] between 0.001 and 0.5 M. The discrepancies of the stability constants obtained from the direct and the indirect methods are discussed.
Preparation of the Co(III) Complexes with a Tridentate Hexaniobato and a Bi- or Tri-dentate Amino Carboxylato Ligand
Authors: Hosokawa Yutaka , Hidaka Jinsai , Shimura Yoichi
Published: July 2006

Twelve new Co(III) complexes containing a hexaniobate ion Nb6O198− as a tridentate ligand were synthesized. The hexaniobato ligand coordinates facially, and the remaining three coordination sites are occupied by a tridentate amino carboxylato ligand or by a bidentate amino carboxylato ligand and NH3 or H2O. Two glycinato complexes, [Co(Nb6O19)(gly)(X)]6− (X=NH3 or H2O), were optically resolved, and a l-valinato complex [Co(Nb6O19)(l-val)(NH3)]6− was separated into two diastereomers. The structures of these complexes were determined from their visible and ultraviolet absorption, circular dichroism, and proton magnetic resonance spectra.
Chemistry of Nitrosoimines. X. Reactions of 3-Substituted 2-Nitrosoimino-2,3,-dihydrobenzothiazoles with Aryl and t-Butyl Grignard Reagents
Authors: Akiba Kin-ya , Kawamura Takayuki , Hisaoka Motoyuki , Inamoto Naoki
Published: July 2006

3-Substituted 2-nitrosoimino-2,3-dihydrobenzothiazoles (1) react with arylmagnesium bromide to give 3-substituted 2,2-diaryl-2,3-dihydrobenzothiazoles as the major product and 2-N′-arylhydrazono-2,3-dihydrobenzothiazoles as a minor product. 1 reacts also with t-butylmagnesium chloride to give 3-substituted 2-t-butyl- and 2-N′-t-butylhydrazono-2,3-dihydrobenzothiazoles and 2,3-dihydrobenzothiazol-2-one. Reaction of 1 with mesitylmagnesium bromide gave a similar result to that with t-butylmagnesium chloride.
Chemistry of Nitrosoimines. XIII. Reactions of 3-Substituted 2-Nitrosoimino-2,3-dihydrobenzothiazoles with Organolithiums
Authors: Hisaoka Motoyuki , Akiba Kin-ya , Inamoto Naoki
Published: July 2006

Reactions of 3-substituted 2-nitrosoimino-2,3-dihydrobenzothiazoles (1) with phenyl- and n-butyllithiums give the corresponding (N-substituted o-amino)phenyl sulfides as the major product due to direct attack on the sulfur atom of the benzothiazoline ring, while that with benzyllithium gives 2,2-dibenzyl derivatives and bis[o-(N-substituted amino)phenyl] disulfides. The difference between the reactions of 1 with Grignard reagents and those with organolithiums has been explained by the difference of the coordination site, thiophilicity and the ionic character of the reagents.
Reactions between Nucleophiles and Sulfonium Ions Containing Electron-withdrawing Substituents
Authors: Matsuyama Haruo , Minato HirosHi , Kobayashi Michio
Published: July 2006

Sulfonium ions containing electron-withdrawing substituents are formed by the reactions between sulfonium ylides and suitable electrophiles. Reactivities of these sulfonium ions (MeR\overset+S–CX(CO2Me)2) with nucleophiles (Y−) are investigated. The products found are those of 1) C-attack (MeSR+YCX(CO2Me)2), 2) Me-attack (MeY+RSCX(CO2Me)2) and 3) R-attack (RY+MeSCX(CO2Me)2). When R is (+)-2-octyl and Y− is bromide ion, the RY found is (−)-2-octyl bromide with 59% optical purity. The mechanism of these reactions are discussed.
The Substituent Effect. VI. Inductive and π-Electronic Effects in the Phenol Hydroxyl Chemical Shifts in DMSO
Authors: Tsuno Yuho , Fujio Mizue , Yukawa Yasuhide
Published: July 2006

