bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis of 1-N-[(S)-4-amino-2-hydroxybutyryl]-3′-deoxyribostamycin (3′-Deoxybutirosin B)
Authors: Ikeda Daishiro , Nagaki Fumiko , Tsuchiya Tsutomu , Umezawa Sumio , Umezawa Hamao
Published: July 2006

3′-Deoxybutirosin B (13) was prepared from ribostamycin by way of the following reaction sequences: 1) selective 3′-O-arylsulfonylation, 3′-iodination, and 3′-deoxygenation; 2) 1,6-cyclic carbamate formation,selective hydrolysis of the carbamate and acylation of the free 1-NH2 group with an active ester of (S)-4-amino-2-hydroxybutyric acid. The structure of 13 was confirmed by comparison of its Δ[M]TACu value with those of butirosin B and 4′-deoxybutirosin B.
Quantitative Analysis of Organocalcium Halides by Double Titration
Authors: Kawabata Nariyoshi , Nakamura Hisao , Yamashita Shinzo
Published: July 2006

The principle of Gilman’s double titration method for organolithium compounds was applied to the quantitative analysis of organocalcium halides. Chloroform was found to be useful as a reactive halide which completely decomposed organocalcium halides, but did not react with other alkali. The method gave satisfactory analysis for methyl-, propyl- and phenylcalcium iodides.
A Study of the Solubilization of Polar Oily Materials by Sodium Dodecyl Sulfate
Authors: Ogino Keizo , Abe Masahiko , Takesita Nobuo
Published: July 2006

The difference due to carbon-chain lengths and kinds of polar groups in the solubilizing phenomenon caused by Sodium Dodecyl Sulfate (SDS) of polar normal fatty acids and polar normal alcohols has been studied in terms of the amount of solubilization, the viscosity, and the surface tension. The amount of solubilization decreased with an increase in the number of carbon atoms in the molecules of oily materials, and it was larger for normal fatty acids than for normal higher alcohols with the same number of carbon atoms in the molecule. It was found that the oily materials of a greater amount of solubilization exhibited a small viscosity and a small rate of the reduction of surface tension.
Nuclear Spin-lattice Relaxation in Sn(CH3)4
Authors: Hasebe Tooru , Soda Gen , Chihara Hideaki
Published: July 2006

Nuclear magnetic relaxation T1 of solid Sn(CH3)4 increased monotonously with temperature between 77 and 217 K. The activation energy for intramolecular methyl reorientation was 2.6±0.3 kJ mol−1. From measurements on the liquid phase, the apparent activation energy associated with the relaxation process was 8.6 kJ mol−1. Differential thermal analyses revealed the existence of another unstable solid phase.
Electrical Conductivity Changes in α-FeOOH and β-FeOOH upon Surface Dehydration
Authors: Kaneko Katsumi , Inouye Katsuya
Published: July 2006

The electrical conductivity of α-FeOOH and β-FeOOH, preheated at 100–140 °C in vacuo, was determined over the temperature range from 0 to 140 °C. The conductivity increased considerably with a rise in the preheating temperature. The increase appears to be due to Fe2+ions produced by surface dehydration in the preheating.
Preparation of γ-FeOOH by Aerial Oxidation of Iron(II) Chloride Solution
Authors: Hamada Shuichi , Kuma Kenshi
Published: July 2006

Detailed conditions for preparing γ-FeOOH by aerial oxidation of iron(II) chloride solution were studied. The upper limit of temperature for obtaining only the γ-FeOOH decreased with increases in the pH value and the initial concentration of Fe(II) ions. The shapes of the prepared γ-FeOOH particles were examined in connection with the oxidizing conditions.
The Relationship between the Atmospheric Carbon Dioxide Concentration and the Carbon-14 Activity in Tokyo
Authors: Ikeda Sakuji , Shirakawa Hideki , Hattori Iwakazu
Published: July 2006

Measurements of the atmospheric CO2 concentration and the 14C activity in Tokyo were carried out. The activity of 14C in the CO2 decreased with an increase in the atmospheric CO2 concentration, indicating that increases in the atmospheric CO2 are caused only by the burning of fossil fuels.
On the Mechanism of Uncatalyzed Reduction of Triphenylmethyl Chloride with Triethylgermane
Authors: Sakurai Hideki , Mochida Kunio
Published: July 2006

Reduction of triphenylmethyl chloride with triethylgermane in benzene proceeds by a free-radical mechanism as evidenced by the observation of an ESR spectrum of the triphenylmethyl radical. However, the reduction involves apparently an ionic mechanism in a polar solvent such as dichloromethane and nitromethane.
Reaction of Tetramethylurea with Photoexcited Carbonyl Compounds
Authors: Tsujimoto Yuji , Nakahara Akihiro , Nishimura Yoshiyuki , Miyamoto Takuji , Odaira Yoshinobu
Published: July 2006

The photoreaction of tetramethylurea (I) with some carbonyl compounds (II) afforded in good yields the respective urea derivatives (III), which were converted into 2-oxazolidinones (IV).
Substituent Effects on Photochemical Extrusion of Phosphorus Group from 3-Phospholene System
Authors: Tomioka Hideo , Nakamura Shigehiro , Ohi Tsutomu , Izawa Yasuji
Published: July 2006

The rate of photo-extrusion of phenylphosphinidene oxide from 1-phenyl-3-phospholene 1-oxide was enhanced by β-methylation. It was found that the photoextrusion can be extended to the generation of phenylphosphinidene, but attempts to generate other phosphorus intermediates i.e., metaphosphite and methylphosphinidene oxide, were unsuccessful.
Synthesis of Dibenzo[d,j]-6,8-bisdehydro-oxa-[13]annulene
Authors: Ojima J\={u}ro , Kimura Akihiko , Ikeguchi Masahiko
Published: July 2006

The title compound (VII or VIII) has been synthesized from o-ethynylbenzaldehyde (II) by the Wittig reaction with the salt (III) followed by the oxidative coupling. The examination of the NMR spectra suggests that both of VII and VIII are atropic molecules.
The Reaction of Benzofuran with Manganic Acetate
Authors: Kasahara Akira , Izumi Taeko , Suzuki Akio , Takeda Toru
Published: July 2006

