bluuebunny/crossref_metadata_2025 huggingface dataset:
Polar Substituent Constants for Substituted Phenyl Groups. The Extended Taft Equation.
Authors: Nagai Yoichiro , Matsumoto Hideyuki , Nakano Taichi , Watanabe Hamao
Published: July 2006

Values of the σ* constants have been defined for some m- and p-substituted phenyl groups from the 29Si–H coupling constants for a series of m- and p-substituted phenylsilanes, phenylmethylsilanes, and phenyldimethylsilanes. The σ* constants for the groups, XC6H4, were found to be directly related to the Hammett σ constants for the ring substituents, X. From this correlation the σ* constants for a number of other substituted phenyl groups have also been calculated. Examples have been presented in which a simple relationship holds between the Taft polar substituent constants including the newly derived σ* constants and molecular properties for a series of compounds covering both aliphatic and aromatic substances. Correlations of reactivities with the extended σ* values have been illustrated and the implications of the results are discussed.
Inositol Derivatives. IV. Synthesis of Anhydro Derivatives of 1,2-O-Cyclohexylidene-inositol
Authors: Suami Tetsuo , Ogawa Seiichiro , Oki Shuichi , Ohashi Kumiko
Published: July 2006

A reaction of 1,2-O-cyclohexylidene-myo-inositol tosylates with sodium methoxide in an appropriate solvent gave nine anhydro derivatives (mono- 6 and di-epoxide 3). The structures of new compounds were determined by proton magnetic resonance (PMR) spectroscopy and the reaction sequences.
Total Syntheses of Carbohydrates, II. Dl-Erythrose and Dl-Threose
Authors: Sonogashira Kenkichi , Nakagawa Masazumi
Published: July 2006

Propargyl alcohol was converted into 4-acetoxy-cis-crotonaldehyde diethyl acetal (III) via three steps, cis-Hydroxylation of III with potassium permanganate followed by acetylation yielded tri-O-acetyl-Dl-erythrose diethyl acetal (IV). Hydrolysis of IV afforded syrupy Dl-erythrose (VI) which could be converted into erythritol (VII) and its dibenzylidene derivative. An acid hydrolysis of III gave 4-acetoxy-crotonaldehyde (VIII) which was converted into triacetyl-Dl-threose diethyl acetal (XI) or Dl-threose pentaacetate (XII). Hydrolysis of XI and XII gave syrupy Dl-threose which could be identified as di-benzylidenethreitol.
Kinetic Studies of Intermolecular Hydrogen Bonding in Carboxylic Acids by Means of Ultrasonic Absorption Measurement. II. Halogeno Carboxylic Acids
Authors: Sano Takayuki , Tatsumoto Nobuhide , Mende Yukio , Yasunaga Tatsuya
Published: July 2006

The ultrasonic absorptions in several halogeno carboxylic acids, such as monochloroacetic, dichloroacetic, trichloroacetic, trifluoroacetic, α-chloropropionic, and β-chloropropionic acids, have been measured in the frequency range from 2.5 to 95 MHz. Excess absorptions were observed in all the acids. The kinetic and the thermodynamic parameters based on the equilibrium between the open dimer and the cyclic dimer were calculated. An application of Taft’s equation, logK=ρ*σ*+sEs, to the results suggests that neither the equilibrium constant nor the rate constant depends on the polarity effect of the alkyl group, but depends mainly on the steric effect, and that the reaction is controlled not only by the enthalpy change, but also by the entropy change.
Syntheses of Benzo[5,6]cyclohept[1,2-b]indol-6-ones
Authors: Yamane Kameji , Fujimori Kunihide
Published: July 2006

The monoarylhydrazones(IIa—c) of benzocycloheptene-5,6-dione (I) underwent Fischer indolization to form 11,12-dihydrobenzo[5,6]cyclohept[1,2-b]indol-6-ones (IIIa—c). The treatment of IIIa—c with N-bromosuc-cinimide gave the benzoindolotropone derivatives (Va—c). Va, Vc, and VI afforded a dibromo compound (VII) on treatment with bromine in acetic acid.
The Powder ESR Spectra of Some Bis(amino acidato)copper(II) Complexes
Authors: Misumi Seizo , Isobe Toshiyuki , Kimoto Shinkichi
Published: July 2006

Copper(II) complexes with some natural amino acids were prepared, and their powder ESR spectra were measured. The pattern types of the ESR spectra of these Cu(II) complexes with amino acids were classified into four types, and by the pattern type, the cis- or trans-isomer was estimated.
Thermal Decomposition of Ammonium Salts of Transition Metal Oxyacids. I. Thermogravimetric Analysis of Ammonium Paramolybdate
Authors: Park Il-Hyun
Published: July 2006