Substituent effects on the NMR chemical shifts of the hydroxyl proton of m- and p-substituted phenols in DMSO have been studied by means of the LSFE equation. The effect of substituents was found to be considerably modified in the DMSO solution as compared with that in aqueous solution through strong substituent-solvent interactions. The LSFE equation was applied to the apparent substituent effects of such solvent-modified systems, and the practical set of parameters for the inductive and the π-electronic effects of the DMSO-modified substituents were estimated. The treatment was successful for +R substituents but not for −R substituents. This may be attributed to the much stronger solvent-substituent interactions. Characteristic features of LSFE treatment were discussed in comparison with Taft and Swain-Lupton treatments. It is suggested that the dual resonance reaction constants for +R and −R  para substituents are required for Taft-type correlations.
X-Ray Photoelectron Spectroscopy of 1,10-Phenanthroline Metal Chelates
Authors: Yoshida Tooru , Sawada Shigemasa
Published: July 2006

Photoelectron spectra of several phenanthroline metal chelates were measured and the shifts of the N(1s) binding energy were plotted against the electronegativities of the metals. The plotted points appeared to fall into two groups, one for transition-metal chelates and the other for the other metal chelater.
Proton Transfer Reactions in Oxygen-Containing Molecules and Ammonia Mixtures
Authors: Matsumoto Akira , Okada Satoshi , Taniguchi Setsuo , Hayakawa Teruo
Published: July 2006

Ion-molecule reactions leading to the formation of NH4+ in a number of mixtures of oxygen-containing molecules and ammonia have been studied using pulsedsource mass spectrometry. Some unique features in the reactivities of C2H4O+ and CHO+ ions from ethylene oxide have been found.
Solvent Effect on the Dimerization of Tetracyanoquinodimethane Anion Radical
Authors: Sakata Tadayoshi , Nakane Akihiro , Tsubomura Hiroshi
Published: July 2006

The thermodynamic quantities of the dimerization of tetracyanoquinodimethane (TCNQ) anion radical in water–ethanol mixtures were determined. The free energy of dimerization −ΔG showed a monotone decrease with an increase in ethanol content, whereas the enthalpy and the entropy of dimerization, −ΔH and −ΔS, showed a maximum. This unusual behavior is explained by proposing a solvation model in which the water molecules are attracted more strongly around the TCNQ− dimer than are the ethanol molecules. The entropy was found to play an important role in the dimerization.
Infrared Band Shape of the C–I Stretching Vibration of Methyl Iodide in Solutions
Authors: Fujiwara Kenji , Fukushi Kohji , Ikawa Shun-ichi , Kimura Masao
Published: July 2006

The infrared band shapes of the fundamental and overtone C–I stretching vibrations of methyl iodide in solutions are well approximated by the superposition of Lorentzian functions. From a comparison of the bandwidths of the ν3(→1), ν3(1→2), and ν3(0→2) transitions, it is pointed out that the vibrational relaxation of the translational-diffusion type proposed by Bratos et al. contributes to the band-widths, in addition to reorientational relaxation. A slight deviation from the Lorentzian function was observed in the low-frequency region of the fundamental band.
Nuclear Quadrupole Resonance of Tellurium Tetraiodide
Authors: Okuda Tsutomu , Yamada Koji , Furukawa Yoshihiro , Negita Hisao
Published: July 2006

The nuclear quadrupole resonance (NQ R) of 127I in tellurium tetraiodide was observed, and the Zeeman effect on a single crystal was examined. Tellurium tetraiodide shows ten resonance lines in the frequency range from 195 to 260 MHz. From the analysis of the zero-splitting patterns, it has become apparent that tellurium tetraiodide crystals contain eight nonequivalent iodine atoms, two of which yield large asymmetry parameters (94.9% and 73.8%) and small quadrupole coupling constants (775.07 MHz and 929.55 MHz) at room temperature. These two may be assigned to the bridging iodine atoms, but they differ markedly from each other in the temperature dependences of e2Q q/h and η. The other six iodine atoms have small η values and coupling constants of about 1600 MHz; they are assigned to the terminal atoms. From these results, it may be concluded that each tellurium atom has three terminal and two bridging iodine atoms.
Microwave Spectrum of Ethylene Oxide in Excited Vibrational States
Authors: Yoshimizu Nobuaki , Hirose Chiaki , Maeda Shiro
Published: July 2006