The oxidation of benzofuran with manganic acetate in a mixture of acetic acid and acetic anhydride yielded four products: 2-(acetoxymethyl)benzofuran, 3a,8b-dihydrofuro[3,2-b] benzofuran-2(3H)-one, bis(2-benzofuranyl)methane, and 2-benzofuranylacetic acid.
Synthesis of 1-Azido-5-methyl-4-hexen-2-one and Its Catalytic Dimerization
Authors: Katagiri Takao , Agata Akira , Takabe Kunihiko , Tanaka Juntaro
Published: July 2006

1-Azido-5-methyl-4-hexen-2-one was synthesized easily from 4-methyl-3-pentenenitrile which was prepared from isoprene. This compound is quite stable. Its catalytic dimerization gave 4,4-bis(3-methyl-2-butenyl)-2-butenolide.
Photoreactions of the Uranyl Ion with Arylaldehydes in Solution
Authors: Matsushima Ryoka , Mori Kenichi , Suzuki Morio
Published: July 2006

Irradiation of benzaldehyde in a deoxygenated aqueous acetone solution in the presence of the uranyl ion with light of λ≥365 nm gives the U(IV) species and benzil (1) as the main photoredox products, and small amounts of 4-hydroxy-4-phenylbutan-2-one (2), trans-4-phenyl-3-buten-2-one (3), and an unidentified product (4). None of them are formed in the absence of the uranyl ion. The products 2 and 3 are assumed to be formed by the uranyl ion-photocatalyzed condensation of benzaldehyde with acetone. Irradiation of acetophenone in the presence of the uranyl ion gives no photoproducts, though the uranyl emission is effectively quenched. p-Methoxybenzaldehyde and p-chlorobenzaldehyde give the corresponding 4,4′-disubstituted benzils respectively by irradiation under similar conditions. The quantum yield for the formation of the U(IV) species decreases whereas the quenching constant increases with the increase in the electron donating power of the substituent. The physical quenching process appears to compete significantly with the chemical (redox) process. The relative importance of the physical quenching to the chemical quenching process has been estimated. As to the photocatalyzed aldol condensation, the excess vibrational energy, which the quencher and/or the quenchee would possess during or immediately after the quenching interactions, may possibly be converted into the energy of the chemical reaction.
Studies of the Effect of 1-Dodecanol on the Micellization of Sodium Dodecyl Sulfate by Gel Filtration
Authors: Suzuki Hitoshi
Published: July 2006

The tail analysis of gel filtration was applied to an aqueous sodium dodecyl sulfate (SDS) solution containing solubilized 1-dodecanol. Commercial SDS containing 1-dodecanol as an impurity showed a maximum micellar size at CMC. The addition of 1-dodecanol caused an increase in the micellar size due to solubilization. The amount of 1-dodecanol impurity was estimated from the elution rate of the micelle, Rm, the result being in agreement with that obtained by surface tension measurements.
Epoxide Rearrangement III. Isomerization of 1-Methylcyclohexene Oxide over TiO2–ZrO2, NiSO4 and FeSO4
Authors: Arata Kazushi , Akutagawa Susumu , Tanabe Kozo
Published: July 2006

The reaction of 1-methylcyclohexene oxide at 108 °C was found to give predominantly 2-methylcyclohexanone (III) over FeSO4, but predominantly allyl alcohols (VI) over TiO2–ZrO2 of various compositions. NiSO4 gave the same amount of both products, III and VI. The selectivities over FeSO4 and NiSO4 were not much varied with calcination temperatures from 150 °C to 700 °C, while the catalytic activities were higher with NiSO4 calcined at low temperature and with FeSO4 calcined at high temperature. FeSO4 and NiSO4 gave the preferential formation of an allyl alcohol with exo-double bond, 2-methylene cyclohexanol (VIa), while TiO2–ZrO2 formed predominantly an allyl alcohol with endo-double bond, 2-methyl-2-cyclohexene-1-ol (VIb). Both the acidity and basicity of TiO2–ZrO2 were observed to increase by mixing each oxide and to correlate with the catalytic activity. The allyl alcohol formation was explained by an acid-base bifunctional mechanism.
Theoretical Calculations of the Infrared Absorption Intensities of Simultaneous Transitions
Authors: Shinoda Hiroyuki , Mitsuya Munehisa
Published: July 2006

The formula of the infrared absorption intensity of a simultaneous transition has been derived on the basis of the vibronic expansion technique, with two simple assumptions. By the use of the foumula, the theoretical calculations of the intensities for the CO2–N2 and CO2–H2 systems have been done, the electronic wave functions being calculated by the CNDO/2 method. In both cases, it was found that the main contribution to the absorption intensity arises from the coupling between the electronic state of CO2 and the nuclear vibration of the homonuclear diatomic molecule. Furthermore, the intensities of the fundamental, first-overtone, and combination bands of CO2 have been calculated according to the formula corresponding to an intramolecular process, and the intensities of the overtone and combination bands caused by the intermolecular process have been calculated. These calculated results have been discussed in comparison with one another.
Inter- and Intramolecular Exciplexes and EDA Complexes in the 9,10-Dicyanoanthracene and Alkylbenzene Systems
Authors: Itoh Michiya , Kumano Yoshiro , Okamoto Toshihiko
Published: July 2006

The exciplex (above ∼150 K) and EDA complex (below ∼120 K) fluorescence were observed in the 9,10-dicyanoanthracene and several alkylbenzene systems and also in the intramolecular system of (9,10-dicyanoanthracene)-(CH2)3-(pentamethylbenzene) in the nonpolar solvents. The exciplex fluorescence lifetimes and maxima both in the inter- and intramolecular systems exhibit the continuous change to those of the corresponding EDA complex, which implies the identical fluorescent state of the exciplex and EDA complex. The fluorescence lifetimes and the fluorescence polarization suggest that the fluorescent state of both exciplex and EDA complex may be mostly locally excited state of electron acceptor.
Photoelectron Ejection and Fluorescence from Molecular “Rydberg” States in Polar Solvents
Authors: Nakato Yoshihiro , Nakane Akihiro , Tsubomura Hiroshi
Published: July 2006