The decomposition of ammonium paramolybdate (APM) has been investigated by using a quartz spring balance in various ambient pressures. APM is decomposed in four or five stages, including a dehydration procedure, depending on the ambient pressures. However, these results do not agree with those of previous reports. This discrepancy may be attributed to the use of a sensitive quartz spring balance, a small amount of a sample, the application of a slow heating rate, or the utilization of DTG curves in the present study. The control of the ambient pressure was effective in investigating the thermogravimetric change in detail, especially in confirming the dehydration reaction. It is also concluded clearly that, in the course of the decomposition process, there is a final decomposition stage which has never been reported. The kinetics of the thermal decomposition was studied. The activation energies of the decomposition of APM under 760 Torr are 38.6, 194.8, 81.9, and 151.2 kcal·mol−1 respectively for the first to the fourth stages.
Reaction of Vinylic Radicals with Oxygen
Authors: Wada Naoto , Tokumaru Katsumi
Published: July 2006

Thermal decomposition of trans-α-phenylcinnamoyl peroxide and t-butyl trans- and cis-α-phenylperoxycinnamates and photolyses of 1,1 -diphenyl-2-iodoethylene and 1,1,2-triphenyl-2-iodoethylene were carried out in benzene under oxygen and their products were determined. The intermediate vinylic radicals, on reaction with oxygen, undergo oxidative cleavage and dioxygenation of their unsaturated bonds. As an example, 1,2-diphenylvinyl radicals give benzaldehyde together with benzoin.
Benzo- and Naphtho-derivatives of Triptycene: Synthesis and Properties
Authors: Sugihashi Makoto , Kawagita Ryosuke , Otsubo Tetsuo , Sakata Yoshiteru , Misumi Soichi
Published: July 2006

Several benzo- and/or naphtho-derivatives of triptycene were prepared in a manner of addition reaction of dehydronaphthalene (XIII) or a new type of aryne, dehydroanthraquinone (XVI) generated from 3-aminoanthraquinone-2-carboxylic acid (XV), with a few acenes. The absorption bands in longer wavelength region of their UV spectra and the chemical shift of bridgehead protons in their NMR spectra led to a conclusion that the spectra of those annelated triptycenes are elucidated in terms of a superposition and a sum of magnetic effects of separated component chromophores, respectively, and thereby indicate a negligible existence of the across-space π-electron interactions, if any, among three aromatic nuclei.
Improved Solid-Phase Synthesis of Tryptophan-Containing Peptides. I. Use of Hydrogen Chloride in Formic Acid as a Reagent for the Cleavage of t-Butyloxycarbonyl Group
Authors: Ohno Motonori , Tsukamoto Sadaji , Makisumi Satoru , Izumiya Nobuo
Published: July 2006

An improved method has been described for the solid-phase synthesis of tryptophan-containing peptides. Hydrogen chloride in formic acid has been introduced as a reagent for the cleavage of the t-butyloxycarbonyl group owing to the stableness of tryptophan and Ni-formyltryptophan in this system. The effectiveness of the new reagent has been demonstrated in the synthesis of the tryptophan-containing heptapeptide, lysylalanylglycyl-leucylglycyltryptophylleucine.
Study on Reverse Osmosis. The Permeation Behavior of Amino Acid Solutions through Cellulose Acetate Membranes
Authors: Kamizawa Chiyoshi , Masuda Hitoshi , Ishizaka Seiichi
Published: July 2006

Transport phenomena of some aliphatic amino acids and aminobenzoic acids were investigated with Loeb type membranes annealed at 60–80°C.

The quantitative relation between permeability through the membrane and dissociation of amino acid was examined. The charged species are rich in the solutions of amino acids such as l-leucine, l-alanine, and l-glutamic acid, regardless of the pH of solution, thus making the rejection by membranes large; the rejection of l-leucine which had a rejection of 35% for NaCl, was 63.2% even for the membrane cured at 60°C. On the other hand, for aminobenzoic acids, the number of uncharged species in solution varied with the change in pH, and the rejection varied with pH. The fluxes of aminobenzoic acids were in linear relation to the calculated amount of uncharged species. The results of adsorption experiments indicate that the amounts of adsorbed aminobenzoic acid to cellulose acetate were in logarithmic relation to calculated amounts of undissociated species. The results support the view that dissociated species are more difficult to be distributed in membrane than undissociated ones.
Kinetics and Stoichiometry of Nitrogen Fixation with TiCl3-Mg and VCL3-Mg in Tetrahydrofuran
Authors: Yamamoto Akio , Go Shigeo , Ookawa Masaharu , Takahashi Mitsuaki , Ikeda Sakuji , Keii Tominaga
Published: July 2006