In the rotational spectrum of ethylene oxide, the five lowest-lying vibrational states are assigned and the vibration-rotation constants and the centrifugal distortion constants are derived. The vibrational frequencies are estimated from relative intensity measurements at νa=803±18 cm−1 and νb=814±23 cm−1 for the antisymmetric species (with respect to the C2 operation) and at νc=872±34 cm−1, νd=1020±33 cm−1, and νe=1109±42 cm−1 for the symmetric species. The intensity measurements of the remaining spectral lines showed that these lines belong to vibrational states at frequencies above about 1000 cm−1. The νa, νb, and νc states are tentatively assigned to ν15, ν12, and ν5, respectively, by taking into account the Goriolis interactions.
Partition Coefficients of Alkanols and Polyoxyethylene Alkyl Ethers in the Dodecane–Water System at 25 °C
Authors: Manabe Masahiro , Koda Masaharu , Shirahama Keishiro
Published: July 2006

The partition coefficients of normal alkanols (RmOH, m=2 to 6) and a number of polyoxyethylene normal alkyl ethers (RmEnOH, n=1,2 m=2 to 5; n=3, 4m=4,5) in the dodecane-water system have been determined at a high dilution at 25 °C. From the finding that the standard free energies of the transfer of the solutes from water to the dodecane phase show a linear relation with the number of methylene and oxyethylene groups, the contribution of the groups to the free energy was obtained as −0.858 for alkanols and −0.808 kcal/mol methylene group for ethers, and 0.655 kcal/mol oxyethylene group respectively. Extrapolation to zero oxyethylene in the linear relationship for the normal alkylethers gave standard free energies of transfer less than those for normal alkanols with the same alkyl chain length. Thus, the alkanol is more hydrophilic than the hypothetical “ether” with no oxyethylene group. The difference in the free energies is discussed from the viewpoint of intramolecular hydrogen-bond formation in the polyoxyethylene chain in the dodecane phase.
Effect of the Viscosity Ratio, μd/μc, on the Particle-size Distribution in Emulsions
Authors: Tsukiyama Shun’ichi , Takamura Akira , Fukuda Yasuko , Koishi Masumi
Published: July 2006

The object of this paper is to investigate the effect of the ratio of the viscosities of dispersed and continuous phases, μd⁄μc, on the particle-size distribution in o/w-type emulsions. The viscosity ratios (μd⁄μc) used were 0.836 : 1, 0.271 : 1, 0.0992 : 1, 0.0280 : 1, and 0.00133 : 1. The size of the dispersed liquid droplets was measured by the microphotographic method. The mean diameter and the particle-size distribution were determined, and, further, the specific interfacial energy was evaluated. When the viscosity ratio was much smaller than unity, the particle-size distribution showed a skewed curve. On the contrary, the specific interfacial energy increased remarkably as the viscosity ratio approached unity.
Circular Dichroism of Chromium(III) Complexes. V. Circular Dichroism of traras-Dihalogenobis(diamine) Complexes with Optically Active Diamines
Authors: Kaizaki Sumio , Shimura Yoichi
Published: July 2006

Nine chromium(III) complexes of trans-[CrX2(N)4] type with three kinds of optically active diamines (R-propylenediamine, S,S-stilbenediamine and S,S-2,4-pentanediamine) were prepared and the absorption and circular dichroism spectra were measured in the region of their d–d transitions. The CD behaviors in the spinallowed transitions were discussed in comparison with the corresponding cobalt(III) complexes and their bands were assigned to the tetragonal components. On the basis of the theoretical correlation between the rotational strengths for the spin-forbidden transitions and for the spin-allowed transitions, the CD peaks in the spin-forbidden transitions were discussed and assigned.
Synthesis and Rearrangement of Ethyl Aryloxyglyoxalate Arylhydrazones
Authors: Shawali A Sami , Eweiss N F , Hassaneen H M , Sami M
Published: July 2006

