bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photoconductivity of Vinyl Polymers with Large Pendant π-Electron Systems. I. Poly-9-vinylacridine
Authors: Moriwaki Saburo , Okamoto Ken-ichi , Kusabayashi Shigekazu , Mikawa Hiroshi 
Published: July 2006

Abstract
The dark- and photo-conductivities of poly-9-vinylacridine (PVAcr) were investigated in comparison with those of poly-N-vinylcarbazole (PVCz). The dark current was ohmic over the whole voltage region studied up to 150000 V/cm. The photocurrent showed a linear dependence on the applied voltage even in fairly high applied fields up to 130000 V/cm and a spectral dependence corresponding antibatically to the absorption spectrum. The magnitude of the photocurrent with positive electrode illumination (iph+) was only 1.5–2 times larger than that with negative electrode illumination (iph−), the behavior differing entirely from that in a PVCz film. The magnitude of the photocurrent of PVAcr was smaller than that of PVCz by several times for iph− and by a hundred times for iph+. The poor photoconductivity of PVAcr was attributed both to the high concentration of the excimer-forming site acting as an effective exciton trap and to the poor electron-donating character.
A Formulation of Chemical Kinetics in Micellar Solutions
Authors: Shirahama Keishiro 
Published: July 2006

Abstract
Reaction kinetics in the presence of micelles is formulated on the basis of a microheterogeneous reaction in accordance with a current model of micellar catalysis. The necessary molecular parameters are the radius of the hydrocarbon core of a spherical micelle, the thickness of a reaction surface layer, the surface and zeta potentials, and a distribution coefficient of a hydrophobic substrate. The derived expression was applied to the hydrolysis reaction of methylorthobenzoate in the presence of sodium dodecylsufate micelle to describe reaction properties such as a rate-surfactant concentration profile, inhibition by added electrolyte, and activation energy. The micellar effect on the reaction rate was explained by a simple concentration effect of the reactants; the stabilization of the transition state by the micellar surface potential need not be taken into consideration. Inhibition of the orthoester hydrolysis by a cationic surfactant is also predicted.
Ion Association of Some 2 : 2 Electrolytes in Water at 25 °C. I. Studies of Magnesium, Calcium, Manganese, and Tris(1,10-phenanthroline)-ruthenium(II) Sulfate Solutions with a Vapor-Pressure Osmometer
Authors: Yokoyama Haruhiko , Yamatera Hideo 
Published: July 2006

Abstract
The osmotic coefficients of aqueous solutions of magnesium, calcium, manganese, and tris(1,10-phenanthroline)ruthenium(II) sulfates were measured at 25 °C by means of a vapor-pressure osmometer. Then the ionassociation constants of these electrolytes were obtained as a function of the closest distance of approach of ions from the measured osmotic coefficients as well as from the available conductivity and cryoscopy data. The best values of the closest distance of approach and the ion-association constant (given in Table 6) were estimated with the help of theories of ion association. The formation of triple-ions and quadrupoles and the hydration of ions are also discussed in connection with the ion-association constant.
Kinetics of Multidentate Ligand-substitution Reactions. XVIII. Substitution Reactions of Triethylenetetraaminehexaacetate (TTHA) with Nickel(II)–Dien, –EDMA, and –NTA Complexes
Authors: Kodama Mutsuo 
Published: July 2006

Abstract
The kinetics of the substitution reactions of TTHA with nickel(II) complexes of diethylenetriamine (Dien), ethylenediaminemonoacetate (EDMA), and nitrilotriacetate (NTA) were studied systematically by employing the polarographic technique. All the substitution reactions were found to have a common reaction mechanism. They were first-order with respect to TTHA and also first-order with respect to a 1:1-ratio nickel(II) complex of Dien, EDMA, or NTA. In all the substitution reactions, the rate constants for the reactions involving a com-pletely-deprotonated TTHA anion were nearly identical to those for the corresponding DTPA (diethylenetriaminepentaacetate) reactions, suggesting that the TTHA reaction has the same reaction mechanism as the DTPA reaction. In the Dien system, the rate constant for the reaction of the quadrivalent TTHA anion is nearly identical to that of the quinquivalent TTHA anion, whereas, in the reactions of NTA and EDMA complexes, the reaction of the quadrivalent TTHA anion is drastically slower than that of the quinquivalent TTHA anion. These facts suggest that the proton transfer from the entering group to the leaving group plays an important role in determining the rate of the multidentate ligand-substitution reaction.
Non-isothermal Studies of Adduct Molecules of Metallic Halides with Oxo Compounds in Solid State. III.
Authors: Chaudhuri N Ray , Mitra S 
Published: July 2006