The kinetics and stoichiometry of nitrogen fixation with TiCl3-Mg and VCl3-Mg in tetrahydrofuran (THF) systems were studied. The systems react with molecular nitrogen at room temperature and normal pressure giving magnesium dichloride and nitrogen-containing complexes of compositions [MNMg2Cl2(THF)], where M=Ti and V, according to the stoichiometry: MCl3(THF)3+\frac52Mg+\frac12N2→[MNMg2Cl2(THF)]+\frac12MgCl2(THF)2. Properties of the isolated nitrogen-containing complexes were examined. Reactions under argon and hydrogen gave hydride-containing complexes. The initial rate of nitrogen fixation was first order with respect to the amounts of MCL3, Mg, and nitrogen pressure. A mechanism involving the complexation of N2 with dimeric M(II) species followed by rate-determining process to react with magnesium is proposed and discussed.
Solvent Shifts of Methyl Proton Resonances of Pinanols and Related Compounds
Authors: Hirata Toshifumi
Published: July 2006

The chemical shifts of methyl protons of a number of bicyclo[3.1.1]heptanols and their acetates were measured on carbon tetrachloride and benzene in order to examine the correlation between the benzene-induced shifts and the spatial arrangements of the functional groups concerned. Thus, the shifts induced by benzene were found to be useful in establishing both the location and the stereochemistry of methyl protons situated in the vicinity of the hydroxyl or the acetoxyl function in a pinane skeleton.
The Reaction of Troponoid with Ylide. III. The Reaction of Tropone with Pyridinium Compounds
Authors: Sugimura Yukio , Soma Nobuo , Kishida Yukichi
Published: July 2006

Phenacylpyridinium ylide (2) reacted with tropone (1) to afford 2-hydroxy-2-phenyl-3-phenacyl-2H-cyclohepta[b]furan (3) which was converted into 2-(1′,2′-dibenzoylethyl)tropone (4). The reactions of tropone with several kinds of pyridinium bromides (7) yielded 2-substituted tropones in the presence of amine, and 1-azaazulene derivatives (9, 10, 11) in a one-step formation in the presence of ammonium acetate.
The Michael Reactions of Substituted 9,9′-Bifluorenylidenes with 2-Iodo-and 2,7-Diiodofluorene, and Some Other Reactions of Iodofluorenes
Authors: Minabe Masahiro , Suzuki Kazuo
Published: July 2006

The Michael-addition reaction between 2-iodofluorene and 9,9′-bifluorenylidene gave exclusively the normal addition product. The same reaction of fluorene with 2,2′-diiodo-9,9′-bifluorenylidene, of 2,7-diiodofluorene with 9,9′-bifluorenylidene, and of fluorene with 2,7,2′,7′-tetraiodo-9,9′-bifluorenylidene afforded not only the normal adducts, but also some abnormal compounds. Some new iodo-substituted fluorenes, -9,9′-bifluorenylidenes, -9,9-bifluorenyls, and -1,4-bis(2,2′-biphenylylene)-1,3-butadienes, were synthesized. The hydrogenolyses of 2- or 2,7-di-iodofluorene with lithium aluminum hydride, Raney nickel, and hydriodic acid were performed relatively smoothly to give fluorene. The Grignard and the Ullmann reactions of 2- or 2,7-diiodofluorene gave the usual, expected compounds, accompanied by some unusual products. The cyano-substituted fluorenes were prepared by the reaction of 2- or 2,7-diiodofluorene with potassium cyanide–cupric cyanide in N,N-dimethylformamide.
Adsorption of Polyethyleneglycol at the Mercury/Solution Interface
Authors: Yoshida Tadashi , Ohsaka Tetsuya , Suzuki Masayuki
Published: July 2006