Ethyl chloroglyoxalate arylhydrazones (III) react with sodium phenolates in ethanol and give ethyl aryloxyglyoxalate arylhydrazones (IV). The latter ester hydrazones rearrange at high temperatures to the hydrazides (V). Structural assignments have been made on the basis of elemental and spectral analyses and independent chemical evidence whenever possible.
Charge-transfer and Proton-transfer in the Formation of Molecular Complexes. XI. Phase Transitions in Hertel’s Picric Acid Complexes
Authors: Matsunaga Yoshio , Osawa Eiji , Osawa Ryuzo
Published: July 2006

The isomerization from true phenolates to charge-transfer complexes by phase transitions in Hertel’s five amine-picric acid complexes was confirmed by spectroscopic examinations. The amines and the estimated heats of transition were as follows: o-bromoaniline, 6.7; o-iodoaniline, 6.2; 1-chloro-2-naphthylamine, 8.0; 1-bromo-2-naphthylamine, 8.2; 1,6-dibromo-2-naphthylamine, 3.3 kcal/mol. The transition temperatures and/or the heats in the naphthylamine complexes were shown to be markedly reduced by crushing the crystals. The chargetransfer complexes have electrical resistivities lower by a factor of many decades than the isomeric phenolates. Phase transitions without isomerization were found in the metastable 1-halo-2-naphthylamine complexes of the charge-transfer type.
An X-Ray Diffraction Study of a Concentrated Aqueous Sodium Iodide Solution
Authors: Maeda Masunobu , Ohtaki Hitoshi
Published: July 2006

X-Ray diffraction measurements of a 7 M NaI aqueous solution showed that iodide ion is surrounded by approximately six water molecules, the I−–H2O distance being 3.60 Å and that sodium ion is bonded to about four water molecules at the distance of 2.4 Å.
Photoelectron Spectra of the cis- and trans-Isomers of Some Ethylene Derivatives
Authors: Kobayashi Tsunetoshi , Yokota Katsuyuki , Nagakura Saburo
Published: July 2006

The photoelectron spectra of cis- and trans-stilbenes, fumaric acid, dimethyl maleate, and dimethyl fumarate were measured and interpreted, special attention being paid upon their difference between the corresponding trans- and cis-isomers. The two characteristics were found for the photoelectron spectra of cis- and trans-stilbenes: (1) the splitting between the first and fifth bands is smaller for the cis-isomer (steric-hindrance effect); (2) the splitting between the second and third bands is larger for the cis-isomer (through-space interaction). The difference in the carbonyl n orbital ionization potentials between dimethyl maleate and fumarate was interpreted in terms of through-bond interaction.
The Triplet-Triplet Absorption Spectra and Electronic Structures of Some Cyano-Substituted Benzenes
Authors: Morita Hiroshi , Matsumoto Satoru , Nagakura Saburo
Published: July 2006

Triplet-triplet (T–T) absorption bands were observed at 300, 297, and 320 nm for m- and p-dicyanobenzenes, and 1,3,5-tricyanobenzene, respectively. The nature of the observed spectra was investigated by calculating the wave functions of the triplet states and by analyzing them by the configuration analysis method. It was concluded that the T–T absorption bands of m- and p-dicyanobenzenes, and 1,3,5-tricyanobenzene correspond essentially to the transition from the locally (within the benzene ring) excited state to the intramolecular charge-transfer state.
Thermal Dehydration and Decomposition Reactions of Bivalent Metal Oxalates in the Solid State
Authors: Nagase Kenzo , Sato Katsuya , Tanaka Nobuyuki
Published: July 2006

