bluuebunny/crossref_metadata_2025 huggingface dataset:
The Photoreaction of Pyrazine Derivatives
Authors: Yamada Kazutoshi , Katsuura Kiyoshi , Kasimura Hideaki , Iida Hirotada
Published: July 2006

The irradiation of the pyrazine derivative with an α-carbonyl substituent (1) under a nitrogen atmosphere gave hydroxypyrazine (2) and two solvent adducts (3 and 4). In the case of 1e, the charge-transfer complex of pyrazine and dihydropyrazine, produced by the reduction of the pyrazine, was isolated. The mechanism of this photoreaction was similar to that of flavine. The attack of oxygen on dihydropyrazine produced 2. Furthermore, the photoreduction with DTT occurred through the intermediate, which was similar to the case of flavine. The reaction rates of various pyrazines were measured. The quenching studies indicate that the photoreaction proceeds via the n-π* triplet state.
The Reaction of Disodium Tetracarbonylferrate(–II) with Carboxylic Esters and Carbothioic Esters
Authors: Watanabe Yoshihisa , Yamashita Masakazu , Igami Mineo , Mitsudo Take-aki , Takegami Yoshinobu
Published: July 2006

The reaction of carboxylic and carbothioic esters with disodium tetracarbonylferrate has been studied. Aryl and thiolic esters reacted with the ferrate under mild conditions to give aldehydes after the reaction mixture had been quenched with acetic acid, but alkyl esters did not. 3-Benzylidenephthalide and phthalide gave 2-phenyl-1,3-indanedione and a dimeric product respectively.
Studies of Enamines. VIII. Reactions of Enamino Ketones with Benzoyl and Thiobenzoyl Isocyanates
Authors: Tsuge Otohiko , Inaba Akitaka
Published: July 2006

The reaction of enamino ketone 1, derived from acetylacetone, with benzoyl isocyanate (4) gave the isomeric benzoylcarbamoyl derivatives 6 and 9, and/or 2-pyridone 7, depending upon the reaction conditions. Similarly, enamino ketone 2, derived from benzoylacetone, reacted with 4 to afford the isomeric benzoylcarbamoyl compounds 12, 13, and/or 2-pyrone 14. It has been found that the carbamoyl compound 12 was thermally converted into 13 and 14. Enamino ketones 1 and 2 reacted with thiobenzoyl isocyanate (5) at room temperature to yield the 2-pyridones 7 and 15, respectively. On the other hand, enamino ketones 3, derived from benzoylacetaldehyde and secondary amines, reacted with 4 to give the corresponding 2-benzoylcarbamoyl-2-penten-2-one compound 18, while in the reaction with 5, 3 gave the 1,3-thiazin-4-one 19 and/or (4+2) cycloaddut 20.
Nitration of Binary and Ternary Schiff Base Complexes of Cu(II)
Authors: Thaker B T , Bhattagharya P K
Published: July 2006

Nitration of the coordinated ligands in the complexes bis[1-(2-hydroxyphenyl)ethylideneamine or its methyl derivative]Cu(II) and N,N′-ethylene or propylene bis[1-(2-hydroxyphenyl)ethylideneaminato]Cu(II) have been carried out. Similar nitration reactions of mixed diamine Schiff base complexes of Cu(II) have also been carried out. The substitution products have been characterized by elemental analyses, comparison with authentic samples in case of binary complexes and by means of magnetic moments, electronic and IR spectral studies. The orientation of incoming substituents in the chelates is found to be the same as that in uncomplexed 2-hydroxyacetophenone or methyl substituted 2-hydroxyacetophenone. Nitration reactions in case of mixed ligand complexes confirm the structure.
Studies with Parchment Supported Membranes. VIII. Determination of the Thermodynamic Effective Fixed Charge Density of Barium Phosphate Membrane by Various Methods and Evaluation of Permselectivity
Authors: Siddiqi Fasih A , Beg M Nasim , Singh Surendra P , Haque Abdul
Published: July 2006

The thermodynamic effective fixed charge density, the most important parameter governing transport phenomena in membranes, was estimated by methods of TMS, Altug and Hair and the most recent one of Kobatake based on the thermodynamics of irreversible processes. Kobatake’s equation has also been utilized for the evaluation of permselectivity of membranes. The two limiting forms of his equation for dilute and concentrated ranges gave identical values of θ (charge density) for barium phosphate membrane. The theoretical predictions for membrane potential by the equation were borne out quite satisfactorily by experimental results obtained with the investigated membranes.
A Study of Self Oscillatory Chemical Reaction of Gallic Acid and Potassium Bromate System
Authors: Babu J Sreekantha , Bokadia M M , Srinivasulu K
Published: July 2006

The oscillatory phenomenon during oxidation of gallic acid with potassium bromate, catalyzed by cerium ion in acid medium with stirring was investigated. The cross section of a three dimensional graph for the regions where the oscillatory behavior can be observed is given. Effect of Ag+and Br− on the oscillatory behavior was studied.
Some New β-Diketone Complexes of Ruthenium(III) with Triphenylphosphine and Triphenylarsine
Authors: Natarajan K , Agarwala Umesh
Published: July 2006

The syntheses of some new β-diketone complexes of Ru(III) with triphenylphosphine and triphenylarsine have been described. Their spectral (IR and visible) and magnetic properties have been reported. Some of them show unusual magnetic moment.
Cathodic Reduction of Nitrobenzene on the Packed-bed Copper Electrode
Authors: Yoshizawa Shiro , Takehara Zenichiro , Ogumi Zempachi , Tsuji Toshio
Published: July 2006

An application of a packed-bed copper electrode to the formation of aniline by the cathodic reduction of nitrobenzene was investigated. As the particles for the packed-bed, spherical particles of an anion exchange resin chemically plated with copper were successfully used. Though the current efficiency for the aniline formation on the packed-bed electrode in a batch cell decreased with continuing electrolysis, the efficiency was improved by the electrolysis under a flowing electrolyte and became very high, i.e., near 100%. This is due to the removal of the accumulated products on the electrode surface by the flowing electrolyte. The effective depth of the bed electrode on which the nitrobenzene reacted cathodically was also determined from the measurement of the potential profile in a packed-bed electrode: the result was about 3 mm. This low value of the effective depth is ascribed to the low conductivity of the electrolyte and to the high electronic conductivity of the packed-bed. This may be improved by using bed particles of lower electronic conductivity and a higher cell capacity may be expected.
The Surface Tension of Aqueous Solutions Saturated with Triacetin–Tributyrin Mixtures
Authors: Funasaki Noriaki , Hada Sakae
Published: July 2006