Absorption and fluorescence spectra and photo-current yield curves of tetraaminoethylenes are studied. The UV absorption of these compounds is mostly attributable to the transitions from the ground state to the “vertical” Rydberg-like and ionized states. Their spectral shapes in ether and in pentane are nearly coincident with each other, showing that these states just after excitation are little affected by the solvent polarity. Based on this result and the results of photo-current measurements, the spontaneous formation of free, solvated electrons from the “vertical” Rydberg-like states in polar solvents has been verified. It is also found that the maximum wave numbers, the lifetimes and the yields of the fluorescence from the lowest “relaxed” Rydberg-like state depend strongly on solvent polarity, temperature and rigidity. These results are explained by taking account of the competition between electron ejection and relaxation processes and of the presence of a non-fluorescent, solvated cation-electron pair. The photo-electron ejection from other organic molecules in polar solvents reported before is shown to be explained by the same scheme as presented here.
Triplet Excimer of Phenanthrene in Fluid Solution. Dynamic Analysis of Time-Resolved Phosphorescence
Authors: Aikawa Masayuki , Takemura Takeshi , Baba Hiroaki
Published: July 2006

The excimer phosphorescence of phenanthrene in isooctane at temperatures over a range of 300–77 K has been studied by means of a photon-counting technique. At temperatures above the melting point of isooctane a broad emission spectrum with its intensity maximum at 525 nm was obtained, which is essentially different from the structured phosphorescence spectrum obtained in rigid media at 77 K. The time dependence of the spectral shape and intensity of the phosphorescence emission affords strong evidence that the broad emission spectrum originates from the triplet excimer. A scheme of the triplet excimer formation involving a self-quenching pathway of the triplet monomer is proposed to interpret the time and concentration dependence of the monomer and excimer phosphorescence.
Sum Rule Consideration of Molecular Photoelectron Spectra: s-Type Bands of Butenes
Authors: Katsumata Shunji , Kimura Katsumi
Published: July 2006

The s-type photoelectron bands of cis-, trans-2-butene, and 2-methylpropene in the gaseous phase have been measured in the region 17–27 eV by a He(II) resonance lamp which was constructed for the present purpose. The vertical ionization energies obtained here from the s-type bands have been interpreted with the H\ddotuckel method involving the Coulomb integrals of carbon 2s atomic orbitals which were estimated on the basis of the idea of sum rule from the available He(II) data of many other hydrocarbons reported by Potts et al.
Substitution Reactions of Several Lead(II)–Polyamine-N-polyacetate Complexes with Indium(III) in Aqueous Solutions
Authors: Nozaki Toru , Suemitsu Nagao
Published: July 2006

The kinetics of the substitution reactions of the lead(II) complexes of EDTA, EDTA·OH, CyDTA, and DTPA with the indium(III) ion have been studied in the pH range from 1.8 to 4.8 at 20 °C and at an ionic strength of 0.1 in the presence of an excess of lead(II) ions. The reaction for the CyDTA system seems to proceed through only the dissociative process, while those for the EDTA, EDTA·OH, and DTPA systems proceed through both the steps forming a binuclear intermediate and the dissociative steps, in which the reactions forming indium complexes proceed mainly through the paths involving InOH2+.
Selective Activation of Methylene or Methine Groups of Tripeptide-Schiff Bases Coordinated around Nickel(II)
Authors: Fujioka Mamoru , Nakao Yasuo , Nakahara Akitsugu
Published: July 2006

Nickel(II) chelates of the Schiff bases derived from salicylaldehyde and tripeptides such as glycylglycylglycine, glycyl-Dl-α-alanylglycine, glycylglycyl-Dl-α-alanine, and Dl-α-alanylglycylglycine have newly been prepared. The reactivity of methylene or methine groups in the tripeptide moieties of those Schiff base chelates has been studied by PMR spectra in D2O. It has been found that the methylene or methine protons of the N-terminal amino acid residues are most effectively activated by the coordination around nickel(II) as compared with those of the C-terminal and central amino acid residues.
An INDO Molecular Orbital Approach to the Proton Affinity of Oxygenated Compounds
Authors: Ohkubo Katsutoshi , Tsuchihashi Kohji , Yoshida Toshiaki , Okada Masahide
Published: July 2006

The correlation between the gas-phase proton affinities of aliphatic oxygenated compounds (alcohols, acids, and esters and their electronic structures was investigated by means of an INDO-MO theory. There appears to be a satisfactory linear-dependence of the proton affinities with the energy difference between the parent molecule and the energetically most stable protonated species and with the bond energy of the oxygen-proton bond, although the above energies are overestimated in comparison with the proton affinities. The proton affinities are also predicted with a sufficient accuracy using the first ionization potential and the electron density of the oxygen atom (especially, the % p-character in the oxygen lone-pairs) of the parent molecule.
The Reactions of 2-Substituted 4-Chloro-6-(2-hydroxy-1-naphthyl)-1,3,5-triazines with Several Nucleophiles
Authors: Tsunoda Shigeo , Hashida Yoji , Sekiguchi Shizen , Matsui Kohji
Published: July 2006

The nucleophilic substitution reactions of 2-methoxy- and 2-diethylamino-4-chloro-6-(2-hydroxy-1-naphthyl)-1,3,5-triazines (1) with aniline, diethylamine, sodium azide, and sodium methoxide were carried out and compared with the reactions of the corresponding derivatives of 4-chloro-6-(4-hydroxy-1-naphthyl)-1,3,5-triazine (2) and 4-chloro-6-(1-naphthyl)-1,3,5-triazine (3). Compound 1 was found to be more reactive than the corresponding (2) and (3), not only in the reactions of a neutral molecule, but also in those of anionic species. The results of the reactions of neutral species are interpreted in terms of the difference in solvation toward the substrates; however, the loss of coplanarity between the naphthalene and triazine nuclei may be responsible for the high reactivity of Compound 1 in the reactions of anionic species.
The Metal-Ion-Catalyzed Alcoholysis of β-Dicarbonyl Compounds
Authors: Uehara Kaku , Kitamura Fujio , Tanaka Makoto
Published: July 2006

