bluuebunny/crossref_metadata_2025 huggingface dataset:
Preparation of Methoxy-substituted Diaryl Ketone Anils via Phenyliminodimagnesium Intermediate
Authors: Okubo Masao , Ueda Sonoko
Published: July 2006

Phenyliminodimagnesium reagent (PhN(MgBr)2) and its o- and p-methoxy derivatives, prepared in THF by treatment of anilines with EtMgBr, were found to be effective for condensation with benzophenones and fluorenone. The corresponding anils (N-(diarylmethylene)anilines) were prepared in good yields.
Kinetics of the Tungstate-catalyzed H2O2 Oxidation of Amines in Aqueous Methanol. Acidity Effect
Authors: Ogata Yoshiro , Tomizawa Kohtaro , Maeda Hirokazu
Published: July 2006

Oxidation of N,N-dimethylaniline and benzylamine with H2O2 catalyzed by Na2WO4 has been kinetically studied in buffered 50% aqueous methanol at 25 °C. The rates with a catalytic amount of Na2WO4fit Eq.: v=k[amine]t[Na2WO4]t[H2O2]0 and the pH profile of rate constant shows no dissociation of peroxotungstate at pH 5–10. N,N-Dimethylaniline gives N-oxide (73%) and benzylamine gives benzaldehyde oxime (65%) under the present kinetic conditions.
Binuclear Metal Complexes. XXXIII. Synthesis, Structure, Spectra, and Magnetism of Binuclear Copper(II) Complexes with 2-[2-(Dialkylamino)ethylthio]ethanol
Authors: Mikuriya Masahiro , Okawa Hisashi , Kida Sigeo
Published: July 2006

Binuclear copper(II) complexes with 2-[2-(dialkylamino)ethylthio]ethanol, Cu{R2N(CH2)2S(CH2)2O}X (abbreviated as Cu(R-nso)X, where R=CH3, C2H5, n-C3H7, n-C4H9; X=Br, Cl, NO3), were prepared and characterized by elemental analyses, infrared and electronic spectra and magnetic susceptibilities (80–300 K). They exhibit a band at 22–26×103 cm−1 characteristic of alkoxo-bridged structure. The magnetic data of Cu(n-C4H9-nso)Cl indicate that a strong antiferromagnetic interaction is operating between the copper ions. However, temperature dependence of magnetic susceptibilities of the other complexes do not obey the equation based on a binuclear structure. The crystal structure of Cu(CH3-nso)Br was determined by the single-crystal X-ray diffraction method. The crystals are monoclinic, space group P21/c, a=10.133(2), b=7.858(2), c=14.893(3) Å, β=118.8(1)°, and Z=2. The structure was solved by the heavy atom method and refined by the block-diagonal least-squares method to an R factor of 0.042. The structure consists of alkoxo-bridged binuclear units, Cu2(CH3-nso)2Br2. The coordination geometry of the copper ion is distorted square pyramid. Since the distances between the binuclear clusters are too long to give rise to an intercluster magnetic interaction, it is suggested that some structural change takes place at low temperature.
Synthesis of 3-(p-Hydroxycinnamoyl)-5-methylfilicinic Acid and Dehydro-3,3′-diacetyl-5,5′-methylenedifilicinic Acid
Authors: Obara Heitaro , Onodera Jun-ichi , Abe Satoshi , Saito Takashi
Published: July 2006

In connection with studies on the structure of carthamin (1), two analogous compounds of 1, 3-(p-hydroxycinnamoyl)-5-methylfilicinic acid and dehydro3,3′-diacetyl-5,5′-methylenedifilicinic acid have been synthesized.
Total Synthesis of Furanoeremophilane and 14-Norfuranoeudesmane Derivatives by a Route Involving Alkylation of 2,4-Dimethyl-3-furoic Acid
Authors: Tada Masahiro , Sugimoto Yayoi , Takahashi Takeyoshi
Published: July 2006

(±)-14-Norfuranoeudesmane-4,6-dione, (±)-furanoeremophilane-3,6-dione, and (±)-furanoeremophilan-14, 6α-olide were synthesized by a route involving alkylation of a dianion obtained from 2,4-dimethyl-3-furoic acid.
Isomerization of Cyclohexene Oxide over Solid Acids and Bases
Authors: Arata Kazushi , Tanabe Kozo
Published: July 2006

The reaction of cyclohexene oxide over solid acids and bases at 108 °C gave five main products, 1,3-cyclohexadiene (1), cyclohexanone (2), cyclohexanol (3), 2-cyclohexen-1-one (4), and 2-cyclohexen-1-ol (5). SiO2–TiO2 and SiO2–TiO2–MgO were highly active for the isomerization, giving a large amount of 1. TiO2–ZrO2 mainly showed selectivity for the formation of 5, and other catalysts formed both 2 and 5. Of the alumina prepared in four different ways, two were highly active, giving 5 predominantly. The results were discussed in comparison with those for an oxide containing a methyl group on the oxide ring, 1-methylcyclohexene oxide. By the experiment using the deuterated epoxide, 1,2-epoxycyclohexane-3,3,6,6-d4, isotope effects for the formation of 2, 3, 4, and 5 over Al2O3’s, SiO2–TiO2 and solid H3PO4 were observed. It has been concluded that the epoxide is adsorbed on both acidic and basic sites, and that allyl alcohol is formed when both the opening of the epoxide ring and the hydrogen abstraction take place simultaneously, while ketone is formed when the former precedes the latter.
Halogenation of Alkyl p-Tolyl Sulfones with Carbon Tetrahalides. Application to the Synthesis of Aromatic Ketones
Authors: Kotake Hiroshi , Inomata Katsuhiko , Kinoshita Hideki , Sakamoto Yasuko , Kaneto Yoko
Published: July 2006

Carbanions of alkyl p-tolyL sulfones reacted with carbon tetrahalides to give the corresponding polyhalogenated products in good yields. Some chlorinated sulfones were converted to unsymmetrical ketones by treatment with silver perchlorate in trifluoroacetic acid.
Monoterpenoid Synthesis by Transition Metal Catalyzed Coupling of Enediylmagnesium with C5-Organic Halides
Authors: Kajihara Yasushi , Ishikawa Katsuhiro , Yasuda Hajime , Nakamura Akira
Published: July 2006