The surface tension of aqueous solutions saturated with triacetin–tributyrin mixtures was measured in order to study the phase equilibria among an adsorbed monolayer (m), an aqueous solution (w), and an oily mixture (1). The variation in the surface tension, γ, of saturated aqueous solutions with an increase in the number of moles, mt, of the added mixtures depended on the mole fractions, x2, of tributyrin in the mixtures; the γ value remained unchanged in the case of x2=0.0027, decreased in the case of x2>0.0027, and increased in the case of x2<0.0027. The results of the theoretical analysis of the γ vs.  mt curves gave the mole fractions, x21, of tributyrin in the oily mixtures. The x21 values thus evaluated agreed with those determined gas-chromatographically. It was found that all of the γ vs.  x2m, γ vs.  x21, and γ vs.  x2w curves have a minimum, at which the γ values are identical and at which x2m=x21>2w. The characteristics of these curves were explained thermodynamically on the basis of the assumption that triacetin and tributyrin form a regular mixture in a monolayer as well as in a liquid.
Localized Molecular Orbital Studies of Chemical Reaction. II. Abstraction and Addition Reactions of Triplet Methylene
Authors: Nagase Shigeru , Fueno Takayuki
Published: July 2006

Energy-localized molecular orbitals (LMO) generated from UHF–INDO wave functions have been used for the studies of the mechanistic details of the abstraction and addition reactions of triplet methylene. The UHF LMO mapping procedure which we have previously developed permits a clear understanding of the nature of the chemical bonds to be formed or broken on reaction. Significance of the three-stage mechanism, which should involve the successive β- and α-spin electron delocalizations between reactants and the concomitant spin polarization of the reacting bond, is emphasized. The whole aspects of the reactions are well in accord with the customarily accepted mechanistic schemes.
The Crystal and Molecular Structure of 1-(2-Thiazolylazo)-2-naphthol
Authors: Kurahashi Masayasu
Published: July 2006

The crystal structure of 1-(2-thiazolylazo)-2-naphthol, C13H9N3OS, has been determined from three-dimensional X-ray data collected by counter methods. The crystals are monoclinic with space group P21/a; cell dimensions: a=17.721(1), b=28.366(2), c=4.699(1) Å, β=91.78(1)°, and Z=8. The structure was solved by the symbolic addition procedure and refined by the least-squares method to give an R value of 0.051 for 2150 observed reflections. There are two crystallographically independent molecules in an asymmetric unit; both of the molecules show a generally similar shape and size, but their structural details differ in planarity and distribution of the bond lengths. Both molecules have the azo and hydrazone character, but the equilibrium is shifted toward the azo tautomer.
The γ-Radiolysis of a Cyclohexene–Carbon Dioxide Mixture in the Liquid Phase at −18 °C
Authors: Wojnarovits Laszlo , Hirokami Shun-ichi , Sato Shin
Published: July 2006

The γ-radiolysis of a cyclohexene–carbon dioxide mixture in the liquid phase at −18 °C has been studied. When the mole fraction of carbon dioxide was low, carbon dioxide behaved as an electron scavenger and slightly suppressed the formation of the hydrogen and hydrocarbon products: 2,2′-bicyclohexenyl, cyclohexane, 3-cyclohexylcyclohexene, bicyclohexyl, 1-cyclohexylcyclohexene, and 1,3-cyclohexadiene. Along with this suppression, the formation of cyclohexanol was observed. At the high mole fraction of carbon dioxide, the main products were carbon monoxide and the oxygen atom-addition products: cyclohexene oxide, cyclohexanone, and cyclopentane-carbaldehyde. The material balance for oxygen atoms was good. The formation ratio of the addition products suggests that the precursors of the addition products are the ground-state oxygen atoms. These oxygen atoms are probably produced by the direct radiolysis of carbon dioxide. As the CO2 mole frcation approached unity, the G-values of the addition products and other oxygenated compounds including 2-cyclohexenone and 2-cyclohexenol sharply increased. This suggests that there is another source of oxygen atoms which is suppressed by the presence of cyclohexene. The reactions may be CO2++CO2−→CO+O+CO2 and CO2++cyclohexene→CO2+cyclohexene+. The formation of 2-cyclohexenone and 2-cyclohexenol may be explained in terms of the reaction between the cyclohexenyl radicals and oxygen molecules eventually produced. To support the elucidation of the reaction mechanism, the radiolysis in the solid phase at 77K and the mercury-photosensitized reaction of a nitrous oxide–cyclohexene mixture in the gas phase have also been studied.
Charge-Transfer Bands of the Mixed Molecular Complex, (Anthracene)1−x(Phenanthrene)x(1,2,4,5-Tetracyanobenzene)
Authors: Wright John D , Ohta Toshiaki , Kuroda Haruo
Published: July 2006

A series of crystalline mixed molecular complexes of composition, (anthracene)1−x(phenanthrene)x(TCNB), with 0.17≤x≤0.63, has been prepared from solutions containing mixtures of the three components. A linear relationship is observed between solution and solid composition, and the melting point data and powder X-ray diffraction patterns suggest the formation of a continuous series of mixed molecular complexes of closely related crystal structure. Polarized crystal spectra of these crystals show two charge-transfer bands characteristic of the interaction between anthracene and TCNB and that between phenanthrene and TCNB, respectively. Their intensity ratio is linearly dependent on composition, and constant for different crystals of the same composition. Discussion is given on these results by using the results of semi-empirical SCF-MO-CI calculations on the three-molecule model, anthracene/TCNB/phenanthrene.
The Absorption and Fluorescence Spectra of the Ion-Pairs of 1,2,4,5-Tetracyanobenzene with Several Methyl Substituted Benzenes
Authors: Matsumoto Satoru , Nagakura Saburo , Kobayashi Takayoshi
Published: July 2006

