bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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&gt;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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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

Abstract
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.