The alcoholysis of β-dicarbonyl compounds of the type CH3COCHRCOR′ is catalyzed by a variety of metal ions. In the presence of a large excess of β-diketone compared with metal ions, the rate is given by the expression: rate=kobsd[M2+][ROH]. The values of kobsd decrease with M2+ in the order Zn2+>Co2+>Ni2+>Cu2+. The reaction rate is remarkably affected by the substituents (R,R′), the kinds of alcohol and solvent used, the addition of a chelating agent, and also by the counter anion of the metal ion. The alcoholysis proceeds more slowly in CH3OD than in CH3OH by a factor of 1.4. These are interpreted in terms of a mechanism in which the β-dicarbonyl compound coordinated to a metal ion is attacked by the alcohol which is also coordinated to the metal ion to cleave the C2–C3 or C3–C4 bond of the dicarbonyl compound. A convenient method for the preparation of β,γ-unsaturated ketones and esters is provided by the alcoholysis of alkenyl substituted β-dicarbonyl compounds in the presence of zinc acetate.
The Reactions of the Dimers of Hexafluoropropene with O-Nucleophiles
Authors: Ishikawa Nobuo , Nagashima Akira
Published: July 2006

The reactions of the dimers of hexafluoropropene with alcohols and phenol in the presence of triethylamine, and with sodium alkoxides and phenolate were carried out. Of the two dimers, perfluoro-2-methyl-2-pentene (Dimer 2) was much more reactive than perfluoro-4-methyl-2-pentene (Dimer 1). While the dimer 2 and O-nucleophiles gave various addition and substitution products very easily, the dimer 1 reacted only with sodium alkoxides to give trialkoxylated products.
Palladium-catalyzed Decomposition of Azides. I. Formation of Nitriles
Authors: Hayashi Hiroshi , Ohno Atsuyoshi , Oka Shinzaburo
Published: July 2006

Palladium metal catalyzes the decomposition of benzyl azide affording benzonitrile, benzylamine, and N-benzylidenebenzylamine. The presence of a suitable hydrogen-acceptor improves the yield of benzonitrile at the sacrifice of benzylamine, whereas the yield of N-benzylidenebenzylamine remains constant. The reaction is applied to the preparation of other nitriles.
Anisotropy of Needle Cokes
Authors: Mochida Isao , Ogawa Masashi , Takeshita Kenjiro
Published: July 2006

The anisotropic properties of several lump needle cokes were studied by means of a X-ray diffractometer, a dilatometer, and a reflected microscope in order to evaluate the anisotropic factors of the needle cokes and to discuss the relations among them. Among them several relations were found, which were well understood on the basis of the structure of the uniaxial arrangement of the crystallites. The change in these factors upon heat treatment was also investigated in order to find how these factors depended on the crystal-growth of the needle coke. Some anisotropic properties of the extruded sample were compared with those of the filler coke, which were observed in a lump shape. The results indicate that the extruded sample had its anisotropic properties considerably lowered. The structure and crystal-growth of the needle cokes are discussed based on these observations.
Preparations and Properties of Some Derivatives of Pseudo-Geminal Ketone of Tris[2.2.2]paraxylylene
Authors: Imashiro Fumio , Yoshida Zen-ichi , Tabushi Iwao
Published: July 2006

Some derivatives of pseudo-geminal ketone of tris[2.2.2]paraxylylene (I) were prepared and their spectral properties were investigated in connection with their structural characteristics. The stereochemistry of two isomers of pseudo-geminal carbinols of tris[2.2.2]paraxylylene (III and V) was determined on the basis of chemical shifts of benzhydryl protons and Ho protons in NMR spectra and also of νO-H bands in IR spectra. The difference in chemical shifts of Hp protons of the two alcohols was explained in terms of the change in electron densities of para carbon atoms.
Nucleophilic Ion Pairs. I. Enhanced Esterolytic Reactivity of Hydrophobic Ion Pairs in Micellar Systems
Authors: Kunitake Toyoki , Shinkai Seiji , Okahata Yoshio
Published: July 2006

The reaction of the dodecyl(2-hydroxyimidophenethyl)dimethylammonium bromide(DHDB) and N-methylmyristohydroxamate (MMHA) anion with p-nitrophenyl acetate was studied mostly in the presence of aqueous nonionic micelles. Addition of a hydrophobic ammonium ion, TMAG, considerably enhanced the reactivity of MMHA but not that of DHDB (a zwitterion). The rate enhancement for MMHA-TMAC and DHDB in nonionic micelles were almost comparable to those in cationic(CTAB) micelles. It was proposed that the large enhancement observed for some anionic nucleophiles in cationic micelles is to a great extent caused by the formation of hydrophobic, desolvated ion pairs.
Reversible CO Insertion into an Ni–C Bond of Alkyl(acetylacetonato)(triphenylphosphine)nickel(II)
Authors: Saruyama Toshio , Yamamoto Takakazu , Yamamoto Akio
Published: July 2006

Reaction of alkyl(acetylacetonato)(triphenylphosphine)nickel(II), RNi(acac)(PPh3)n (R=C2H5, n=1 (1a); R=CH3, n=2 (1b)) with carbon monoxide gives acyl(acetylacetonato)(triphenylphosphine)nickel(II) RCONi(acac) (PPh3) (R=C2H5 (2a); R=CH3 (2b)). Elemental analysis, IR and NMR spectra, and chemical properties of the acylnickel complexes support the structure. A variable temperature NMR spectroscopic study has revealed that the acac ligand in the acyl complexes exchanges rapidly in solution on NMR time scale. The acylnickel complexes 2a and 2b tend to decarbonylate at room temperature, the decarbonylation tendency of 2b being greater than 2a. They undergo further disproportionation according to the stoichiometry: 3RCONi(acac)(PPh3)→RCOR+Ni(CO)2(PPh3)2+Ni(acac)2+RNi(acac)(PPh3). The mechanism involving the cross coupling of the acylnickel complex with the alkylnickel complex is proposed for the reaction on the basis of formation of CH3COC2H5 on reaction of 2a with 1b.
Hydroquinone and Quinone Derivatives of the (Z)- and (E)-β-Thiocrotonates
Authors: Campaigne E , Abe Yasuo
Published: July 2006

Addition of ethyl thioacetoacetate to p-benzoquinone and 1,4-naphthoquinone gave satisfactory yields of the expected ethyl(Z)-β-(2,5-dihydroxyphenylthio)crotonate and ethyl(Z)-β-(1,4-dihydroxynaphthyl-2-thio)crotonate respectively. In the latter case, at higher temperatures the isomeric ethyl(E)-β-(1,4-dihydroxynaphthy 1-2-thio)crotonate was the major product. Oxidation of these compounds with chromic acid gave the corresponding Z-and E-isomeric quinone derivatives, but oxidation of the Z-isomer of the phenyl compound at higher temperatures gave the (E)-quinone derivative. All eight isomers in these two series have been isolated, characterized and identified by NMR assignment.
ESR Spectra of Nitric Oxide Adsorbed on ZrO2, CeO2, and ThO2
Authors: Niwa Miki , Minami Takashi , Murakami Yuichi
Published: July 2006