The absorption and fluorescence spectra and the fluorescence decay times were measured at 77 K for the photoirradiation products of the 1,2,4,5-tetracyanobenzene (TCNB) complexes with hexamethylbenzene (HMB), durene, mesitylene, and toluene. The absorption spectra of the photoproducts are similar in shape to that of the TCNB anion and have maxima at 469, 467, 466, and 465 nm for the TCNB complexes with HMB, durene, mesitylene, and toluene, respectively. The fluorescence maximum wavelengths and decay times of the photoproducts are also similar to those of the TCNB anion (505 nm, 19.6 ns for the TCNB-mesitylene system; 505 nm, 20.7 ns for the TCNB-toluene system). The red shift of the absorption maximum and the decrease in the fluorescence decay time by changing the electron donors from toluene to HMB are discussed in terms of ion-pair formation.
Relation between Amounts of Chemisorbed Water and Ammonia on Zinc Oxide
Authors: Nagao Mahiko , Morimoto Tetsuo
Published: July 2006

The adsorption isotherm of NH3 was measured at 25 °C on ZnO surfaces with a controlled amount of surface hydroxyls. It was found that NH3 can be chemisorbed at 25 °C on the dehydroxylated sites of ZnO in a 1 : 1 molecular ratio of adsorbed NH3 to desorbed H2O. H2O can be chemisorbed for prechemisorbed NH3 through exchange reaction to form surface hydroxyls and gaseous NH3. The physisorption of NH3 at 25 °C can take place only on a limited part of ZnO surfaces which were fully hydroxylated or ammoniated.
Copper Nuclear Quadrupole Resonance Spectra of Tris(tetramethylthiourea)copper(I) Tetrafluoroborate and Perchlorate
Authors: Hiyama Yukio , Watanabe Noriyuki , Niki Eiji
Published: July 2006

63Cu, 65Cu NQR spectra of tris(tetramethylthiourea)copper(I) tetrafluoroborate ([Cu(tmtu)3]BF4) and tris(tetramethylthiourea)copper(I) perchlorate ([Cu(tmtu)3]ClO4) have been observed. The resonance frequencies are 27.390 MHz and 25.341 MHz in the BF4 compound, 27.390 MHz and 25.340 MHz in the ClO4 compound (23.0 °C). These results indicate that the crystal structure of [Cu(tmtu)3]ClO4 is very similar to that of [Cu(tmtu)3]BF4 and the copper valence has sp2 hybridization with pπ–dπ bonding. The temperature dependence of 63Cu NQR of [Cu(tmtu)3]BF4 has been studied from −100 to +100 °C. A discontinuous point has been discovered at −11 °C.
Carbon Monoxide Oxidation over Chromium Sesquioxide. I. Nature of Oxygen Adsorbed on Cr2O3
Authors: Kobayashi Masayoshi , Kobayashi Haruo
Published: July 2006

The nature of oxygen species adsorbed on Cr2O3 surface in the temperature range 131–163 °C was studied in detail by application of the transient response method with simultaneous measurements of the electrical conductivity of the catalyst as a p-type semiconductor. The distribution of oxidation power of the adsorbed oxygen species was also measured. The mode of the distribution curve of oxidation power indicates that the oxygen can be classified into two groups which differ in oxidation power as well as in the catalytic activity for the oxidation of CO. From the comparison between the results of the transient response and the oxidation power measurements, it is concluded that the rapidly and slowly adsorbed oxygen groups observed by the transient response method correspond to those of oxygen species of higher and lower oxidation power, respectively. Kinetic analysis of the conductivity response curve caused by the adsorption of oxygen leads to the conclusion that the dissociative adsorption of oxygen associated with electron transfer from the catalyst takes place simultaneously on two different kinds of adsorption sites at substantially different rates.
Carbon Monoxide Oxidation over Chromium Sesquioxide. III. Kinetics of the Reaction
Authors: Kobayashi Masayoshi , Kobayashi Haruo
Published: July 2006

Based on the experimental findings in Parts I and II, mechanisms of carbon monoxide oxidation over α-Cr2O3 were proposed with which the reaction takes place simultaneously through two parallel reaction paths. Overall reaction consists of five elementary steps, and the rate constants of all ellementary stepes were determined from the analysis of appropriate transient response data. The simulation of transient response with these rate constants proved the validity of these mechansims and the results of kinetic analyses.
The Complexing of Indium(III) by Cysteine: Evidence for Sulfurbridged and Protonated Complexes
Authors: Kojima Nakao , Sugiura Yukio , Tanaka Hisashi
Published: July 2006

The complex formation of the cysteine–In(III) system has been investigated by potentiometric titration and by PMR, IR, and UV spectroscopic measurements. The InL, InL2 and InLH species are predominantly formed at the metal concentrations from 0.00025 to 0.0005 M. At higher concentrations of the metal ion (0.0025–0.005 M), however, the InL species is negligible and the InL2, InL3, InL(LH), and In(LH)2 species are predominant. The formation constants calculated with a non-linear, least-squares program were logβ110=14.12, logβ120=27.26, logβ130=32.20, logβ11−1=18.46, logβ12−1=31.78, and logβ12−2=35.74 for InL, InL2 InL3, InLH, InL(LH), and In(LH)2 respectively. The IR and UV spectra revealed that the amino group of the coordinating cysteine was protonated. The [In3L4(OH)(H2O)] complex was isolated.
Spectrophotometric Study of the Zirconium–Pyrocatechol Violet–Tridodecylethylammonium Ternary Complex
Authors: Shijo Yoshio
Published: July 2006

The zirconium–pyrocatechol violet chelate anion is extracted with tridodecylethylammonium bromide in butyl acetate to form a ternary complex. The ternary complex has an absorption maximum at 586 nm in the organic layer. The optimum pH range for the extraction is from 5 to 6. Beer’s law holds for 0.4–9 μg of zirconium in 5 ml of the organic phase. The molar absorptivity of the ternary complex is 3.9×104 mol−1 at 586 nm. The composition of the ternary complex is estimated to be ((Remark: Graphics omitted.).
Glass Formation and Crystallization in Ternary Phosphate Systems Containing Al2O3
Authors: Kishioka Akira , Hayashi Masao , Kinoshita Makio
Published: July 2006