Abstract
Non-isothermal studies of some adduct molecules of metallic halides with ethylene glycol dimethyl ether of the type MX2(EGDME)y in solid state were carried out with a derivatograph, where M=Mn(II), Co(II), Ni(II), Cu(II) or Cd(II), X=Cl− or Br−, EGDME=ethylene glycol dimethyl ether and y=0.5–1. These adduct molecules lost ethylene glycol dimethyl ether in single or multiple steps upon heating. Thermally stable intermediate products were isolated and characterised by elemental analysis and IR spectral measurement. The activation energy for each step of decomposition of the adduct was evaluated from the analysis of TG, DTG and DTA curves of the respective derivatograms. Enthalpy change was evaluated from the DTA peak area and the order of reaction was found to be unity for each step of decomposition. Thermal parameters for the above adducts were compared with those for the corresponding type of adducts with oxo-compounds like dioxane or tetrahydrofuran.
Oxidative Cleavage of Aromatic Methoxy Compounds with Photo-excited Aromatic Nitro Compounds
Authors: Saito Isao , Takami Masaaki , Matsuura Teruo 
Published: July 2006

Abstract
Photochemical addition of the aromatic nitro group with aromatic methoxy compounds leading to the cleavage of the aromatic ring was studied. The oxidative cleavage occurs selectively at 1,2-bond with respect to a methoxy group of methoxybenzenes and methoxynaphthalenes. Aromatic nitro compounds having the lowest π,π* triplet are more effective to the oxidative ring cleavage of the methoxynaphthalenes than those having the lowest n,π* triplet. A mechanism involving charge-transfer complex is proposed. The scope and limitation on the use of these photochemical reactions are discussed.
α,β-Unsaturated Carboxylic Acid Derivatives. X. The Synthesis and Reaction of α-Azido-diethoxyphosphinyl-α- and β-alkenes
Authors: Shin Chung-gi , Yonezawa Yasuchika , Sakamoto Hiroshi , Yoshimura Juji 
Published: July 2006

Abstract
α,β-Dibromo-β-diethoxyphosphinylalkane (2) was obtained as a stereo-isomeric mixture (erythro : threo=50 : 50) by the bromination of β-diethoxyphosphinyl-α-alkene, composed of the E-isomer and the Z-isomer (50 : 50). It was found that the reaction of 2 with sodium azide proceeded stereoselectively to give only the. E-isomer of α-bromo-β-diethoxyphosphinyl-α-alkene, which could then be converted into α-azido-β-diethoxyphosphinyl-α-alkene (4), and α-azido-β-diethoxyphosphinyl-β-alkene, whose configuration was determined by the coupling constants between the phosphorus atom and the vinyl protons. Moreover, the irradiation of 4 yielded a new type of β-diethoxyphosphinyl-α-alkene-α-imine, which later rearranged into the corresponding nitrile.
Aminocyclitols. 32. Synthesis of Inosadiamine-1,4
Authors: Suami Tetsuo , Tadano Kinnichi , Horiuchi Sumio 
Published: July 2006

Abstract
Three new inosadiamines have been prepared by nitromethane cyclization of dialdehyde, followed by catalytic hydrogenation. Their structures were established to be scyllo-1,4, myo-1,4, and epi-inosadiamine-3,6 by PMR spectra.
The Synthesis of 1,3,4-Oxadiazolo[3,2-b]isoquinoline and 1,3,4-Thiadiazolo-[3,2-b]isoquinoline Derivatives from Homophthalic Anhydride
Authors: Takahashi Masahiko , Shinoda Takamitsu , Osada Hideshi , Nakajima Toshio 
Published: July 2006