ESR spectra of nitric oxide adsorbed on ZrO2, CeO2, and ThO2 were measured at −196 °C, and g⊥, g⁄⁄ and splitting constants were determined.
The Spectrophotometric Determination of Beryllium with Chromazurol S and Polyoxyethylenedodecylamine
Authors: Nishida Hiroshi , Nishida Taeko , Ohtomo Hiroshi
Published: July 2006

A sensitive and selective method for the spectrophotometric determination of beryllium with Chro mazurol S (CAS) and polyoxyethylenedodecylamine(POEDA) in the presence of EDTA and perchlorate is proposed.
The Mercury-photosensitized Reaction of Hydrogen with Nitric Oxide
Authors: Tadasa Kohji , Imai Naomi , Inaba Tetsuo
Published: July 2006

The Hg-photosensitized reaction of a mixture of H2 and NO has been studied mainly at room temperature. The quantum yield of the H2O formation is nearly unity, independent of the pressures of both H2 and NO. The quantum yield of the N2 formation is proportional to the NO pressure, while that of N2O decreases with the NO pressure; both of them are independent of the H2 pressure. In order to interpret the results concerning the H2O formation, the following process is proposed:

(i) NO3+NO→2NO2

NO2+HNO→OH+2NO

OH+HNO→H2O+NO

in addition to the well-established H2O-forming process:

(ii) 2HNO→H2O+N2O

NO2, one of the reactants in Process (i), is formed by the chain process proposed by Arden and Phillips:

(iii) H+NO+M→HNO+M

HNO+2NO→N2+H+NO3

The (ii) and (iii) processes also coincide with the results of the N2O and N2 formations respectively.
The Crystal and Molecular Structure of Zinc Complex of 2-Chlorobenzoic Acid. I. The Crystal and Molecular Structure of Bis(2-chlorobenzoato)zinc(II)
Authors: Nakacho Yoshifumi , Misawa Takeshi , Fujiwara Takaji , Wakahara Akio , Tomita Ken-ichi
Published: July 2006

The crystal of bis(2-chlorobenzoato)zinc(II) is monoclinic, space group P21/c, a=7.284, b=10.480, c=19.091 Å, β=95.59°, and Z=4. The structure was solved by usual heavy atom method and refined to the final R-value of 0.052. In the crystalline state, the complex forms a chain. Each zinc atom is bonded to four oxygen atoms from four different ligands.
Magnetic Two-dimensionality and Antiferromagnetism in the DANO Crystal
Authors: Takizawa Osamu
Published: July 2006

An organic free radical crystal, the di-p-anisyl nitric oxide (DANO) crystal, was found to exhibit the characteristics of the two-dimensional Heisenberg spin system in its magnetic susceptibility at low temperatures and in its angular dependence of the ESR line width at room temperature. A distinct minimum of magnetic susceptibility due to a phase transition to antiferromagnetic spin ordering was observed at 1.67 K; this is consistent with the results of the NMR measurements, while another unexplainable anomaly was found near 2.7 K. The magnetic anisotropy field, HA, along the a-axis, perpendicular to the magnetic easy-plane, was determined to be (3±1)×102 Oe at 0 K from the analysis of the antiferromagnetic resonance; it was attributed to the magnetic field originating from the spin magnetic dipoles distributed over the radical molecules. The ratio of the anisotropy field to the exchange field within the magnetic two-dimensional plane, HA⁄HE, and that of the Néel temperature to the Weiss temperature, TN⁄θ, were found to be 5×10−3 and 0.34 respectively. The ratio of the inter-plane exchange interaction to the intra-plane one, J′⁄J, was estimated therefrom to be of the order of 10−3.
A Structure Analysis of a Bromoacetate of Hydroxypiperenone by the X-Ray Diffraction Method
Authors: Matsui Kuniaki , Fukuyama Keiichi , Tsukihara Kumiko , Tsukihara Tomitake , Katsube Yukiteru , Munakata Katsura
Published: July 2006

The structure of a bromoacetate of hydroxypiperenone, C24H31O7Br, has been determined by the X-ray diffraction method. The compound crystallized in the space group P21 with a=8.296, b=13.247, c=11.400 Å, and β=102.8°. The structure was solved by the heavy-atom method and refined to R=0.075 for 1614 reflections. The present analysis has established that the five- and six-membered rings are fused in the cis fashion. The absolute configuration of the molecule has been determined by using the anomalous dispersion effect of the bromine atom for Cu Kα radiation.
The Crystal and Molecular Structure of Tris-(2,2,6,6-tetramethylheptane-3,5-dionato)lutetium(III)
Authors: Onuma Shigeki , Inoue Hironao , Shibata Shuzo
Published: July 2006

The crystal and molecular structure of tris-(2,2,6,6-tetramethylheptane-3,5-dionato)lutetium(III) has been determined by X-ray diffraction method. The space group is Pmn21, and the unit cell is orthorhombic with a=17.713(4), b=10.638(2), c=9.973(3) Å, and Z=2. The structure is isomorphous with the erbium analogue. The atomic parameters of the molecule (except for hydrogen atoms) were refined by the block-diagonal least-squares method to an R of 0.053. Three chelate rings are planar. One of them lies in the crystallographic mirror plane, and the other two rings are symmetrically related to each other with respect to this mirror plane. Six oxygen atoms of the three β-diketones form a distorted trigonal prism around the central lutetium ion, the average Lu–O distance being 2.19 Å.
A High-Resolution Vacuum Spectrometer for the Infrared
Authors: Fujiyama Tsunetake , Nakagawa Jun , Suzuki Isao , Nakagawa Ichiro , Shimanouchi Takehiko
Published: July 2006