A series of isoprene coupling dimers bonded at 1-2, 1-3, 1-4, 2-4, 3-4, or 4-4 position was prepared by regiocontrolled catalysis of trasition metals or without catalysts in the reaction of 2-methyl-2-butene-1,4-diylmagnesium or 3-methyl-2-butenylmagnesium chloride with C5-alkenyl halides.
CNDO and INDO Calculations of the Magnetic Circular Dichroism of Several Purine Derivatives
Authors: Kaito Akira , Hatano Masahiro
Published: July 2006

Calculations of the magnetic circular dichroism(MCD) of methylpurines and methyladenines were carried out not only by the CNDO/S-CI procedure, but also by the INDO/S-CI procedure. The CNDO/S-CI procedure correctly predicted the signs and magnitudes of the MCD spectra of 1-, 3-, and 7-methylpurines and of 9-methyladenine which cannot be improved by the parameter adjustment. On the other hand, the signs of the MCD spectra and transition energies of all these purine derivatives were clearly explained by the INDO/S-CI procedure.
The Kinetics of Oxygen-exchange Reaction between Chromate Ions and Water
Authors: Okumura Akiko , Kitani Mie , Toyomi Yuiko , Okazaki Nobukazu
Published: July 2006

The oxygen-exchange reaction between chromate ions and water has been studied under the following conditions: 25 °C, pH=7–12, [Cr(VI)]=0.075 mol dm−3, I=0.2 and 1 mol dm−3. The rate law of the exchange reaction has been found to be:

R=k_1[CrO_4^2-]+k_2[HCrO_4^-]+k_3[H^+][HCrO_4^-]+k_4[HCrO_4^-][CrO_4^2-]+k_5[HCrO_4^-]^2.

The exchange rate has been analyzed in terms of this rate law to obtain the values of k1–k5. The presence of the third-order rate term in [Cr(VI)] has been suggested. The activation energy of the overall exchange reaction (I=1 mol dm−3) is (25.5±0.7) kJ/mol at pH 7.4 and (98.9±1.0) kJ/mol at pH 11.0. The salt effect is negative at pH<10.5 and absent at pH>10.5.
Ylide–Metal Complexes. IV. The Preparation and Properties of IIb-group Metel (Zn, Cd, Hg) Complexes of Alkylidenetriphenylphosphoranes
Authors: Yamamoto Yoshihisa , Sugimoto Hideo
Published: July 2006

Ylide-IIb-group metal (Zn, Cd, Hg) complexes, bis(triphenylphosphonium alkylide)metal dichloride, (Remark: Graphics omitted.) (M: Zn, Cd, Hg), and chloro(triphenylphosphonium isobutylide)metal dichloride, (Remark: Graphics omitted.) (M: Zn, Cd), have been obtained from alkylidenetriphenylphosphoranes, (C6H5)3P=CH–R (R: H, CH3 CH(CH3)2), and ZnCl2, CdCl2, or HgCl2. In these organometallic complexes, the alkylidenetriphenylphosphoranes are attached to the IIb-group metals atom through the carbanionic donor atom. They are thermally stable.
The Regiospecific Mono Tosylation of Cyclodextrins
Authors: Onozuka Shigeharu , Kojima Masayoshi , Hattori Kenjiro , Toda Fujio
Published: July 2006

α- and β-Cyclodextrins were tosylated with tosyl chloride in an alkaline solution. The products were confirmed to be monotosylated compounds, and the tosyl group was introduced at the C-3 position of one glucose unit of the cyclodextrin molecule. The 1:1 complex formation of cyclodextrin with tosyl chloride was observed spectrometrically.
The Synthesis of 2-Styrylazulene and Its Derivatives by the Condensation of 2-Methylazulene Derivatives with Benzaldehydes
Authors: Saito Motoyasu , Morita Tadayoshi , Takase Kahei
Published: July 2006

The reaction of 2-methylazulene derivatives, such as dimethyl 2-methylazulene-1,3-dicarboxylate, methyl 3-cyano-2-methylazulene-1-carboxylate, and 1-cyano- and 1-carbamoyl-2-methylazulenes, with benzaldehyde in the presence of alkoxide resulted in condensation to give 2-styrylazulene derivatives. 2-Styrylazulene, a parent hydrocarbon, and its p-nitro and p-dimethylamino derivatives were also synthesized.
Polar Effects in the Reactions of a Series of Substituted Diphenyldiazomethanes with Chloranil
Authors: Oshima Takumi , Nagai Toshikazu
Published: July 2006

The kinetics and products of the reactions of fifteen meta- and para-substituted diphenyldiazomethanes with chloranil were investigated in tetrahydrofuran. The second-order rate constants, k, increased with the electron-donating ability of the substituents, and the values could be correlated with the Yukawa-Tsuno equation: logk⁄k0=−1.67(σ0+0.66Δ\barσR+)+0.009, (r=0.996). The ρ value, −1.67, indicates the large development of a positive charge at the diazo carbon in the transition state, while the R value, 0.66, confirms the considerable stabilization of the positive charge by the π-electronic contribution of the para substituents. The products of these reactions were the corresponding 2,3,5,6-tetrachlorohydroquinone poly(benzhydryl)ethers, but these polyethers were easily hydrolyzed into the corresponding benzophenones and tetrachlorohydroquinone(HQ). On the other hand, the initial presence of water or methanol as an additive changed the reaction features to give benzophenone or α,α-dimethoxydiphenylmethane, together with HQ. Reaction mechanisms which account for the results are discussed.
Substitution and Elimination Reactions via One Electron Transfer Process. A New Olefin Synthesis from β-Nitro Sulfones
Authors: Ono Noboru , Tamura Rui , Nakatsuka Tamon , Hayami Jun-ichi , Kaji Aritsune
Published: July 2006

gem-Bromonitro compounds or gem-dinitro compounds couple with carbanions derived from α-cyano sulfones or α-carbonyl sulfones to give β-nitro sulfones. The nitro and sulfonyl groups are eliminated from the coupling products on treatment with reductive one electron transfer reagents to give α,β-unsaturated carbonyl compounds or nitriles.
Synthesis of 3-Mono- and 3,5-Difunctionalized Noriceanes (Tetracyclo[5.3.1.02,6.04,9]undecanes) via Oxymetallation of 3,5-Dehydronoriceane (Pentacyclot[5.3.1.02,6.03,5.04,9]undecane). Oxidation of Bicyclo[2.1.0]pentane System by Mercury(II), Thallium(III), and Lead(IV) Acetates.
Authors: Katsushima Takeo , Yamaguchi Ryohei , Iemura Satoshi , Kawanisi Mituyosi
Published: July 2006