Abstract
The synthesis of 1,3,4-oxadiazolo[3,2-b]isoquinoline and 1,3,4-thiadiazolo[3,2-b]isoquinoline derivatives is described. The reaction of homophthalic anhydride (1) with acylhydrazines (2) afforded 2-acylamino-1,2,3,4-tetrahydroisoquinoline-1,3-diones (3) or 1-(o-carboxyphenylacetyl)-2-acylhydrazines (4). The treatment of 3 or 4 with polyphosphoric acid gave 2-substituted 1,3,4-oxadiazolo[3,2-b]isoquinolin-5(5H)-ones (5) in quantitative yields. The treatment of 3 or 4 with phosphorus pentasulfide gave 2-substituted 1,3,4-thiadiazolo[3,2-b]-isoquinoline-5(5H)-thiones (6). 2-Phenyl-1,3,4-oxadiazolo[3,2-b]isoquinoline-5(5H)-thione (9) was obtained by the reaction of 5a with phosphorus pentasulfide.
Ungewöhnliche Wichterle-Reaktionen. Eine Neue Synthese von Phenalenonen
Authors: Kobayashi Makoto , Matsumoto Takeshi 
Published: July 2006

Abstract
Beim Erhitzen von 1-Methyl-1-(3-chlor-2-butenyl)-5-methoxy-2-tetralon(10) in HCO2H in Gegenwart von HClO4 wurde 4,7-Dimethyl-1-phenalenon(11) erhalten, während das Desmethoxy-Analogon, 1-Methyl-1-(3-chlor-2-butenyl)-2-tetralon(5) ein Phenanthren-Derivat ergibt. Es wurde gezeigt, dass die Bildung von Phenalenon liber die Zwischenprodukte 2,3,9,9a-Tetrahydro-7,9-dimethyl-4-methoxy-1-phenalenon(13) und 2,3-Dihydro-4,7-dimethyl-1-phenalenon(17) verläuft. Unter den gleichen Bedingungen wurde 1-(3-Chlor-2-butenyI)-5-methoxy-2-tetralon(21) über 2,3-Dihydro-7-methyl-4-methoxy-1-phenalenon(23) in 7-Methyl-4-methoxy-1-phenalenon(24) umgewandelt.
The Responses of the Monovalent Cation-sensitive Glass Electrode to the Cationic Activities in Different Solvents
Authors: Nakamura Toshio 
Published: July 2006

Abstract
The responses of the glass electrode to the cationic activities in different solvents have been studied for several monovalent cations in several dipolar aprotic and protic solvents by comparing the potentials of the amalgam electrode with those of the glass electrode.
The Conversion of Penicillin S-Oxides into Cephalosporin S-Oxides
Authors: Ishimaru Toshiyasu , Imamoto Tsuneo 
Published: July 2006

Abstract
The reaction of penicillin S-oxides (1a,b) with N-bromosuccinimide afforded sulfinyl bromides (2a,b) in high yields. The bromides were converted into cephalosporin S-oxides (4a, 4b, 6a, and 7a) in fairly good yields.
Metal Derivatives of Amidoximes. VII. Synthesis of Bis(1,3,5,2-Oxadiazaborol-2-yloxy)tetrabutyldistannoxanes
Authors: Goel A B , Gupta V D 
Published: July 2006

Abstract
Bis(1,3,5,2-oxadiazaborol-2-yloxy)tetrabutyldistannoxanes have been synthesized by the reaction of amidoxime, boric acid and dibutyltin oxide. A probable structure for the dimeric species has been proposed on the basis of molecular weight and IR spectral data.
Topochemical Studies. VII. The Crystal and Molecular Structures of Tetrachlorophthalic Acid Hemihydrate and Tetrabromophthalic Anhydride
Authors: Ito Kuniaki , Moriya Keigo , Kashino Setsuo , Haisa Masao 
Published: July 2006