A high-resolution vacuum spectrometer for the near and medium infrared has been designed and built with capability of resolving 0.03 cm−1. The spectrometer consists of the fore-optics with a built-in White cell, a 2.5 m Littrow-McCubbin type monochromator which utilizes a 31.6 lines/mm echelle grating with the ruled area of 102 mm×206 mm, and an order-sorter which is essentially a prism spectrometer of Wadsworth mount. Details of the design, construction, and performance of the instrument are described.
Dielectric Relaxation in p-Substituted Thiophenols in the Liquid State
Authors: Roy Subir K , Sengupta Kamalendu , Roy S B
Published: July 2006

The dielectric absorption in 4-methylthiophenol and 4-chlorothiophenol in the liquid state has been studied in 0.8, 1.25, 1.62 and 3.49 cm microwave regions. Molecular and intramolecular relaxation times, their relative weight factors and the heats of activation have been determined. The results have been discussed and compared with other related molecules.
Influence of Added Alcohols on the Pfeiffer Effect of Tris(1,10-phenanthroline)zinc(II)-l-Malic Acid and -d-Tartaric Acid Systems in Water
Authors: Miyoshi Katsuhiko , Kuroda Yasushige , Isoe Yuji , Yoneda Hayami
Published: July 2006

Influence of lower alcohols (methanol to butanol) was examined on the Pfeiffer effect of the [Zn(phen)3]2+-l-malic acid and -d-tartaric acid systems in water at 25 °C (phen=1,10-phenanthroline). It was found that the Pfeiffer rotation αp decreases linearly with molar concentration CA of added alcohols for both systems, and that the logarithm of the rate of the decrease in αp with CA is a linear function of the number of methylene groups in added alcohol molecules. This is well interpreted on the assumption that added alcohol molecules adhere to [Zn(phen)3]2+ ion, thereby preventing the complex and chiral acid from coming into contact with each other. The enthalpy change per methylene group on passing from the alcohol environment to the complex environment was estimated to be ca. 0.7 RT.
The Photo-Enolization of β-Disubstituted αβ-Unsaturated Ketone
Authors: Tada Masaru , Miura Kyo
Published: July 2006

γ-Methyl groups of mesityl oxide (I), dypnone (II), 2-isopropylidenecyclopentanone (III), and pulegone (IV) were deuterated by ultra-violet irradiation in methanol-d. It has been claimed that these ketones are not enolized by photo-excitation, but the formation of enol by irradiation was proved by infrared spectroscopy at a low temperature and was correlated to the photo-deuteration. The photo-enolization was deduced to occur from an n–π* singlet excited state.
The Air Oxidation of Catecholamines by Flavin Mononucleotide
Authors: Takahashi Fujio , Rahman M B , Maeda Hirotoshi
Published: July 2006

Polarographic studies of the aerobic oxidation of catecholamines under the influence of FMN in various concentrations, and spectrophotometric investigations of the formation of FMN–catecholamine complexes, have been carried out. By following the course of the oxidation reaction polarographically, the rate constants have been found. The oxidation of catecholamines by air was found to be disturbed through complex formation and to be facilitated by light illumination. The equilibrium constants for the formation of some catecholamine complexes with FMN have been calculated.
The Reaction of Tris(diethylamino)bismuthine with Carbonyl Compounds and the Reactivity Comparison of Several Metal Amides
Authors: Ando Fumio , Ohashi Kumao , Koketsu Jugo
Published: July 2006

Tris(diethylamino)bismuthine (I) reacted with the sterically unhindered carbonyl compounds to give the corresponding enamines. The reactivity of the metal amides M(NR2)n (M=As, Sb, Bi, and Ti; R=Me and Et) toward the carbonyl compounds was examined. The order of reactivity: Bi>Sb>Ti>As was observed for the addition reaction that took place as the first step in the reaction. On the other hand, the order of enamine formation was Sb>Ti>As>Bi. The effectiveness of the amination reaction depends both on the reactivity of metal amides to carbonyl groups and also on the affinity for oxygen of metal atoms. Although bismuth amide gives the addition product very rapidly, because of its poor affinity for oxygen, the addition products decompose thermally on prolonged standing or on distillation giving large amounts of starting carbonyl compounds along with small amounts of enamines.
Effect of Spiro Ring Size on the Photochemical Ring Expansion of Dispiro Substituted Cyclobutane-1,3-diones
Authors: Kimura Koji , Takamura Masakazu , Koshibe Shigeru , Juro Masayoshi , Fukuda Yoshihiro , Odaira Yoshinobu
Published: July 2006

The photochemical ring expansion of dispiro substituted cyclobutane-1,3-diones in methanol has been investigated. The formation of ring expansion product was strongly dependent on the spiro ring size of dispiro substituent. The ring expanded acetal was obtained in a low yield when the spiro ring of dispiro substituted cyclobutane-1,3-diones was a five- or seven-membered ring. This is the first example of photochemical ring expansion from cyclobutane-1,3-diones. A mechanism is postulated.
Double 1,3-Dipolar Cycloaddition Reaction of 3-Phenylsydnone with 1,3-Dienes
Authors: Haneda Akira , Imagawa Takeshi , Kawanisi Mituyosi
Published: July 2006

Thermal reaction of 3-phenylsydnone with isoprene or 2,3-dimethylbutadiene gave 2-methyl- or 2,6-dimethyl-7-phenyl-1,7-diazatricyclo [2.2.1.02,6]heptane, together with 3-isopropenyl-1-phenylpyrazole. The former is the product of the double 1,3-dipolar cycloaddition. A similar reaction with 1,3-butadiene gave only 3-vinyl-1-phenylpyrazole.
Cyclopentadienylsodium and Phenylethynylsodium as Cocatalysts in Olefin Metathesis
Authors: Ichikawa Kazuaki , Takagi Toru , Fukuzumi Kazuo
Published: July 2006

Cyclopentadienylsodium and phenylethynylsodium are effective cocatalysts with WCl6 in the homogeneous olefin metathesis. The optimum mole ratios of C5H5Na and PhC≡CNa to WCl6 ranged more widely—from 1.5 to 3.0 and from 1.5 to 2.5 respectively—than that of BuLi to WCl6. The formation of the Friedel-Crafts products was extremely small—such as 1—%, if the cocatalyst/WCl6 ratio was about 2. The new catalyst systems were less poisoned by ether than the other catalyst systems and were hardly deactivated in the course of the reaction. The characteristics of these catalyst systems were discussed.
Semi-empirical UHF-MO Studies of the Spin Distribution and the Bonding Character of Iron-group Fluorides and Some Other Similar Transition Metal Halides
Authors: Sakaki Shigeyoshi , Kikkawa Hisamichi , Kato Hiroshi , Yoshida Satohiro
Published: July 2006