Glass formation and crystallization were investigated in two types of three-component systems, M2O–Al2O3–P2O5 (M=Li, Na, and K) and MO–Al2O3–P2O5 (M=Mg, Ca, and Ba). In the Li2O–Al2O3–P2O5 and MO–Al2O3–P2O5 systems, wide regions of glass formation were found in compositions containing more than 50 mol% of P2O5. In the Na2O–Al2O3–P2O5 and K2O–Al2O3–P2O5 systems, the two peaks in Al2O3 content were found in the regions of glass formation corresponding to about 35 and 65 mol% of P2O5. In the devitrified products of the glasses with 60 and 70 mol% of P2O5, AlPO4, Al(PO3)3, and alkaline earth metaphosphate (in the MO–Al2O3–P2O5 system) were found by X-ray powder diffractometry. The crystalline phases in the samples obtained as mixtures of glass and crystal consisted of AlPO4 in the composition containing 60 mol% of P2O5, while those with a P2O5 composition of 70 mol% consisted of Al(PO3)3. By heating those samples at 700–900 °C, the X-ray diffractions of AlPO4 and Al(PO3)3 were intensified. On the other hand, in the samples with 37.5, 40, and 50 mol% of P2O5, all the crystalline phases consisted of AlPO4, and the intensities of these X-ray diffractions decreased after the samples were heated at 600–700 °C. Thus, there is a marked structural difference between the two peak-regions in the Na2O–Al2O3–P2O5 and K2O–Al2O3–P2O5 systems.
Water-Participation in the Crystalline-State Photodimerization of Cinnamic Acid Derivatives. A New Type of Organic Photoreaction
Authors: Nakanishi Fusae , Nakanishi Hachiro , Tsuchiya Michio , Hasegawa Masaki
Published: July 2006

A new type of organic photoreaction, a water-participation reaction in the crystalline state, has been investigated. The photoirradiation of p-formylcinnamic acid (p-FCA) crystals in the presence of water leads to 4,4′-diformyl-β-truxinic acid (p-FCA dimer) which has one molecule of crystal water. A comparison of the photodimerization carried out in the presence/absence of water revealed the effects of the water molecule on the reaction. That is, the water molecule is incorporated into the p-FCA dimer during the photodimerization process. Furthermore, the water accelerates the reaction rate of photodimerization, leading to the formation of the crystalline dimer, whereas only the water-free amorphous dimer results in the absence of water. In addition, by heating at 100–110 °C, the p-FCA dimer with a water molecule is converted into a water-free crystalline dimer, which is not attainable from a water-free amorphous dimer. The photodimerization of several β-form crystals of cinnamic acid derivatives has been examined from the viewpoint of water-participation: p-nitro, p-chloro, and 3,4-dichlorocinnamic acid were found to photodimerize in the same manner as p-FCA.
Studies of Peptide Antibiotics. XXXIII. Syntheses of Gramicidin S Analogs Containing N-Methyl-l-valine in Place of l-Valine
Authors: Abe Hayao , Sato Kazuki , Kato Tetsuo , Izumiya Nobuo
Published: July 2006

Two analogs of gramicidin S, [1-N-methyl-l-valine]–gramicidin S and [1,1′-di-N-methyl-l-valine]–gramicidin S, were prepared for the purpose of investigating the contribution of NH group of l-valyl residue in gramicidin S to antibacterial activity. They exhibit weak activity as compared with gramicidin S in the antibacterial test toward microorganisms. The optical rotatory dispersions of these analogs and gramicidin S were measured in ethanol and 8 M urea. It was suggested that both analogs have a different molecular conformation from that of gramicidin S, and that the NH group of valyl residues is necessary for stabilizing the conformation to exhibit biological activity.
The Preparation and Reactions of α-Thiocarbonyl Dimethyloxo-sulfonium Ylides
Authors: Yoshida Hiroshi , Yao Terutaka , Ogata Tsuyoshi , Inokawa Saburo
Published: July 2006

α-Thiocarbonyl dimethyloxosulfonium ylides IIIa–e were prepared in moderate yields. The ester-stabilized ylides, IIIa–c, were mixtures of E and Z isomers, and IIIe was Z. The methylation of III with methyl iodide gave S-methylated products, IV, in quantitative yields. The thermal decomposition of IVa and IVe gave I(R=Me) and V respectively in good yields. The treatment of IIIb–e with carbon disulfide afforded 1,2-dithiole-3-thiones VIIIb–e in moderate yields.
The Photochemical Reaction of 1,1,4,4-Tetramethyl-2,3-tetralindione with Hydrogen Donors
Authors: Maruyama Kazuhiro , Takahashi Tomoji
Published: July 2006

The photochemical reaction of 1,1,4,4-tetramethyl-2,3-tetralindione, 1, with hydrogen donors, such as xanthene and aldehyde, in the liquid phase has been investigated. When xanthene was selected as the hydrogen donor, the main products were the “1,2-adduct,” photo-reduced α-keto alcohol, and 9,9′-bixanthenyl. The photolysis of 1 and an aldehyde gave the mixture of the “1,2-adduct” and the “1,4-adduct.” However, in the reaction with isobutyraldehyde another type of “1,2-adduct” was obtained, i.e., a combination product between the semidione radical and the isopropyl radical resulting from the decarbonylation of the isobutyryl radical, together with propene and carbon monoxide. The usual type of “1,2-adduct,” the “1,4-adduct,” and the photo-reduced product (α-keto alcohol) were the minor products in the reaction. It was also confirmed that the original “1,4-adduct” obtained from 1 and acetaldehyde rearranged photochemically to a different type of “1,2-adduct,” but no reverse rearrangement was observed under the present conditions. The mechanisms of the reactions were discussed on the basis of product analysis and the examination of the reaction by means of CIDNP.
Nucleophilic Displacement Catalyzed by Transition Metal. III. Kinetic Investigation of the Cyanation of Iodobenzene Catalyzed by Palladium(II)
Authors: Takagi Kentaro , Okamoto Tadashi , Sakakibara Yasumasa , Ohno Atsuyoshi , Oka Shinzaburo , Hayama Naomi
Published: July 2006