Abstract
The crystal structures of tetrachlorophthalic acid hemihydrate (TCPH) and tetrabromophthalic anhydride (TBPA) have been determined from visually estimated CuKα data. The crystals of TGPH are monoclinic, space group A2/a, a=19.81(1), b=7.091(5), c=16.22(1) Å, β=101.2(2)° and Z=8. Those of TBPA are monoclinic, space group P21/n, a=13.39(3), b=6.19(2), c=12.66(3) Å, β=91.1(3)° and Z=4. The structures of TGPH and TBPA were solved from the sharpened Patterson maps, and refined by the block-diagonal least-squares method to R values of 0.112 and 0.112 for 1287 and 1278 non-zero reflections, respectively. The molecules of TCPH related by a twofold screw axis are linked together by hydrogen bonds between the carboxylic groups to form a chain along the b axis and the chains are held together by hydrogen bonds through water molecules to form a sheet parallel to the (100) plane. The sheets are stacked by van der Waals forces. The dihedral angles of the carboxylic groups with the benzene ring are 68.2 and 48.9°. The crystals of TBPA are isomorphous to those of tetrachlorophthalic anhydride. The benzene ring of TBPA are distorted by the attachment of five membered ring. There is considerable molecular overlap in TCPH, while in TBPA there is no overlap.
An Evaluation of the Effects of the Phosphorus Ligands on the Stereoselectivity of a Nickel-catalyzed Reaction. The Reaction of Norbornadiene with Acrylonitrile
Authors: Yoshikawa Susumu , Aoki Kunihiro , Kui Jitsuo , Furukawa Junji 
Published: July 2006

Abstract
The effects of nineteen phosphorus ligands on the nickel-catalyzed 4+2 cycloaddition reaction of norbornadiene to acrylonitrile have been studied. The cone angle and the νco stretching frequency of Ni(CO)3L (where L is the phosphorus ligand) are used as measures of their steric and electronic parameters respectively. The steric factor of the phosphorus ligands is correlated with the ratio of the exo- and endo-isomers of the product. Consequently, this effect is important in determining the steric course of the reaction. The electronic property and the solvent effect are less influential.
The Interpretation of Surface Tension Data for Solutions of Ionic Surfactants in the Presence of Electrolyte
Authors: Hall Denver G , Pethica Brian A , Shinoda Kozo 
Published: July 2006

Abstract
An improved method is presented for interpreting surface tension data on solutions of an ionic surfactant to which has been added an electrolyte whose co-ion has the same valence as the surfactant ion. Adequate account is taken of co-ion adsorption and of deviations from ideality of the solution. When a monolayer of surfactant ions is formed and the distributions of free surfactant ions and co-ions in the region adjacent to it are determined predominantly by electrostatic repulsion, it is shown that the separate contributions to the total Gibbs excess of surfactant ions from the monolayer and the adjacent region can be obtained. Finally some experimental data are re-examined and a simple explanation is given for the minimum reported to occur in co-ion adsorption as the surfactant ion concentration is increased at constant co-ion concentration.
Ethanol and Lactic Acid Sensors Using Electrodes Coated with Dehydrogenase—Collagen Membranes
Authors: Suzuki Shuichi , Takahashi Fujio , Satoh Ikuo , Sonobe Nobuyuki 
Published: July 2006

Abstract
Electrochemical and enzymatic reactions were studied for the purpose of making sensors of ethanol and lactic acid. The dehydrogenase–collagen membrane coated onto a platinum plate was prepared by the electroshaping method. The substrates were dehydrogenated and nicotinamide adenine dinucleotide (NAD) was reduced to form the reduced NAD (NADH) by an enzymatic reaction on the collagen membrane. Flavin mononucleotide (FMN) was chosen as an electroactive substance which could oxidize NADH to return NAD. The reduced FMN (FMNH2) was easily oxidized at the anode and a current was obtained. From the above reactions, the concentrations of ethanol and lactic acid in solutions were found to be determined by a current-substrate concentration relation. The accuracy was estimated to be within 10% error. The activity and stability of enzymes immobilized in the collagen membrane were investigated.
Chemistry of Nitrosoimines. XI. Reactions of 3-Substituted 2-Nitrosoimino-2,3-dihydrobenzothiazoles with Benzyl and Allylic Grignard Reagents
Authors: Hisaoka Motoyuki , Akiba Kin-ya , Inamoto Naoki 
Published: July 2006