Oxymercuration of 3,5-dehydronoriceane (1) followed by sodium borohydride reduction gives exclusively endo-3-noriceanol in 80% yield. The trans-1,3-addition organomercury intermediate is isolated as endo-3-acetoxy-exo-5-(chloromercurio)noriceane. Oxidation of 1 with thallium(III) acetate gives three diacetates, exo,exo- and endo,exo-3,5-diacetoxynoriceanes [(9) and (10)] and endo,exo-4,5-diacetoxytetracyclo[5.3.1.02,6.03,9]undecane (11) in a ratio of 6:61:27 in 68% combined yield. The analogous oxidation of 1 with lead(IV) acetate gives 9, 10, and 11 in a ratio of 50:25:25 in 80% combined yield. On the basis of the stereochemistry of the products as well as the products distribution, we propose that 1,3-bridged metal ion intervenes and plays an important role in the oxymetallation reaction of bicyclo[2.1.0]pentane system.
Halogenation of 3,5-Dehydronoriceane (Pentacyclo[5.3.1.02,6.03,5.04,9]undecane. Front Side Attack on the Bicyclo[2.1.0]pentane System by Halonium Ion and Corner Side Attack by Halogen Radical
Authors: Katsushima Takeo , Yamaguchi Ryohei , Iemura Satoshi , Kawanisi Mituyosi
Published: July 2006

Halogenations of 3,5-dehydronoriceane (1) in dichloromethane in the dark exclusively or predominantly give endo,exo-4,5-dihalotetracyclo[5.3.1.02,6.03,9]undecanes; these results provide a decisive evidence for the front side attack on the bicyclo[2.1.0]pentane system by halonium ion. On the other hand, the corner side attack on the bicyclo[2.1.0]pentane system by halogen radicals takes place in photohalogenations of 1, which give endo,endo- and endo,exo-3,5-dihalonoriceanes. In addition, the halogenation of 1 in the dark is found to be sensitive to the solvent polarity and the ionic nature of the halogen used. Bromination of 1 in nonpolar solvents in the dark likely proceeds through intervention of the 1,3-bridged bromonium ion.
An Investigation of the Power Characteristics in Heterogeneous Electrochemical Photovoltaic Cells for Solar-energy Utilization
Authors: Inoue Tooru , Weber Claude , Fujishima Akira , Honda Kenichi
Published: July 2006

A heterogeneous electrochemical photovoltaic cell was constructed using the system of cadmium sulfide(CdS)/sulfides reducing agents//oxidizing agents/platinum. The output power characteristics were investigated focusing upon the redox potentials of the oxidizing agents in the cathodic half-cell and then discussed from the point of view of the solution-electrode junction. Though this type of cell intrinsically has a negative free energy for redox reactions of redox agents in an anodic and a cathodic compartment, it has a characteristic point that a larger open-circuit output than the intrinsical electromotive force determined by a redox couple was obtainable in operation under illumination. For example, in the CdS/S2−/S//Fe2+⁄3+/Pt system we found the open-circuit photovoltage of ca. 2.0 V, which is ca. 83% of a band gap (2.4 eV) of CdS. These measurements showed that a larger open-circuit photovoltage was obtained, though, of course, it was smaller than the band-gap energy of CdS, when the oxidizing agent of the more positive redox potential was dissolved in the cathodic compartment.
ESR Studies of Temperature Dependent Zero-field Splitting in Yang’s Biradical
Authors: Mukai Kazuo , Ishizu Kazuhiko , Nakahara Mizue , Deguchi Yasuo
Published: July 2006

The ESR absorptions of Yang’s biradical in a few organic solvents have been studied in detail as a function of temperature, and the effect of temperature on the symmetry of the biradical molecule has been discussed on the basis of the temperature dependence of the zerofield splitting parameters.
Catalysis by Heteropolyacid. III. Acylation and Sulfonylation of Aromatic Compounds Catalyzed by Keggin-structure Heteropolyacids
Authors: Nomiya Kenji , Sugaya Yoshio , Miwa Makoto
Published: July 2006

Catalytic acylation and sulfonylation reactions of aromatic compounds by Keggin-structure heteropolyacids, H4[SiMo12O40], H3[PMo12O40] and H4[SiW12O40], have been studied. Tungsten is more effective than molybdenum for the reactions.
The Fraction of Bound Segments and the Chain Motion of Adsorbed Poly(methyl methacrylate) at the Solution-Solid Interface as Studied by Electron Spin Resonance
Authors: Sakai Harutoshi , Fujimori Toshihiko , Imamura Yoshio
Published: July 2006

The configuration of poly(methyl methacrylate) adsorbed on silica from dilute solution (CCl4, benzene, and CHCl3) was studied from the point of view of the chain motion by a spin-labeling technique. The ESR spectrum of the adsorbed polymer was found to be composed of three portions, which had considerably different degrees of the motional freedom of the local chain segments. The rotational correlation times corresponding to the three portions were estimated by the line shape analysis and the rapid passage technique. These times were 1×10−9, 5×10−9, and longer than 10−6 s, and were attributed to the motions in the long loop, short loop, and train, respectively. The large fractions of the bound segments, obtained in all the cases of low surface coverage, showed highly flattened structures of the adsorbed chain molecules. In the adsorption from a poor solvent (CCl4), a strongly compressed structure with a large number of the short loops was found. The adsorbed layer thickness, indicated by the fraction of the segments in the three states, became much smaller with an increase in the solvent power and a decrease in the surface coverage.
Laser Induced Biphotonic Dissociation of Nitrobenzene Derivatives in Solution
Authors: Yokoyama Kenji , Nakamura Junko , Kobayashi Takayoshi , Nagakura Saburo
Published: July 2006