The nucleophilic displacement of iodobenzene with potassium cyanide was carried out in HMPA in the presence of palladium(II) acetate. The reaction obeys the following kinetics;

d[C_6H_5CN]/dt=k[Pd(OAc)_2]_0(M_KCN)^2/3

A reaction scheme composed of two cycles has been proposed: in one cycle Pd0 activates iodobenzene and in the other cycle Pd2+ assists the dissolution of potassium cyanide.
The Synthetic Reactions of Aliphatic Nitro Compounds. XI. The Synthesis of β-Amino-α-hydroxycarboxylic Acids and γ-Aminocarboxylic Acids
Authors: Kaji Eisuke , Igarashi Akira , Zen Shonosuke
Published: July 2006

The O-alkylation of some nitroparaffins, 2-nitropropane, 2-nitrobutane, 1-nitropropane, and phenylnitromethane, with methyl bromoacetate in dipolar aprotic solvent led to α-hydroxy-β-nitrocarboxylates, which were converted into β-amino-α-hydroxycarboxylic acids. Several γ-aminocarboxylic acids were synthesized from the corresponding γ-nitrocarboxylates which were obtained via  C-alkylation of the nitroparaffins with methyl β-bromo-propionate.
New Sesquiterpene Lactones of Eremophilane-Type from Ligularia Fauriei (Fr.) Koidz.
Authors: Moriyama Yoshihiko , Takahashi Takeyoshi
Published: July 2006

Two new sesquiterpene lactones of eremophilane-type were isolated from Ligularia Fauriei (Fr.) Koidz., and their structures including absolute stereochemistry were shown to be 8β-hydroxyeremophil-7(11)-ene-12,8α;14β,6α-diolide (1) and eremophil-7(11)-ene-12,8α;14β,6α-diolide (2), respectively. The isolation of the two known lactones, 6β,8β-dihydroxyeremophil-7(11)-en-12,8α-olide (3) and 6β-hydroxyeremophil-7(11)-en-12,8α-olide (4), is also described. The photosensitized autoxidation of the known furanoeremophilan-14β,6α-olide (5) gave 1 and 8β-methoxyeremophil-7(11)-ene-12,8α;14β,6α-diolide (18).
Layered Compounds. XXXVII. Syntheses and Properties of Quadruple-layered Metaparacyclophanes
Authors: Kannen Naoki , Otsubo Tetsuo , Misumi Soichi
Published: July 2006

Six quadruple-layered [2.2]metaparacyclophanes have been synthesized by photo-induced desulfurization or the Hofmann elimination method. Their electronic spectra exhibit stronger transannular electronic iteractions than those of the corresponding triple-layered [2.2]metaparacyclophanes and considerable dependence on the bridge substitution mode of the inside ring. The absorption spectra of the charge transfer compleses of a series of layered metaparacyclophanes and tetracyanoethylene have been studied with regard to the donor characters. It is concluded that the electron release from meta to para ring is significant, while the reverse is less effective.
Studies of the Removal of Oily Soil by Rolling-up in Detergency. II. On Binary Soil Systems Consisting of Oleic Acid and Liquid Paraffin
Authors: Ogino Keizo , Shigemura Ken-ichi
Published: July 2006

The rolling-up mechanism of oily soil from the surface of a polypropylene (PP) sheet in an aqueous solution of sodium dodecylbenzenesulfonate (LAS) was studied by the observation of the contact angle (θ). A binary system consisting of cis-9-octadecenoic acid (oleic acid)–liquid paraffin (Nujol) was used as an example of oily soil. The time required for the removal of the oily soil mixture from the PP sheet by rolling-up became shorter with the increase in the liquid paraffin content of the mixture. The oily soil with binary components was more easily removed from the substrate than a single-component oily soil.
Sulfoxonium Ylide Chemistry. VIII. A Novel Rearrangement of Dimethylsulfoxonium Ylides
Authors: Ide Junya , Hiraoka Tetsuo , Kishida Yukichi
Published: July 2006

Reduction of dimethylsulfoxonium 3-ethoxycarbonyl-1-[1,2-bis(methoxycarbonyl)vinyl]-2-phenylallylide (1) and dimethylsulfoxonium 3-ethoxycarbonyl-1-[2-(ethoxycarbonyl)vinyl]-2-phenylallylide (5) with zinc in acetic acid gave (Z)- and (E)-3-methoxycarbonyl-4-ethoxycarbonyl-5-phenyl-3,5-hexadienoic acid methyl ester (6a and 6b), and (Z)- and (E)-4-ethoxycarbonyl-5-phenyl-3,5-hexadienoic acid ethyl ester (7a and 7b), respectively, whose structures were determined by the NMR spectral data and further chemical transformations. The reaction mechanism of the reductive rearrangement was proposed to proceed through an anion radical to form a four membered intermediate (11), which cleaved to non-conjugated dienes leading to Z and E conjugated products.
Threshold Switching of Violanthrone in a Sandwich-type Cell
Authors: Sadaoka Yoshihiko , Sakai Yoshiro
Published: July 2006

Threshold switching between two impedance states has been observed at room temperature in a sandwich-type cell of violanthrone thin film with the use of silver electrodes. The conductivity of the “on state” is larger than that of the “off state” by a factor of 104.
Absorption Spectrum of the Aggregated Radical Anion of Sulfur Dioxide Produced by γ-Irradiation
Authors: Ito Osamu , Kuwashima Shigeru , Matsuda Minoru
Published: July 2006

By γ-irradiation of sulfur dioxide in 2-methyltetrahydrofuran at −196 °C, blue glassy solution was obtained, although the monomer radical anion of sulfur dioxide was colorless. The absorption spectrum of the blue species was identical with that of the stable radical anion produced by the amalgam reduction of sulfur dioxide, which was attributed to the dimer or trimer radical anion.
Resolution of Amino Acids. XII. Preparation of l-2-Amino-5-arylpentanoic Acids, Constituent Amino Acids in AM-Toxins
Authors: Shimohigashi Yasuyuki , Lee Sannamu , Izumiya Nobuo
Published: July 2006