CNDO- and INDO-type UHF-MO calculations are carried out on MF6n− (M=V(II), Cr(III), Mn(II), Fe(III), Ni(II)), NiCl64−, MnCl64−, MnCl42−, MnBr64−, and CuCl42−. The calculated spin fractions on the ligand orbitals agree well with the experimental values, with a few exceptions. Spin transfers to ligands are mainly attributed to the spin delocalization (SD) mechanism, except those to the 2s and 2pσ, orbitals of the F ligand in CrF63− and VF64−, in which spin transfer to those orbitals results from the spin polarization (SP) mechanism. Unpaired electrons are also transferred into the 4s and 4p orbitals of the central metal ion by the SP mechanism. The spin transfers to the ligand due to both the SD and SP mechanisms increase in the order of F<Cl<Br in MnX64− and NiX64−. The following characterisities of metal-halogen bonds are established; (1) the covalent interaction between the metal d-orbital and the fluorine atom increases in the order Ni(II)<Mn(II)∼ Fe(III)Cl>Br, while the p-character increases in the same order.
The Synthesis of Cubebol from (−)-Carvone by Introducing the Electrochemical Acetoxylation Reaction
Authors: Torii Sigeru , Okamoto Tsutomu
Published: July 2006

The synthesis of cubebol and the related compounds from (−)-carvone is described. In the preparation of the key intermediate, 7,10-trans-2,6-epi-2-acetoxy-7-isopropyl-10-methyltricyclo[4.4.0.01,5]decan-4-one (10) the electrochemical acetoxylation reaction could be used as an effective method for introducing the acetoxy group at C-2 carbon atom instead of the carboxy function of 7,10-trans-2,6-epi-4-oxo-7-isopropenyl-10-methyltricyclo-[4.4.0.01,5]decan-2-carboxylic acid (6a). The condensation of (+)-p-menth-8-en-2-one (2a) prepared from (−)-carvone with dimethyl succinate afforded Stobbe half-ester 3, which provided the diazoketone 4 smoothly. Thermal decomposition of 4 in benzene gave intramolecular adducts 5a and 5b (4 : 1). Hydrolysis of 5a afforded 6a in ca. 40% yield. Electrolysis of 6a in AcOH-t-BuOH-Et3N (2 : 1 : 0.1) using platinum electrodes gave 10 in 72% yield. Elimination of acetic acid gave two isomers 11a and 11b (3 : 1) in 87% yield and subsequent methylation of 11a afforded 7-isopropyl-4,10-dimethyltricyclo[4.4.0.01,5]deca-2-en-4-ol (12) in 82% yield, which on hydrogenation gave the desired product 1a (36.5%) along with the epimer 1b (36.5%).
The Bromination and Mercuration of bis-Dimethylglyoxymato(alkyl)pyridinecobalt(III), Alkyl Cobaloxime
Authors: Shinozaki Hiraku , Ogawa Hiroki , Tada Masaru
Published: July 2006

The bromination and mercuration of cis-2-methoxycyclohexyl(pyridine)cobaloxime (I) gave trans-1-bromo-2-methoxycyclohexane (V) and trans-2-methoxycyclohexylmercury(II) chloride (VII), along with other byproducts derived from the cyclohexene formed by β-elimination. β-Elimination is an exclusive degradation path with trans-2-hydroxycyclohexyl(pyridine)cobaloxime(II). The reaction of cis and trans-4-t-butylcyclohexyl(pyridine)cobaloximes (III and IV) gave trans and cis-1-bromo-4-t-butylcyclohexanes (X and XI), and trans and cis-4-t-butylcyclohexylmercury(II) chloride, with an exculsive or preferential inversion at the reaction center. These results show that the SE2 reaction of alkyl cobaloxime takes a stereochemical course of inversion.
Chromatography of Inorganic Ions on TEAE-cellulose Layers in Hydrochloric Acid Media
Authors: Kuroda Rokuro , Takahashi Toshiaki , Oguma Koichi
Published: July 2006

The ion-exchange behavior of inorganic ions on TEAE-cellulose was investigated in hydrochloric acid media with and without methanol. Adsorbabilities are low relative to those on strongly basic ion-exchange resin, varying with acid concentration in line with gradual building-up of chlorocomplexes.
The Preparation and Properties of Some Triorgano(oxinato)antimony Hydroxides
Authors: Kawasaki Yoshikane
Published: July 2006

Some new triorgano(oxinato)antimony hydroxides, R3Sb(L)OH (R=CH3, C6H5 and p-CH3C6H4: L=Ox, 2-Me-Ox, and 5-Cl-Ox), have been prepared, and the UV, IR, and NMR spectra of these compounds have been measured. These compounds have a hexa-coordinate configuration around antimony. The effects of the hydroxyl group on the IR and NMR spectra are discussed.
The Photo-induced Diels-Alder Reaction of 2-Cycloocten-1-one and 2-Cyclohepten-1-one
Authors: Shinozaki Hiraku , Arai Susumu , Tada Masaru
Published: July 2006

trans-2-Cycloocten-1-one and trans-2-cyclohepten-1-one, which are supposed to be formed by the ultra-violet irradiation of cis-2-cycloocten-1-one and cis-2-cyclohepten-1-one, give Diels-Alder addition products with cyclopentadiene and isoprene.
Tri(hetero)substituted Carbonium Ions. XI. A Novel Synthetic Route to 2-Dialkylamino-4-alkyl-1,3-dithiolium Salts
Authors: Nakai Takeshi , Hiratani Kazuhisa , Okawara Makoto
Published: July 2006

Pyrolysis of 2-dialkylamino-4-(α-bromoalkyl)-1,3-dithiolanylium bromides (2) readily prepared by bromination of the β,γ-unsaturated dithiocarbamates (1) affords 2-dialkylamino-4-alkyl-1,3-dithiolium salts (3) in good yields, providing a useful way to prepare dithiolium salts.
The Syntheses of 4- and 5-(α- and β-Naphthyl)tropolones
Authors: Tsunetsugu Josuke , Sato Masaru , Ebine Seiji
Published: July 2006