By irradiation with a focused laser beam, p-nitroanisole and N-[2-(p-nitrophenoxy)ethyl] aniline (2) in acetonitrile were found to show new reactions yielding nitroso compounds different from the case of the defocused laser beam irradiation. The laser intensity dependence of the product yield shows that the new reaction of 2 proceeds via a biphotonic process. The quenching effects of oxygen and cis-1,3-pentadiene upon the reaction rate indicate that the intermediate state is an excited singlet state.
A Kinetic Study on the Proton-transfer Reactions of Bis(dimethyl-glyoximato)cobalt (III) Complex Ions in Dioxane–Water Media
Authors: Yoshida Noboru , Fujimoto Masatoshi
Published: July 2006

The proton-transfer reactions of bis(dimethylglyoximato)cobalt(III) complex ions, [CoIII(dmgH)2X2]n, with hydroxide ion, OH−, were studied in dioxane–water media by means of a temperature-jump method. The rate constant, kf, for the direct proton-transfer from [CoIII(dmgH)2X2]n to OH− was found to be 1.6×105–2.9×106 mol−1 dm3 s−1 in aqueous solution. The value of kf for [CoIII(dmgH)2(CN)2]− anion decreased gradually from 1.6×105 to 4.0×104 mol−1 dm3 s−1 for the change in the mole fraction of dioxane, xdiox, from 0 to 0.174. On the other hand, with increase in xdiox, the value of kf for [CoIII(dmgH)2(NH3)2]+ cation gradually decreased from 2.9×106 to 1.1×107 mol−1 dm3 s−1 in a region of lower xdiox, and then increased from 1.1×106 to 1.6×106 mol−1 dm3 s−1 in a region of higher xdiox. The dependence of kf on xdiox is interpreted in connection with reaction mechanism.
The Thermal Decomposition of Ammonium Chloride Tetrachlorozincate and the Formation of Tetrachlorozincate Complexes of Alkali Metal by Means of Solid Reactions with Alkali Chlorides
Authors: Ichiba Sumio , Oshima Satoshi , Negita Hisao , Tanaka Haruhiko
Published: July 2006

Ammonium chloride tetrachlorozincate, (NH4)3Cl[ZnCl4], decomposes to ZnCl2 in two stages through an intermediate phase (NH4)2[ZnCl4]. In the first stage, 1 mol of NH4Cl is lost by one-dimensional diffusion mechanisms with the activation energy of 138 kJ mol−1, and in the second stage the release of two moles of NH4Cl is controlled by a random nucleation reaction with the activation energy of 126 kJ mol−1, corresponding to the bondbreaking. Anhydrous alkali metal tetrachlorozincate complexes, M2[ZnCl4](M=Na, K, Rb, Cs), are obtained by solid reactions with alkali chlorides when (NH4)3Cl[ZnCl4] decomposes. A dry chemical method using (NH4)3Cl[ZnCl4] as a starting material is proposed for the preparation of the anhydrous chlorozincate complexes, which have thus far been difficult to synthesize.
Kinetic Studies of Fast Equilibrium by High-performance Liquid Chromatography I. Ternary Complex Formation of N,N-Disubstituted Dithiocarbamate Chelates of Ni(II) and Cu(II)
Authors: Moriyasu Masataka , Hashimoto Yohei
Published: July 2006

The equilibrium of labile ternary complex formation of metal dialkyldithiocarbamate chelates (MA2+MB2\oversetk\undersetk−\ightleftharpoons 2MAB, K=[MAB]2/[MA2][MB2]) has been investigated by high-performance liquid chromatography, the separation process of which is so fast that kinetically unstable ternary complexes can be eluted with no disproportionation during the course of chromatography. High-performance liquid chromatography makes it possible to halt the progress of considerably fast reactions at the moment when the solution of reaction system is injected into the column. Thus, chromatograms obtained indicate the concentration of each species before chromatography, facilitating the determination of equilibrium constant K of Ni(II) and Cu(II) chelates. The equilibrium constants obtained are always 4.0, suggesting that ternary complex formation is controlled by a statistical factor. Disproportionation takes place by collision of two ternary metal chelates, the rate constants being of the order 101–102 M−1 s−1 (Ni(II) chelates) and 103 M−1 s−1 (Cu(II) chelates). The activation parameters of ternary complex formation have been obtained.
Synthetic Photochemistry. XIX. The Synthesis of Protoilludanes by Photocycloadditions, Protoillud-7-ene and Several Oxygenated Derivatives
Authors: Takeshita Hitoshi , Kouno Isao , Iino Mitsuaki , Iwabuchi Hisakatsu , Nomura Danji
Published: July 2006

Unlike ethylene, 1,1-dimethoxyethene, an electron-rich olefin, has been photocycloadded to a cis-hexahydroindenone to form a norprotoilludane derivative with a correct stereostructure. Methylation and subsequent chemical transformations yielded several oxygenated derivatives, from which the parent hydrocarbon, protoillud-7-ene, was obtained by deoxygenation. Independent evidence for the stereostructures of the synthetic derivatives has been provided by the X-ray crystallographic analysis of a dihydroxy acetal.
The Stereochemical Course of the Photochemical Berson-Willcott Rearrangement of exo-1-Methoxycarbonylmethyl-3-t-butyl-1a,7b-dihydro-1H-cyclopropa[a]naphthalene to 7-Methoxy-carbonylmethyl-5-t-butyl-7H-benzocycloheptene
Authors: Kato Masahiko , Takatoku Keizo , Ito Satoru , Funakura Mitsuru , Miwa Toshio
Published: July 2006

The photolysis of (1S)-exo-1-methoxycarbonylmethyl-3-t-butyl-1a,7b-dihydro-1H-cyclopropa[a]naphthalene gave (7S)-5-t-butyl-7-methoxycarbonylmethyl-7H-benzocycloheptene by a 1,5-sigmatropic shift, proving the rearrangement to proceed with the inversion of the configuration of the migrating center.
New Monoterpene Lactones of the Iridane Type from Actinidia polygama Miq.
Authors: Sakai Tsutomu , Nakajima Kimiko , Sakan Takeo
Published: July 2006

Fourteen iridoid monoterpene lactones including eight new compounds were isolated from the volatile oil of fresh fruits of the cat- and lacewing-attracting plant Actinidia polygama Miq., and their structures were established on the basis of spectral evidence and chemical transformation.
Synthesis and Stereochemistry of 2,3,4,6-Tetra-O-benzyl-d-gluco-pyranosylidene Acetals of α-Diols and Monosaccharides
Authors: Tamaru Masatoshi , Horito Shigeomi , Yoshimura Juji
Published: July 2006