The thermal dehydration and decomposition of the oxalates of Mg(II), Ca(II), Sr(II), Ba(II), Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) were investigated by means of TG, DTA, DSC, EGA, X-ray powder diffraction analysis, and reflectance and infrared spectroscopies. In general, the temperature at which the oxalates were dehydrated increased with 1/r, where r denotes the radius of metal ion. The heats of dehydration (ΔHH2O) of the alkaline earth metal oxalates increased with 1/r, but those of transition metal oxalates decreased as 1/r increased. By considering the decomposition products, the reactions of anhydrous oxalates were classified into three groups and the relations between the decomposition temperatures and 1/r were discussed for each group.
Photochemical Deuteration of ortho-Substituted N-(Diphenylmethylene)acetamides
Authors: Saeki Masaru , Toshima Naoki , Hirai Hidefumi
Published: July 2006

The alkyl hydrogens of N-(2-alkyldiphenylmethylene)acetamides were found to be readily replaced with deuterium on irradiation in deuteriomethanol (CH3OD). It is proposed that the deuteration proceeds via an enamide isomer produced by intramolecular hydrogen transfer from the o-alkyl group to the excited C=N double bond. An intermolecular hydrogen atom abstraction pathway was excluded because neither N-(4-methyldiphenylmethylene)acetamide in deuteriomethanol(CH3OD) nor diphenylmethane in deuteriomethanol(CH3OD) in the presence of N-(diphenylmethylene)acetamide was deuterated. Intramolecular hydrogen abstraction is essential for the deuteration, because no deuteration occurs on irradiation of 2-methylbenzophenone semicarbazone which undergoes no photoreduction. The difference in reactivities of the ortho-substituted imines between in solution and in a rigid matrix is discussed from the viewpoint of syn-anti isomerization.
Hetera-p-carbophanes. III. Conformation of Amide Groups in and Internal Rotation of Diaza[n]paracyclophanes with Two Alkoxy Groups at the Benzene Ring
Authors: Sakamoto Kazuhiko , Oki Michinori
Published: July 2006

A series of diazadioxo[n]paracyclophane derivatives with two alkoxy groups at the benzene ring were prepared. The conformation of amide groups in these compounds were studied by infrared, PMR, and 13C NMR spectra to draw a conclusion that both amide groups are s-trans. Thus the infrared absorptions at 3430 and 3405 cm−1 are attributed to N–H···π interacting and N–H···O bonded trans forms, respectively. NCH2 protons, which are separated by 5 bonds from the asymmetric center, as well as benzylic protons, were found to be non-equivalent when the rotation of the aromatic ring was slow. PMR spectra of the compounds studied at various temperatures indicate that introducing alkoxy groups in place of methyls at the benzene ring increases the barrier to rotation of the aromatic ring to a great extent.
The Crystal Absorption Spectra of Some Hexachloroiridate(IV) Salts
Authors: Urushiyama Akio , Nakahara Masayoshi , Kondo Yukio
Published: July 2006

The absorption spectra of the single-crystals of several hexachloroiridate(IV) salts and the doped crystals of the hexachlorostannate(IV) salts and the hexachloroplatinate(IV) salt with the IrCl62− anion were measured. Distinct dichroisms appeared in the polarized absorption spectra of all the anisotropic crystals studied. The splittings of the bands and the dichroisms of the spectra were interpreted in terms of the lowering of the symmetry of the IrCl62− anions in the crystal. The absorption bands at 19760 and 20000 cm−1 in the spectra of (CH3NH3)2-Sn(Ir)Cl6 could be assigned to the E′g→E″u and E′g→E′u transitions respectively from their polarizations in the double group, D3d*. Similarly, the bands at 23100, 23500, and 24500 cm−1 were assigned to the E′g→E′u, E′g→E″u, and E′g→E′u transitions respectively. The polarized absorption spectra of Na2IrCl6·6H2O and Na2Pt-(Ir)Cl6·6H2O were also interpreted, assuming that the IrCl62 anions in these crystals were of the D4d symmetry.