4- And 5-(α- and β-naphthyl)tropolones have been synthesized via naphthyl-tropilidenes, -tropones, and -aminotropones.
The Acid-Catalyzed Rearrangement of 1-Allylindoles. A Hypothesis for the Biogenesis of Echinulin-Type Compounds
Authors: Inada Seisaku , Nagai Kunio , Takayanagi Yasuo , Okazaki Mitsuo
Published: July 2006

The aluminum chloride-catalyzed rearrangement of 1-allyl- (1a) and 1-(trans-2-butenyl)indole (1b) produced 3-allyl-(3a) and 3-(1-methylallyl)indole (3b) in 58 and 43% yields, respectively. Based on this, a hypothesis for the biogenetic mechanism of echinulin is proposed.
Substituted Tetrahydropyridine and Dihydropyridobenzoxazine Ring Syntheses
Authors: Sakurai Akio , Midorikawa Hiroshi
Published: July 2006

The ternary condensation of ethyl acetoacetate, 3-methoxysalicylaldehyde, and substituted benzaldehydes in the presence of ammonium acetate gave 1,2,5,6-tetrahydropyridine (1) and 6H-8,9-dihidropyrido[1,2-c][1,3]-benzoxazine (2) derivatives.
A Zwitterionic Alkaloid from Daphniphyllum Teijsmanni Zollinger
Authors: Yamamura Shosuke , Toda Masaaki , Hirata Yoshimasa
Published: July 2006

A zwitterionic alkaloid, the hydration product of daphnilactone-B, has been isolated from the fruits of the plant Daphniphyllum teijsmanni Zollinger, and its structure also been determined on the basis of its spectral and chemical properties.
The Initiation Reaction of Electro-initiated Polymerization of Acrylamide in the Kolbe Electrolysis System
Authors: Ogumi Zempachi , Tari Isao , Takehara Zenichiro , Yoshizawa Shiro
Published: July 2006

The mechanism of electro-initiated polymerization of acrylamide in the Kolbe electrolysis system was investigated in detail and the reaction path of the intermediate radicals was clarified by product analysis and a measurement of the consumption rate of the monomer. The Kolbe intermediate radical, CF3·, reacts first preferentially with the monomer. Next, the radical thus formed reacts with other species to produce CF3CH2CH2CONH2, CF3CH2CH(CF3COO)CONH2 and CF3CH2CH(CONH2)CH(CF3CH2)CONH2. The first reaction is fast, but the reaction of CF3COO· with the monomer appears to be unreasonable. These reactions proceed on the electrode surface and in the layers below the diffusion layer, i.e., in layers of the same order as the depth of unevenness on the platinized platinum electrode.
X-Ray Photoelectron Spectroscopic Studies of Catalysts—Chromia–Alumina Catalysts—
Authors: Okamoto Yasuaki , Fujii Masaki , Imanaka Toshinobu , Teranishi Shiichiro
Published: July 2006

The XPS studies of chromia–alumina catalysts were carried out to elucidate the surface of these catalysts. Photoreduction was found to occur during the XPS measurements. Therefore, all spectra were measured rapidly to prevent any photoreduction. It was found that the information about the spin-orbit splitting of the Cr2P level is very useful for determining the valence state of chromium. The surface state of chromium in chromia–alumina catalysts calcined at 500 °C for 5 h is predominantly Cr6+ at low chromia concentration catalysts. However, the Cr3+ phase appears in catalysts of higher chromium content, and the surface concentration of Cr3+ increases with increasing content of supported chromia. The XPS spectra due to Cr5+ were observed after mild reduction of the catalysts. Moreover, it was found that almost all surface chromium is present as Cr5+ at low chromia content catalysts after mild reductions. Qualitatively, the results obtained by the XPS technique, which gives information about the surface of catalysts, agree well with the results obtained by ESR and other techniques, which gives information about the bulk of catalysts, especially low chromium concentration catalysts. These findings indicate a high dispersion of chromium on γ-Al2O3 for low chromium content catalysts.
Concentration Depolarization of the Fluorescence and Phosphorescence of Acridine Orange Cations
Authors: Komiyama Tomoko , Mori Yuji
Published: July 2006

Concentration depolarization of fluorescence and phosphorescence has been studied for Acridine Orange cations in PVA films. Depolarization can be observed with concentrations above 10−6 M. For concentrations ranging from 10−6 M to 10−4 M both depolarization of fluorescence and of phosphorescence obey the Weber equation. The results indicate that singlet-singlet energy transfer is responsible for depolarization of fluorescence, as well as of phosphorescence. Above 10−4 M, the effect of the exchange interaction cannot be ignored due to the formation of higher aggregates.
Activity Coefficients of Hydrochloric Acid in Hydrogen Chloride-Metal Perchlorate-Water Systems
Authors: Teruya Kiichi , Shiraogawa Kikuo , Nakamori Issei
Published: July 2006

In the HCl–LiClO4–H2O, HCl–NaClO4–H2O, HCl–Mg(ClO4)2–H2O, HCl–Ba(ClO4)2–H2O, HCl–LiClO4–NaClO4–H2O, HCl–NaClO4–Ba(ClO4)2–H2O, and HCl–LiClO4–NaClO4–Ba(ClO4)2–H2O systems, the mean activity coefficients of hydrochloric acid, γ±HCl have been obtained at 25 °C by emf measuremts of the cell:

H2(Pt)⁄HCl,MClO4,M′(ClO4)2,···⁄AgCl,Ag(M=Li,Na;M′=Mg,Ba)

Moreover, the following relation has been examined with the experimental results:

logγ±HCl=logγ°±HCl+\underseti∑ai(HCl)mi (i\eweqH,Cl)

where γ°±HCl is the mean activity coefficient of hydrochloric acid in a solution containing only hydrochloric acid at the same ionic strength as the mixture; mi is the molality of the i ion, and ai(HCl) is the parameter assigned to the three-ion system of hydrogen, chloride, and i ions, but is independent of the ionic strength. The results of the examination with aM(HCl) determined in our previous paper showed that aClO4(HCl) may be about zero regardless of the kind of metal ion coexisting in the solution. The activity coefficients calculated by the above relationship with the determined parameters agree, with deviation of only about 5%, with the experimental results for all the systems.