The title compounds were synthesized by addition of 2,3,4,6-tetra-O-benzyl-d-glucono-1,5-lactone to epoxides and by direct dehydration between the lactone and diols in the presence of concentrated sulfuric acid as a catalyst. Stereochemistry of these spiro cyclic acetals was discussed.
Classification of the External Magnetic Field Effects on the Photodecomposition Reaction of Dibenzoyl Peroxide
Authors: Sakaguchi Yoshio , Hayashi Hisaharu , Nagakura Saburo
Published: July 2006

The external magnetic field effects upon product yields in the singlet sensitized photolysis of dibenzoyl peroxide in toluene were studied. The observed field dependencies were classified into four types, and were interpreted in terms of the electronic Zeeman and hyperfine interactions in the intermediate radical pair. Especially large magnetic field effects were observed for the yields of dimethylbiphenyls, new products in this reaction.
Intramolecular Cycloaddition Reactions of N-Sulfonyl Nitrile Imides Bearing Alkenyl Groups
Authors: Shimizu Tomio , Hayashi Yoshiyuki , Nagano Yoshio , Teramura Kazuhiro
Published: July 2006

The reaction of the p-tolyl(or phenyl)sulfonylhydrazones of some 2-(alkenyloxy)benzaldehydes with lead tetraacetate leads, via the nitrile imide intermediates, Ar–\overset+C=N–\overset−N–SO2–C6H4–X-p, to intramolecular 1,3-dipolar cycloadducts and 1-acetyl-2-aroyl-1-[p-tolyl(or phenyl)sulfonyl]hydrazines in 20–65% and 7–70% yields respectively, while the intermolecular reactions of the benzaldehyde p-tolylsulfonylhydrazone with a dipolarophile such as acrylonitrile or styrene in the presence of lead tetraacetate gives only 1-acetyl-2-benzoyl-1-(p-tolylsulfonyl)hydrazine. The treatment of the N-(p-tolylsulfonyl)-o-(allyloxy)benzohydrazonoyl chloride (10) with triethylamine or by refluxing a benzene solution of 10 also gives an intramolecular 1,3-dipolar cycloadduct in a good yield.
Light Scattering Study of Local Structure in Solutions. Importance of Temperature Dependency Measurements
Authors: Kato Tadashi , Yano Katsuaki , Fujiyama Tsunetake
Published: July 2006

Light scattering spectra have been observed for binary solutions of acetic acid and carbon tetrachloride at several concentrations and temperatures. The Rayleigh intensities were reduced to concentration fluctuations. The observed concentration and temperature dependencies of concentration fluctuation were interpreted by assuming association equilibria involving both cyclic dimers and linear polymers. The simultaneous measurement of concentration and temperature dependencies of concentration fluctuation are necessary to determine local structures in solutions where different types of local structure coexist.
Ab Initio Studies of the Hydrogen Atom Addition to Ethylene
Authors: Nomura Okio , Iwata Suehiro
Published: July 2006

The ethyl radical formation from hydrogen and ethylene was studied with ab initio open shell SCF and CI methods. At first, the minimal basis set (STO-6G) was used to determine a minimal energy path. The calculated exothermicity and the height of the barrier were 72.3 kcal/mol and 16.9 kcal/mol, respectively. After the full geometry optimization with the double zeta basis set the calculated exothermicity became 38.3 kcal/mol, which is in agreement with the experimental value (40.1 kcal/mol), but the barrier height (16.5 kcal/mol) was no better than that obtained by the minimal basis set. After the extensive CI calculations along Sloane and Hase’s path with the minimal basis set, the calculated height of the barrier became only 5.1 kcal/mol. The small but finite barrier height is important in this reaction. The successive hydrogenation to form ethane was also studied and no barrier was found in the reaction.
Absorption Spectra of the Polyacetylene Films Doped with BF3
Authors: Tanaka Masashi , Watanabe Atsushi , Tanaka Jiro
Published: July 2006

Optical absorption measurements are carried out on pure and BF3 doped polyacetylene films over a wide wavelength region (200 cm−1–54000 cm−1). In the lightly doped polymer, the extra peak appears at 870 cm−1 and it is assigned to the transition from the valence band to the impurity level. This band becomes more intense at low temperature. For the heavily doped films, the dc conductivity of the (CH)x fibril is optically estimated to be σ0=104 Ω−1 cm−1. This value is in good agreement with the calculated value (σ0=0.8×104 Ω−1 cm−1) due to the tight binding model.
Equilibrium Study of Iron Vanadium Sulfides in the Iron-rich Portion of the Composition Triangle of FeS–VS–S
Authors: Wada Hiroaki
Published: July 2006

An equilibrium study of a part of the Fe–V–S system at sections with atomic Fe: V ratios of 1:0, 9:1, and 4:1 was carried out by means of thermogravimetry. The thermochemical data which were obtained in the range of log(PS2/atm)=−4 to −0.8 at temperatures between 520 and 814 °C are presented. The compositional limits of the univariant assemblage of Fe1−δS–FeS2–(Fe,V)3S4 were determined at 570 °C on the basis of X-ray analyses of the quenched specimens. The rate of FeS2 formation under the experimental conditions employed was studied qualitatively from the point of view of the sulfidation kinetics of iron vanadium sulfides.
Transition Metal Alkoxides. Preparation and Properties of Bis(aryloxo)iron(II) and Bis(alkoxo)iron(II) Complexes Having 2,2′-Bipyridine Ligands
Authors: Komiya Sanshiro , Tane-ichi Shoshiro , Yamamoto Akio , Yamamoto Takakazu
Published: July 2006