Abstract
3-Substituted 2-nitrosoimino-2,3-dihydrobenzothiazoles (1) react with benzylmagnesium chloride to give 3-substituted 2,2-dibenzyl- (2), 2-N′-benzylidenehydrazono- (3) and 2-N′,N′-dibenzylhydrazono-2,3-dihydrobenzothiazoles (4). The main reaction (formation of 3 and 4) occurrs on the nitroso group of 1, which proceeds via 1,2-addition intermediate (B). Allylmagnesium bromide and cinnamylmagnesium chloride also react with 3-methyl derivative (1a) to afford 2-N′,N′-diallyl- and 2-N′-(1-phenyl-2-propenyl)hydrazono-3-methyl-2,3-dihydrobenzothiazoles, respectively.
The Dehydration and Dehydrogenation of Ethanol Catalyzed by TiO2–ZrO2
Authors: Arata Kazushi , Sawamura Hiromitsu 
Published: July 2006

Abstract
Ethanol was converted into ether, ethylene, and butadiene over TiO2–ZrO2 with various contents of ZrO2in a flow system. Maximum acidity and activity were obtained at 50% ZrO2. The butadiene formation was explained by both dehydration and dehydrogenation reactions on acidic and basic sites, implying that TiO2–ZrO2 is an acid-base bifunctional catalyst.
Topological Index as Applied to π-Electronic Systems. II. Topological Bond Order
Authors: Hosoya Haruo , Murakami Miyuki 
Published: July 2006

Abstract
Topological bond order plT is proposed to be defined for a bond l in the graph corresponding to the carbon atom skeleton of a hydrocarbon. This quantity is obtained by hand calculation of the topological indices of the graph and its subgraphs. The plT value is linearly correlated well with the Coulson bond order plC for both the chain and cyclic compounds. If the bonds with the same Pauling bond order plP are compared this linear relationship is greatly improved and one gets an empirical relation as
p_l^C=A  p_l^T + B  p_l^P.
Direct Measurement of Interaction Energy between Solids and Gases. I. Heat of Adsorption of Ammonia on Zeolite
Authors: Tsutsumi Kazuo , Koh Hong Qui , Hagiwara Seiichi , Takahashi Hiroshi 
Published: July 2006

Abstract
The differential heat of adsorption of ammonia on synthetic zeolites was calorimetrically measured and the distribution of the surface acidity was discussed in relation to the catalytic activity for cumene-cracking as a function of zeolite compositions. A newly designed apparatus, a twin-conduction-type calorimeter equipped with a semiconductor thermoelement and an adsorption apparatus, was used for the direct measurement of the differential heat of adsorption. The differential heat of adsorption of ammonia decreased with the increase in surface coverage, the acid site on the surface becoming stronger up to 27 kcal/mol for ammonia-adsorption when the ratio of silica to alumina was higher and the content of exchanged ammonium ions was higher. The cumene-cracking reaction was effectively catalyzed by zeolites having such sites with heat of adsorption of ammonia exceeding 25 kcal/mol.
Studies on Interaction of Isocyanide with Transition Metal Complexes. XIII. Preparation of Carbene Complexes of Nickel, Iron, and Cobalt through Protonation of Monoimino and Polyimino Type Complexes
Authors: Yamamoto Yasuhiro , Yamazaki Hiroshi 
Published: July 2006

Abstract
Reactions of η-C5H5Ni(CNR1)[C(R)=NR1] (R=CH3,p-ClC6H4; R1=C6H11, (CH3)3C) and η-C5H5Fe(CO)2-[C(CH2C6H4X-p)=NC6H11] (X=H, Cl) with HBF4 gave the cationic carbene complexes, η-C5H5Ni(CNR1)-[C(R)NHR1]BF4 and η-C5H5Fe(CO)2[C(CH2C6H4X-p) NHC6H11]BF4. η-C5H5Co[–C(=NR)–CPh=CPh–C(=NR)–] (1a; R=2,6-(CH3)2C6H3: 1b; R=p-CH3C6H4) reacted with HBF4 to give η-C5H5Co[–C(NHR)–CPh=CPh–C(=NR)–]BF4 (2a, b). Compound 2a exists as two isomers, induced by the restricted rotation about the C–N bond. Treatment of 1a with HCl gave η-C5H5Co[–C(NHR)–CPh=CPh–C(=NR)–]Cl (3b). The H(N) proton showed some fluxional behavior in its proton NMR spectrum. Reaction of 1b with CF3COOH gave the dicationic complex η-C5H5Co[–C(NHR)–CPh=CPh–C(NHR)–](CF3COO)2 4b. Compound 2 reacted with R1NC(R1=(CH3)3C, 2,6-(CH3)2C6H3) to give η-C5H5Co(CNR1)[–C(=NR)–CPh=CPh–C(=NR)–]5. Reaction of 5 with HBF4 gave again the cationic carbene complex η-C5H5Co(CNR1)[–C(NHR)–CPh=CPh–C(=NR)–]BF4.
Optical Activation of α-Substituted Carbonyl Compounds by Asymmetric Transformation
Authors: Matsushita Hajime , Noguchi Masao , Saburi Masahiko , Yoshikawa Sadao 
Published: July 2006