The l-forms of 2-amino-5-(p-methoxyphenyl)pentanoic acid (Amp), 2-amino-5-phenylpentanoic acid (App), and 2-amino-5-(p-hydroxyphenyl)pentanoic acid (Ahp) are constituent amino acids in AM-toxins. The O-methyl linkage of l-Amp was hydrolyzed gradually by heating with hydrochloric acid. A procedure without drastic acid treatment is given for the synthesis and resolution of Amp. Diethyl [3-(p-methoxyphenyl)propyl]acetamidomalonate (3a) was saponified to the corresponding malonic acid (5a), and 5a was converted into acetyl-l-Amp (l-6a) by decarboxylation. The Dl-6a and acetyl-Dl-App were resolved by acylase to afford l-Amp and l-App, respectively. The l-Ahp was prepared from l-Amp by acid treatment.
The Stereoselective Synthesis of threo-3-Hydroxy-4-amino Acids
Authors: Katsuki Tsutomu , Yamaguchi Masaru
Published: July 2006

Two threo-3-hydroxy-4-amino acids, dl-4-amino-3-hydroxy-6-methylheptanoic acid (1) and dl-4-amino-3-hydroxy-2-methyl-5-(3-pyridyl)pentanoic acid (2), the optically active forms of which had been isolated by the acid hydrolysis of some antibiotics, were synthesized stereoselectively from l-leucine and Dl-3-(3-pyridyl)alanine respectively through 2-pyrrolidinone intermediates.
Heterocycles by Cycloaddition. IV. Cycloaddition Reactions of Mesoionic Compounds with a 7-Azabicyclo[2.2.1]heptadiene, and Double Fragmentation of the Adducts
Authors: Matsukubo Hiroshi , Kato Hiroshi
Published: July 2006

Cycloaddition of some five-membered mesoionic compounds with dimethyl 7-tosyl-7-azabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate occurs only across the unsubstituted double bond. Pyrolysis of the adducts resulted in a double fragmentation reaction to give two five-membered aromatic heterocycles. A dithiolone adduct gave the S-oxide, which was pyrolyzed to the corresponding thiopyran-2-one.
Determination of the Solubility of Oxygen in Copper by the Coulometric Method
Authors: Wada Tetsuya , Fueki Kazuo , Mukaibo Takashi
Published: July 2006

The solubility of oxygen in copper was determined at 800–1000 °C by means of the coulometric method. The data obtained is represented by the following equation: logN(atom fraction)=−2.164–1820⁄T
X-Ray Photoelectron Spectroscopy of Aminobenzoic Acids and Anthranilic Acid Chelates
Authors: Yoshida Tooru , Sawada Shigemasa
Published: July 2006

Photoelectron spectra of three isomers of aminobenzoic acid and several metal chelates of o-isomer were measured. It was confirmed that o- and p-isomers exist in the non-polar form and m-isomer in the dipolar. In the chelates the trend was for the N(1s) chemical shifts to increase in parallel with the metal electronegativities.
An MO-theoretical Study on the Hydration of Simple Olefins
Authors: Hirono Ichiro , Kikuchi Osamu , Suzuki Keizo
Published: July 2006

The acid-catalyzed hydration of simple olefins was studied on the basis of a semi-empirical SCF NDDO method. The substituent effect on the activation energy agreed well with experimental result.
NMR Studies of the Pyridine Exchange Reaction in the Pyridine Adduct of Bis(salicylaldehydato)nickekl(II)
Authors: Iwaizumi Masamoto , Migita Kouto , Isobe Taro
Published: July 2006

The pyridine exchange reaction in the pyridine adduct of bis(salicylaldehydato)nickel(II) becomes appreciably slower and its activation energy increases with the decrease of the electron donor properties of the in-plane ligand. However, changes in the spin delocalization onto the coordinated pyridine by the in-plane ligand appear small.
Reaction of Mercury(II)–Ethylenediaminetetraacetate–Capriquat Complex with Potassium Iodide in 1,2-Dichloroethane and Its Application to the Spectrophotometric Determination of Mercury(II)
Authors: Shimazaki Akira , Sugawara Masao , Kambara Tomihito
Published: July 2006

A mercury(II)-ethylenediaminetetraacetate-methyltrioctylammonium chloride (Capriquat) complex in 1,2-dichloroethane reacts quantitatively with potassium iodide and forms an ion-pair of tetraiodomercurate(II) with a capriquat cation. The composition of the extracted species was determined to be [Hg(edta)(Cq)2]. The reaction was applied to the spectrophotometric determination of mercury(II).
Some Aspects of the Solid-solid Reaction Products between MgO and V2O3
Authors: Oshima Hirotoshi , Yamamura Hiroshi , Shirasaki Shin-ichi
Published: July 2006

This report is concerned with the characterization of the metastably occurring reaction products with the spinel structure of a solid-solid reaction between MgO and V2O3 in an H2 atmosphere. The measurements of the lattice constants and the magnetic properties suggest that the oxygen framework of the product is formed in an early stage of the reaction, followed by the ordering of the magnetic ions in the tetrahedral sites.
Asymmetric Oxidation of Benzyl p-Tolyl Sulfide with Active Halogeno Compounds in the Presence of Optically-Active Alcohols
Authors: Sato Yoshiyasu , Kunieda Norio , Kinoshita Masayoshi
Published: July 2006

The oxidation of benzyl p-tolyl sulfide with active halogeno compounds such as N-bromosuccinimide, N-chlorosuccinimide and t-butyl hypochlorite, affords optically-active benzyl p-tolyl sulfoxide. The absolute configuration of the sulfoxide obtained depends on the chirality of the alcohols used.
Heterocycles by Cycloaddition. III. Dihydroisoindolequinone, the Correct Structure of the Proposed Azatetracyclononanedione
Authors: Matsukubo Hiroshi , Kato Hiroshi
Published: July 2006

Pyrolysis of a cyclopentadienequinone–oxazolone adduct (3) gives a 5,6-dihydro-4,7-isoindolequinone (7) and not an azatetracyclic cage compound (4). The dihydroquinone (7) was dehydrogenated to the corresponding isoindolequinone (9), which was synthesized via alternative routes.
Studies on Heterocyclic Chemistry. XX. Photo-reactions of 5-Benzylideneamino-3-arylisoxazoles in Trialkylamine
Authors: Nishiwaki Tarozaemon
Published: July 2006

Irradiation of 5-benzylideneamino-3-arylisoxazoles at 254 nm in a mixture of trialkylamine and nitrile gives diaminoethanes (reduction), benzamides (oxidation), and isoxazolo[5,4-b]pyridine (cyclization).
Oxidative Ring Cleavage of 3,5-Di-t-butyl-catechol and -o-benzoquinone by Base-Catalyzed Oxygenation
Authors: Nishinaga Akira , Itahara Toshio , Matsuura Teruo
Published: July 2006