A series of bis(aryloxo)iron(II), 2a–2g, and bis(alkoxo)iron(II), 2h–2k, complexes with 2,2′-bipyridine ligands (Fe(OC6H4X)2(bpy)n and Fe(OR)2(bpy)n) have been prepared by the reactions of diethylbis(2,2′-bipyridine)iron(II) (1) with corresponding p-substituted phenols and alcohols, respectively. (X=NO2, CN, Cl, C6H5, H, and CH3; R=CH3, C2H5, iso-C3H7, and CH2C6H5). These compounds were characterized by IR and NMR spectroscopies and elemental analyses as well as by chemical reactions. Kinetic investigation of the reactions of 1 with phenols by a visible spectroscopic method supports a mechanism involving partial dissociation of the 2,2′-bipyridine ligand, followed by coordination of phenol and activation of the Fe–C2H5 bonds giving the bis(phenoxo)iron(II) compound. Thermolysis of bis(alkoxo)iron(II) complexes gives not only disproportionation products of the alkoxo ligands (alcohols and aldehydes) but also organic products which are obtained as the result of C–O bond cleavage of the alkoxo groups. Interactions of 2 with acyl and alkyl halides lead to the formation of corresponding esters and ethers. Reactions of these iron(II) complexes with various organic acetates give corresponding acetates via an alkoxo exchange reaction. Bis(aryloxo)iron(II) complexes, 2, are hydrolyzed with H2O to yield phenols. Catalytic trans-esteriflcation between ester and alcohol and Tishchenko type dimerization of benzaldehyde are effectively promoted under mild conditions by the bis(phenoxo)iron(II) and bis(benzyloxo)iron(II) complexes, respectively.
Physical Properties and Various Reactions of Thionitrites and Related Substances
Authors: Oae Shigeru , Shinhama K\={o}ichi , Fujimori Ken , Kim Yong Hae
Published: July 2006

Several new sulfonyl or sulfonyl derivativives, thionitrates (RSNO2), sulfonyl nitrites (RSO2NO), were successfully isolated by treating corresponding thiols and sulfinic acids with dinitrogen tetraoxide (N2O4). Spectroscopic data of both stable and many rather unstable compounds were determined and compared with those of corresponding alkyl nitrites (RONO) or alkyl nitrates (RONO2). Chemical reactivities of these uncommon, novel S-nitroso and S-nitro compounds were investigated.
Chemiluminescence of a Cypridina Luciferin Analogue, 2-Methyl-6-phenyl-3,7-dihydroimidazo[1,2-a]pyrazin-3-one, in the Presence of the Xanthine–Xanthine Oxidase System
Authors: Goto Toshio , Takagi Tetsuyuki
Published: July 2006

The title compound chemiluminesces in aqueous solutions (pH 5–6.5) in the presence of xanthine–xanthine oxidase system; O2− and not 1O2 was proven to be the active species. Quantitative determination of xanthine and xanthine oxidase as low as 5 nmol and 10−5 unit, respectively, is possible by measurement of the chemiluminescence light yield and the reaction rate.
The Coprecipitation of Antimony(III or V) with Iron(III) Hydroxide
Authors: Inoue Yoshikazu , Munemori Makoto
Published: July 2006

The coprecipitation of antimony(III or V) with iron(III) hydroxide as a function of the pH in the range from 4 to 12 was studied in the presence of the chloride ion. Antimony(III) is coprecipitated more easily at any given pH value than antimony(V). The coprecipitation of antimony(III) is quantitative in the pH range from 4 to 10 and is not affected by the chloride ion. On the other hand, the coprecipitation of antimony(V) is affected not only by the pH range, but also by the chloride-ion concentration.
An X-Ray Diffraction Study on the Structures of Bis- and Tris(ethylenediamine)cadmium(II) Complexes in Solution
Authors: Fujita Tadao , Ohtaki Hitoshi
Published: July 2006

The structures of cadmium(II) complexes with ethylenediamine(en) have been determined by means of X-ray diffraction. The measurements were performed at 25 °C for aqueous ethylenediamine solutions of cadmium nitrate, the mole ratios (en/Cd) in the solutions being 2.188 and 3.387. In the solution of the lower en/Cd mole ratio, the bis(ethylenediamine)cadmium(II) complex was predominant, whereas in the other solution the tris(ethylenediamine)cadmium(II) complex was contained as the main species. From the analysis of the X-ray scattering data of the solutions, it was shown that in the bis-complex four nitrogen atoms within the two ethylenediamine molecules were tetrahedrally coordinated to the cadmium(II) ion at a distance of 2.339(4) Å. The nonbonding Cd···C distance within the bis-complex was also determined to be 3.04(1) Å. In the tris-complex the cadmium(II) ion was coordinated with six nitrogen atoms and the Cd–N and Cd···C distances were 2.371(5) and 3.19(1) Å, respectively. The strength of the Cd–N bond with changing coordination number of the complexes was discussed in terms of the frequencies of the Cd–N bond in the Raman spectra of these solutions and the bond lengths found from the X-ray scattering measurements.
An Application of the Extended Principal Component Analysis to Circular Dichroism and Optical Rotatory Dispersion. A Case of Poly(α-l-glutamic acid) in the Helix-Coil Transition Region
Authors: Yamaoka Kiwamu , Matsuda Takumi , Takatsuki Mineo
Published: July 2006

The extended principal-component-analysis (PCA) method has been applied to circular dichroism (CD) and optical rotatory dispersion (ORD). The validity of this method has been examined with ideal binary and ternary equilibrium systems, for which the data CD spectra and ORD curves were computer-generated. Satisfactory results were obtained for these multicomponent optically active systems. As an example, the ultraviolet CD spectra of poly(α-l-glutamic acid) in the pH-induced helix-coil transition region were analyzed with the PCA procedure. By the extended PCA method, the pure CD spectra for both helix and random-coil conformations and the helix fractions in the transition region were determined from eight experimentally obtained CD spectra. By introducing an empirical parameter α into the Henderson-Hasselbalch equation, the helix-coil transition curve was reproduced reasonably well.
The Removal and Solidification of Halogenide Ions Using a New Inorganic Compound
Authors: Kodama Hiroshi
Published: July 2006

The present paper discusses a new method for removing and solidifying halogenide ions from solution by a reaction with Bi5(NO3)O7. Since this compound is isostructural with Bi5(I)O7 or Bi5(Br)O7, an ion exchange of the halogen ions with NO3− is expected.

Bi5(NO3)O7 was reacted with aqueous halogenide ions at 25, 50, and 75 °C. The iodide ion was removed almost perfectly at 50 and 75 °C. The reactions were completed after 15 h. The bromide ion was also removed almost perfectly at 25, 50, and 75 °C. The reactions at 50 and 75 °C were completed after 24 h. The chloride ion was also removed by reactions at 50 and 75 °C, which were almost completed after about 48 h. The fluoride ion was not removed.