Abstract
Immonium salts of enamines of racemic α-substituted carbonyl compounds with optically active acids gave, on hydrolysis with water, the corresponding optically active carbonyl compounds. Several reaction conditions were examined and a plausible reaction mechanism, an asymmetric transformation, was proposed. Rates of racemization for the (+)-α-pheiiylpropionaldehyde were also determined.
Micellar and Metal Ion Catalysis in the Pyridoxal-Promoted α,β-Elimination of S-Phenylcysteine
Authors: Murakami Yukito , Kondo Hiroki 
Published: July 2006

Abstract
The effects of metal ions and detergents on the pyridoxal-catalyzed α,β-elimination reaction of S-phenylcysteine have been investigated in 0.01 M borate buffer at 50 °C (the copper ion catalysis at 40 °C in the presence of CTAB micelles). Both copper(II) and nickel(II) ions markedly accelerated the elimination reaction of S-phenylcysteine. Since the catalytic efficiency of nickel(II) seems to be obtained due to the poor coordination ability of the leaving group in the present reaction, the previous working hypothesis which was provided for the elucidation of catalytic roles of metal ions in the α,β-elimination of O-phosphothreonine has now been approved. Among cationic, anionic, and non-ionic detergents employed in this work as apoenzyme models, only CTAB of cationic nature showed a considerable rate acceleration even in the absence of metal ions. The micellar binding constant was evaluated from the saturation-type correlation between reaction rate and CTAB concentration. The surfactant micelles demonstrated some enzyme-like features of catalysis in the pyridoxal-promoted α,β-elimination reaction, where the reaction is controlled by the entropy term. The CTAB catalysis was greatly inhibited by organic and inorganic anions due to the electrostatic nature of the micellar surface. The catalytic mechanisms for the micellar reactions and their significance as an enzyme model system are discussed.
A Method for Determining the Degree of Dissociation of Symmetrical Associated Electrolytes from the Conductivity and Activity Data
Authors: Tamamushi Reita 
Published: July 2006

Abstract
A method is presented for determining the degree of dissociation of symmetrical associated electrolytes from a set of conductivity and activity data. The method was applied to the determination of the dissociation constants of several metal sulfates in aqueous solutions.
Semi-empirical SCF–MO Studies of Platinum Hydrides and the Insertion Reaction of Ethylene into the Pt(II)–H Bond
Authors: Sakaki Shigeyoshi , Kato Hiroshi , Kanai Hiroyoshi , Tarama Kimio 
Published: July 2006

Abstract
Semi-empirical SCF–MO calculations were carried out on trans-PtHX(PH3)2 (X= halogen and CN−). The absolute value of Ept-H decreases in the following order: F&gt;Cl&gt;Br&gt;I&gt;CN; this agrees with the order of the bond strength of the Pt–H bond. The electron density on the H ligand is remarkably large in all the complexes (ca. 1.25 e) and decreases in this order: F&gt;Cl&gt;Br&gt;I&gt;CN. An insertion reaction of ethylene into the Pt–H bond was investigated by the use of the MO method. The intermediate five-coordinate π-olefinic hydride complex has a trigonal bipyramid structure in which Cl and H ligands are positioned trans to each other. Three reaction paths of the insertion were investigated, and the following reaction path seems the best: The H ligand starts first to approach ethylene and then the Cl ligand starts to move to the trans-position of the H ligand. The reactivities of trans-PtHX(PH3)2 increase in this order: F&lt;Cl&lt;Br&lt;I&lt;CN. MO calculations also reveal that the catalytic ability of trans-PtHK(PH3)2 increases as follows in the hydrogen-deuterium exchange reaction of ethylene: F&lt;Cl&lt;Br&lt;I