The oxygenation of 3,5-di-t-butyl-catechol and -o-benzoquinone in t-BuOH with t-BuOK leads to the direct oxidative cleavage of the C1–C2 bond affording 2,4-di-t-butyl-4-carboxymethyl-2-buten-4-olide, a muconic acid derivative. The reaction is rationalized by assuming the reaction of 3,5-di-t-butyl-o-benzosemiquinone with oxygen.
Studies on Organic Semiconductors. XVIII. Photoconductivity of Heteroaromatic Compounds and Their Substituted Derivatives
Authors: Sugimoto Akira , Kato Shinji , Inoue Hiroo , Imoto Eiji
Published: July 2006

The effects of hetero atoms and substituents on the photocurrents of the parent compounds were investigated by comparison of the photocurrents of 52 specimens of the aza-benzenoid and oxa-benzenoid compounds.
Modification of the Packed-bed Electrode and Its Potential Distribution
Authors: Yoshizawa Shiro , Takehara Zenichiro , Ogumi Zempachi
Published: July 2006

The packed-bed electrode has been investigated in order to scale up the cell capacity by introducing three-dimensional electrode. The reactions of aniline formation by cathodic reduction of nitrobenzene and Fe(II) ion formation by cathodic reduction of Fe(III) ion were studied. When bed particles with high electric conductivity were used, the effective depth of the packed-bed where the electrode reaction took place was very small. However, when particles with moderate resistance were used, the effective depth increased. This is because the potential distribution in the bed material is the same as that in the electrolyte in the bed, the potential difference between particles and electrolyte thus being maintained constant at any position in the bed. From the standpoint of scaling up the cell capacity, this type of electrode can be effectively applied.
Electronic States of Fluorene, Carbazole and Dibenzofuran
Authors: Tanaka Masashi
Published: July 2006

The polarized reflection spectra of the fluorene, carbazole, and dibenzofuran crystals have been measured from 30000 to 53000 cm−1 and the absolute intensity of the absorption parallel to the a, b, and c axes of these crystals has been obtained by the Kramers-Kronig transformation; these data allowed an interpretation to be made for the solution spectra. Furthermore, the influence of the intermolecular interaction on each level has been examined. This analysis shows that the lowest excited state of the fluorene molecule is the B2 state, while those of the carbazole and dibenzofuran are the A1 states. In fluorene, the sum of the oscillator strengths of the transition to two lower excited states (α and α* states) is 0.39 in the molecule and 0.61 in the crystal. Such hyperchromism is also observed in the α, p, and β states of carbazole and the β state of dibenzofuran. On the other hand, the α* state of dibenzofuran is hypochromic and the oscillator strengths in the molecule (0.87) decrease to 0.36 in the crystal. However, the factor group splitting and the crystal field shift are small and a one to one correspondence can easily be obtained between the solution and crystalline spectra.
Hydrogen Atom Transfer in the Quenching of Pyrene Fluorescence by Amines
Authors: Okada Tadashi , Mori Takeshi , Mataga Noboru
Published: July 2006

The mechanism of the quenching of pyrene fluorescence by primary and secondary amines has been studied by means of fluorescence measurements and transient absorption measurements with the use of laser photolysis as well as conventional flash photolysis methods. It has been confirmed that 1-hydro-1-pyrenyl radicals and amino radicals are produced in the course of the fluorescence quenching reaction. The relative yields of 1-hydro-1-pyrenyl radicals for various amine quenchers were estimated.
Studies of MoO3–Al2O3 Catalysts in Ethylene Polymerization. IV. Kinetics and Stoichiometry of the Reduction
Authors: Hashimoto Keizi , Watanabe Shozi , Tarama Kimio
Published: July 2006

In order to reveal the formation mechanism of the active species in ethylene polymerization, the reduction of three kinds of molybdenum oxides, I, II, and III, which are insoluble in aq 10 M-NH3, soluble in aq NH3 but insoluble in water, and soluble in water respectively, was studied under a hydrogen pressure of 170 Torr over the temperature range 350–450 °C. The reduction rate of oxides I and II followed Elovich kinetics with a variable activation energy which increased with the progress of reduction, while that of III followed Elovich kinetics in the multiple kinetic stages and the minimum in apparent activation energy for the reduction lies at the reduction extent of MoO2.7−2.6. The final states of reduction of I, II, and III were MoO2.8−2.6, MoO2.0 and MoO2.2−2.1, respectively. The amount of Mo(V) in each oxide was determined by ESR measurements. The results indicate that Mo(V) in the II is related to the decrease of the apparent activation energy on reduction of III through their mutual interaction. A formation mechanism of the active species, Mo(V) in III, was proposed.
Photochemical Reaction of Ethyl 3-Methyl-3-phenylglycidate in Methanol and Ether Solvents
Authors: Chung Vo Van , Tokuda Masao , Suzuki Akira , Itoh Mitsuomi
Published: July 2006

Irradiation of ethyl 3-methyl-3-phenyl-glycidate (1) in methanol gave an ionic addition product of the solvent, whereas in ether solvent different reaction paths leading to β-keto esters and carbene were observed.
The Chlorination of Norbornadiene by Various Chlorinating Agents
Authors: Onoe Akira , Uemura Sakae , Okano Masaya
Published: July 2006

The chlorination of norbornadiene by CuCl2, TlCl3·4H2O, SbCl5, SeCl4, and VCl4 in CCl4 or CH3-CN afforded mainly trans-3,5-(1) and exo-cis-3,5-dichloronortricyclene (2). In the reaction with PbCl4, Cl2, SO2Cl2, and PCl5, appreciable amounts of exo-5-syn-7-(3) and/or exo-cis-5,6-dichloronorbornene (4) were obtained besides 1 and 2.
Extractive Spectrophotometric Determination of Chromium(III) with 1-(2-Pyridylazo)-2-naphthol
Authors: Subrahmanyam B , Eshwar M C
Published: July 2006