The iodide and bromide ions reacted with Bi5(NO3)O7 to form Bi5(X)O7 (X = I or Br), provided that their concentrations were below 2.0 and 1.0 mol dm−3, respectively. The chloride ion formed other types of compounds, such as Bi12(Cl2)O17 or Bi3(Cl)O4.

The ion-exchange capacities of iodide, bromide and chloride ions were observed at 50 and 75 °C.
Crystal Structures of trans- and cis-Anionobis(ethylenediamine)nitrosylruthenium(II) Complexes
Authors: Tomizawa Hiroshi , Miki Eiichi , Mizumachi Kunihiko , Ishimori Tatsujiro
Published: July 2006

The structures of trans-[RuX(en)2NO]X′2 (X = OH (1), Cl (3), or NCS (4), en = ethylenediamine, X′ = Br (1), Cl (3), or NCS (4)), trans-[Ru(H2O)(en)2NO]Cl3 (2), cis-[RuX(en)2NO]XPF6 (X = Cl (5), or Br (6)), and cis-[Ru(NCS)(en)2NO]I2·H2O (7) were determined by X-ray diffraction. In two pairs of the geometrical isomers (3 and 5, and 4 and 7), the Ru–Cl or the Ru–N(NCS) bond for the trans isomer was shorter than that for the cis isomer due to a trans-strengthening effect of the NO; this effect was not observed for the corresponding Ru–N(en) bond. These facts indicate that the effect is mainly caused by both σ- and π-bonding interactions of the ligand trans to NO through Ru, and is not caused by only the σ-donation of the ligand.
Studies on Mixed Chelates. XXII. Five-Coordinate Copper(II) Chelates with N,N,N′,N″,N″-Pentamethyldiethylenetriamine and β-Diketonates
Authors: Shintani Noriko , Nukui Etsuko , Miyamae Hiroshi , Fukuda Yutaka , Sone Kozo
Published: July 2006

Mixed Cu(II) chelates with N,N,N′,N″,N″-pentamethyldiethylenetriamine (pmdt) and five β-diketonate (dike) ligands, i.e., dipivaloylmethanate (dipm), acetylacetonate (acac), pivaloyltrifluoroacetonate (pfac), trifluoro- and hexafluoroacetylacetonate (tfac and hfac, respectively), were prepared and studied. Their general formula, [Cu(dike)(pmdt)]ClO4, suggests that they are five-coordinated; X-ray crystal analyses confirmed that the chelates with acac and tfac are distorted square pyramidal, with the axial site occupied by one of the O atoms of dike. Similar structures are presumed for the remaining chelates on the basis of spectral similarities. In solutions, these five-coordinated chelates are solvated to various extents, showing a characteristic solvatochromism.
Ion-Associate Solvent Extraction and Separation of Lanthanides(III) with 2,3-Naphthalenediol and Benzyldimethyltetradecylammonium Chloride
Authors: Takayanagi Toshio , Yotsuyanagi Takao
Published: July 2006

In order to improve the separation factors among lanthanides(III), ion-associate extraction system for them was studied using 2,3-naphthalenediol (H2L) as a diprotic chelating reagent and benzyldimethyltetradecylammonium chloride (Z+Cl−) as an ion-associate reagent at 298 K and the ionic strength of 0.1 (NaCl). Lanthanide ions, Pr3+, Eu3+, and Yb3+, are extracted at weakly acidic pH region as Z+2Na+[ML3]3−. Sufficiently large separation factors among them are obtained. This system has a sharp pH dependence, with a slope of 6 for the plots of log {[M3+](T, o)/[M3+]} against pH at a constant concentrations of H2L(o), Z+Cl−(o), and NaCl, where the subscripts T and o indicate the total concentration of lanthanide ions and the species in the organic phase, respectively. Details of the extraction system are discussed.
Axial Substitution Reaction of Substituted Pyridine on Chloro(5,10,15,20-tetraphenylporphinato)chromium(III) in Toluene with Special Reference to the Substituent Effect
Authors: Inamo Masahiko , Sugiura Sachio , Fukuyama Hiroshi , Funahashi Shigenobu
Published: July 2006

Equilibria and kinetics for the axial substitution reaction of pyridine and substituted pyridines (L) coordinated to chloro(5,10,15,20-tetraphenylporphinato)chromium(III) [Cr(tpp)(Cl)] by 1-methylimidazole as an entering ligand in toluene have been studied spectrophotometrically. Equilibrium constants, rate constants, and activation parameters for the substitution of L from the six-coordinated [Cr(tpp)(Cl)(L)] complex have been obtained. It has been demonstrated that equilibrium constants of the substitution reaction depend on the basicity of the axial ligands and that a good linear relationship between the activation parameters and the basicity of L is in accord with the reaction mechanism with a limiting dissociative activation mode.
Rubidium and Cesium Selenocarboxylates: Synthesis and Characterization
Authors: Kawahara Yasuyuki , Kato Shinzi , Kanda Takahiro , Murai Toshiaki
Published: July 2006

Rubidium and cesium selenocarboxylates (2 and 3) were found to be synthesized in good to high yields from the reaction of O-trimethylsilyl selenocarboxylates with rubidium and cesium fluorides. The spectroscopic properties of 2 and 3 are also given.
2-(1-Pyrrolyl, Diazolyl, and Triazolyl)-Substituted 5-Nitropyridines for Nonlinear Optical Materials
Authors: Okazaki Masaki , Fukunaga Hiroo , Ishihara Makoto , Kubo Kazumi
Published: July 2006

2-Azolyl-5-nitropyridines (the generic name “azoles” is hereafter used for pyrrole, diazoles, and triazoles, and “azolyls” for any substituents derived from them) were examined from the viewpoints of the UV-vis absorption properties, the molecular hyperpolarizabilities (β), the second-harmonic generation (SHG) activities and the crystal structure compared with N-(4-nitrophenyl)azoles. In the azolyl-5-nitropyridines, although an expected remarkable hypsochromic shift of the absorption maxima (λmax) was not observed, a hypsochromic shift of the absorption edge (λcutoff) was observed. All of derivatives discussed in the present paper, except for 2-(3,5-dimethyltriazolyl)-5-nitropyridine (14), did not show any SHG activity. The inactive results in SHG suggest that the displacement of benzene to pyridine causes a significant change in the molecular arrangement in the crystalline state. The phase-matchable property in the SHG of 14 is suggested by its crystal structure as well as an SHG experiment.
Synthesis and Crystal Structure of [(IrCp*)2(μ-OH)3]2(Cr2O7)·8H2O (Cp* = η5-C5Me5). A Novel Two-Dimensional Hydrogen-Bonding Network
Authors: Park Joon T , Nishioka Takanori , Suzuki Takayoshi , Isobe Kiyoshi
Published: July 2006