1-(2-Pyridylazo)-2-naphthol reacts with chromium(III), on heating at 80–90 °C for 35 min, at a pH of 3.2–3.7 in presence of acetate buffer. The reddishbrown chelate, extracted into 1-butanol, has two absorption maxima at 555 and 600 nm of equal intensity. The complex obeys Beer’s law in the range 0.3–2.0 μg/ml, has molar absorptivity 1.28×104 at 555 nm.
The Crystal and Molecular Structures of Dichloro-1,2-bis(di-t-butylphosphino)ethaneplatinum(II) and its Chlorobenzene Solvate
Authors: Harada Masahiro , Kai Yasushi , Yasuoka Noritake , Kasai Nobutami
Published: July 2006

X-Ray crystal structure analyses of [PtCl2{(t-Bu)2P(CH2)2P(t-Bu)2}] (I) and [PtCl2{(t-Bu)2P(CH2)2P(t-Bu)2}, C6H5C1] (II) have been carried out. Crystals of I belong to monoclinic system: a=20.595(3), b=7.917(3), c=14.885(2) Å, β=109.03(1)°, space group P21/c with Z=4. II forms monoclinic crystals, P21/c: a=14.873(2), b=13.193(2), c=15.314(2) Å, β=98.75(1)°, Z=4. Both structures, solved by the heavy-atom method, have been refined anisotropically by least-squares procedure to R=0.067 and 0.078 for I and II respectively. There is no essential difference between the structures of [PtCl2{(t-Bu)2P(CH2)2P(t-Bu)2}] molecules in I and II. The coordination around the platinum atom is square-planar; Pt–P=2.262(3) and 2.265(3) Å and Pt–Cl=2.374(4) and 2.365(4) Å. The molecule has a pseudo-C2 symmetry: the platinum atom and the center of the C–C bond in the P–C–C–P lie on this pseudo-C2 axis.
Crystal Vibrations and Intermodular Interactions of CH3X and CD3X (X=Cl, Br, and I)
Authors: Takeuchi Hideo , Bribes Jean-Luc , Harada Issei , Shimanouchi Takehiko
Published: July 2006

Normal coordinate treatments of the crystal vibrations of methyl chloride, methyl bromide, methyl iodide, and their perdeuterated analogs have been made. The values of force constants of non-bonded atom interactions have been determined so as to give the best fit to the lattice frequencies and the splitting frequencies of the intramolecular vibrations. It has been found that the dipole-dipole interactions are essential to account for the splittings of some internal modes, but their effects on lattice frequencies are negligible.
Studies of Nitrogen–Phosphorus Compound. XXVII. Synthesis of N4P4(NH2)8 and Its Hydrolysis
Authors: Kobayashi Etsuro
Published: July 2006

The method for synthesis of N4P4(NH2)8 by the reaction between (NPCl2)4 and ammonia and its hydrolysis behavior were investigated. The reaction of (NPCl2)4 with liquid ammonia took place violently at first, and the resulting product contained more than several percents of an insoluble material. The extract from this product had a rather low yield, about 20–25%. However, such a drastic reaction could be avoided by the addition of a small amount of dioxane to the reaction system; then the insoluble material did not form, and the yield increased to 55–66%. The final product contained P 37–38% and N 50–51%; thus the mole ratio of N to P was exactly 3 : 1 and the composition agreed with that of N4P4(NH2)8·H2O. When an aqueous solution of N4P4(NH2)8 was refluxed at 100 °C, the compound was initially hydrolyzed to PO(NH2)3 and P2O2NH(NH3)4, these being converted into PO(ONa)(NH2)2. At room temperature, the rate of hydrolysis was quite slow, but the composition of the hydrolysis products was similar to that at 100 °C. In a sodium hydroxide solution, N4P4(NH2)8 was converted directly into PO(ONa)(NH2)2 at an elevated temperature. The rate of the alkali hydrolysis obeyed a first-order equation, with the rate constants of 1.0×10−3, 2.5×10−3, 1.9×10−2, and 4.2×10−2 at 50, 60, 80, and 90 °C, respectively. These values were about 2.7 times that of N3P3(NH2)6. The activation energy of the reaction was 20.8 kcal/mol. The acid hydrolysis behavior resembled that in the neutral hydrolysis, but the reaction was accelerated with acid strength. The formation of tetrametaphosphimate by the hydrolysis of N4P4(NH2)8, that had previously been claimed, could not be reproduced in this study.
Structure of Ziegler-Natta Catalysts for the Polymerization of Isoprene
Authors: Uetsuki Masao , Fujiwara Yuzuru
Published: July 2006

Structural investigation was carried out by means of 1H-NMR, ESR, and chemical ionization mass spectrometry on the complexes formed by the reaction of alkylaluminum with titanium(IV) t-butoxide or vanadium(IV) t-butoxide as a catalyst for polymerization of isoprene. The t-butoxide was monomeric in benzene, and reduced to form a bivalent complex via trivalent ones on addition of the alkylaluminum to the solution followed by the formation of two kinds of binuclear aluminum complexes. In the trivalent state the complexes caused polymerization of isoprene to form five kinds of polymers, 1,4-polymerization of isoprene being likely caused by tris[di-μ-t-butoxo-dialkyltitanium(III)]aluminum, or the corresponding vanadium(III) complex. The final product of the reduction of vanadium(IV) t-butoxide was bis(di-μ-alkyl-dialkylaluminum)vanadium(II), which exhibits no catalytic activity.
Photoelectrochemical Reactions at SrTiO3 Single Crystal Electrode
Authors: Watanabe Tadashi , Fujishima Akira , Honda Ken-ichi
Published: July 2006

Electrode characteristics of strontium titanate (SrTiO3) single crystal have been investigated under illumination with light of its intrinsic absorption region. It has been found that the photosensitized electrolytic oxidation of water, known heretofore uniquely on the TiO2 electrode, can proceed also at the SrTiO3 electrode whose anodic dissolution being negligible. Although the photosensitivity of the SrTiO3 electrode is confined to a little shorter wavelength region than that of the TiO2 electrode, the formal quantum efficiency of the photosensitized electrolytic oxidation of water is comparable for these two semiconductor electrodes under intrinsic absorption. In contrast to the case of the TiO2 electrode, the electrochemical photocell consisted of the SrTiO3 anode and platinum cathode can work efficiently even when the pH values of the anodic and cathodic compartments are close to each other. This point is discussed in terms of the flatband potential of these semiconductor electrodes.