The title complex, prepared from a reaction of [(IrCp*Cl)2(μ-Cl)2] with K2CrO4 in water, has been characterized via a single-crystal X-ray diffraction study. In the solid state the tri-μ-hydroxo-diiridium complex cations, the dichromates having the staggered conformation, and the water molecules of crystallization are entirely connected by hydrogen bonds forming a novel two-dimensional layer structure.
Crystal Structure and Conformation of N-(t-Butoxycarbonyl)-l-Alanyl-S-Benzyl-l-Cysteine Methyl Ester
Authors: Sukumar N , Ponnuswamy M N , Jayakumar R
Published: July 2006

The dipeptide, N-(t-butoxycarbonyl)-l-alanyl-S-benzyl-l-cysteine methyl ester (Boc–Ala–Cys(Bzl)–OMe) has been crystallized in orthorhomic space group P212121 with cell dimensions of a = 9.565(1), b = 43.282(1), and c = 5.096(1) Å. The structure was determined by direct methods and refined to an R-factor of 0.049. The molecules are packed in a parallel-pleated sheet arrangement and stabilized by N–H···O hydrogen bonds.
Surface Microstructure of Oxide-Coated Electrodes for Chlorine Evolution
Authors: Takasu Yoshio , Kameyama Kohichi , Onoue Satoshi , Ueno Mitsuo , Murakami Yasushi , Yahikozawa Kiyochika
Published: July 2006

By use of high-resolution scanning electron microscopy and electron probe X-ray microanalysis, the surface structure of RuO2–IrO2-TiO2/Ti electrodes has been clarified. It is composed of highly grown Ti-deficient crystallites and ultrafine Ti-rich oxide particles of 5—20 nm in diameter, forming a porous structure.
Partnerships in Training
Authors: Merrick Jason R. W. , Hardin Jill R. , Walker Russell
Published: July 2006

Capital One Financial Corporation supplies credit products in the US. Since 1995, it has followed an information-based strategy, collecting and analyzing data to improve its business decisions. To continue this successful strategy, it must train its analysts in analytical techniques. In a partnership between Capital One and the Department of Statistical Sciences and Operations Research at Virginia Commonwealth University, we developed three training courses in forecasting, optimization, and simulation. These courses have been well received by the analysts and have led to considerable early return on investment with one class project forecasted to reduce costs at the firm’s Richmond, Virginia mail center by more than $2 million annually.
Caterpillar’s Building Construction Products Division Improves and Stabilizes Product Availability
Authors: Keene Susan , Alberti David , Henby Gary , Brohinsky A. J. , Tayur Sridhar
Published: July 2006

In 2001, Caterpillar’s Building Construction Products Division (BCPD) began a project to reduce and stabilize order-to-delivery times (termed product availability within Caterpillar) while reducing cost and inventory. Using a six-sigma method and a multiechelon inventory optimization model, BCPD sets dynamic inventory policies for assembled machines stocked at the assembly plant and for subassemblies and components stocked at the assembly plant and at supplier locations. The project has improved product availability, reducing the mean time for orders with identified customers by 20 percent and reducing the standard deviation of product availability for all orders by 50 percent. BCPD’s initial implementation and resulting improved product availability enabled BCPD to win more orders (a two percent increase in revenues) and reduce total chain inventory by 16 percent, and it has motivated other Caterpillar manufacturing and assembly facilities to replicate this project across their supply chains.
Concerns Over the Allocation Methods Employed in the US Low-Income Home Energy Assistance Program
Authors: Kaiser Mark J. , Pulsipher Allan G.
Published: July 2006

The Low-Income Home Energy Assistance Program (LIHEAP) is the largest federal energy assistance program in the United States and forms an important component of the social safety net for low-income households. The manner in which LIHEAP funds are allocated to states has been a contentious issue since the inception of the program. The distribution of funds among states is not proportionate to the need for assistance based on commonly accepted standards of fairness, with states in the Northeast and Midwest receiving more, and states in the South and West, less than they should. We derived and evaluated the formula by which states receive LIHEAP funding, and we found that unanticipated circumstances, not congressional intent, have perpetuated an inequitable distribution. In 1984, Congress corrected the formula it had hastily enacted in 1981 using a rational and equitable allocation system. It also added provisions, however, that prevented the improved system from being activated. As Congress considers future reauthorizations of LIHEAP, it has three options: to fully implement the intent of the 1984 reform of the program; to acknowledge that LIHEAP is primarily a heating-assistance program and adopt a heating-only formula to distribute LIHEAP funding; or to significantly increase LIHEAP funding. The history of LIHEAP appropriations does not imply that the reforms incorporated in the 1984 legislation should be thwarted; it implies that Congress should remove or reduce the legislative provisions that have produced the unintended result. Congress can fully implement the 1984 reform by removing the trigger appropriation or reducing the threshold to $1 billion or less.
Inbound Logistic Planning: Minimizing Transportation and Inventory Cost
Authors: Berman Oded , Wang Qian
Published: July 2006

In today’s competitive environment, supply chain management is a major concern for a company. Two of the key issues in supply chain management are transportation and inventory management. To achieve significant savings, companies should integrate these two issues instead of treating them separately. This paper considers the problem of selecting the appropriate distribution strategy for delivering a family of products from a set of suppliers to a set of plants so that the total transportation, pipeline inventory, and plant inventory costs are minimized. With reasonable assumptions, a simple model is presented to provide a good solution that can serve as a guideline for the design and implementation of the distribution network. Due to the plant inventory cost, the problem is formulated as a nonlinear integer programming problem. The problem is difficult to solve because the objective function is highly nonlinear and neither convex nor concave. A greedy heuristic is proposed to find an initial solution and an upper bound. A heuristic and a branch-and-bound algorithm are developed based on the Lagrangian relaxation of the nonlinear program. Computational experiments are performed, and based on the results we can conclude that the performance of the algorithms are promising.