The adsorption of polyethyleneglycol (PEG) was investigated at the mercury/solution interface by the observation of the differential capacity and the inhibitive action on the deposition of cadmium or copper. From the differential capacity measurements, the adsorption of PEG was found to be controlled by the diffusion of the adsorbate to the dropping mercury electrode under the present experimental conditions. The relation between the time required to attain the saturated adsorption and the bulk concentration (a) was explained approximately by the Koryta equation, though its deviation from the Koryta equation was somewhat larger than that for polyvinylpyrrolidone. When the maximum surface concentration and the mean molecular weight of PEG were expressed by Γm and \barM respectively, the plot of logΓm-log\barM revealed two linear parts crossing each other at \barM=ca. 600. The slope for \barM≥600 was ca. −1, which implied the relation of “\barM·Γm=const.”, i.e., the segment numbers of PEG molecules adsorbed per unit area were constant, independently of \barM, in the region of \barM≥600. The configuration of PEG of \barM<600 at the interface was considered to be different from that of PEG of \barM≥600 because the slope for \barM<600 was different from that for \barM≥600. From the polarographic current measurements i.e., the inhibitive effect on the reduction of Cd2+ or Cu2+), the time (tmi) needed to achieve the maximum inhibition was obtained; it was then compared with that obtained from the capacity data. The relation of “loga=(−1⁄2)logtmi+const.” based on the Koryta equation was approximately applicable to the cases with a relatively large \barM value.
Monolayers of Copolymers of Methyl Acrylate and n-Butyl Acrylate and Mixed Monolayers of Thier Homopolymers
Authors: Hironaka Seiichiro , Kubota Takashi , Meguro Kenjiro
Published: July 2006

Poly(methyl acrylate), poly(n-butyl acrylate), and their copolymers were prepared by radical polymerization. The monolayers of these polymers and the mixed polymers were studied at the air/water interface. The limiting areas obtained experimentally for various copolymers corresponded well to the theoretical values as calculated from the areas per methyl acrylate and butyl acrylate residues. However, those obtained for their corresponding polymer mixtures were larger than the theoretical limting areas.
Comparison of the Electronic Spectra of Geometric Isomers. II. 1,2-Disubstituted Ethylenes
Authors: Fueno Takayuki , Yamaguchi Kizashi
Published: July 2006

The ultraviolet absorption spectra of the cis and trans isomers of various 1,2-disubstituted ethylenes were measured in isopentane solution. Each isomer showed a single intense band assignable to the lowest π–π* transition. For the majority of the compounds studied, both energy and oscillator strength of transition are found to be greater for trans isomers than for the corresponding cis isomers, in accord with the general trend predicted by the Pariser-Parr-Pople calculations. Existence of some anomalous cases which contradict the generalization indicates a limited validity of the usual assumption of virtual orbitals.
The Mechanism of Decomposition of Hydrogen Peroxide by Iodine in Acid Solutions. The Rates of Associated Reactions
Authors: Matsuzaki Isao , Simic Radmilo , Liebhafsky Herman A
Published: July 2006

For the purpose of isolating elementary reactions responsible for the decomposition of hydrogen peroxide by iodine and its compounds, the reaction at 50°C of acid solutions containing I2, I−, HIO, etc. with [I−] and [I2] controlled by use of TlI(s) and I2(s) was studied. The rates of the evolution of oxygen, consumption of hydrogen peroxide and production of H+ were subjected to measurement and led to a formulation of a complex mechanism consisting of the following reactions: HIO2+H2O2→HIO+H2O+O2; H2OI++H2O2→HIO2+H++H2O; HIO+H2O2→H++I−+H2O+O2; HIO2+H++I−→2HIO; H2OI+\ightleftharpoonsHIO+H+; I−+H++H2O2→HIO+H2O; and I2+H2O\ightleftharpoonsHIO+H++I−. Absolute or relative rate constants for the first four reactions were evaluated by using equilibrium and rate constants of the others.
The Crystal Structure of the Polymerization Catalyst of Acetaldehyde and Its Derivatives. II. The Crystal and Molecular Structure of the Trimethylamine Oxide Adduct of Dimethylaluminum N-Phenylbenzimidate, [(CH3)2Al·O·C(C6H5):N(C6H5), ON(CH3)3]
Authors: Kai Yasushi , Yasuoka Noritake , Kasai Nobutami , Kakudo Masao
Published: July 2006

The molecular structure of a stereospecific (isotactic) polymerization catalyst of the acetaldehyde-Lewis base adduct [Me2Al·O·CPh:NPh,ONMe3] has been determined from three-dimensional X-ray data collected on a single crystal diffractometer. The crystal belongs to the triclinic system (space group P\bar1), with two formula units in a cell with dimensions of; a=8.517±0.004, b=10.096±0.005, c=12.256±0.005 Å, α=104.67±0.04, β=106.97±0.04, and γ=98.10±0.04°. The structure was solved by the symbolic addition method and refined by the block-diagonal, least-squares procedure. The molecule is monomeric, and both amide and ONMe3 groups are connected to the aluminum atom through oxygen atoms. The amide moiety has an imino-ether type structure and two adjacent benzene rings take trans configuration about the N–C bond. The co-ordinated ONMe3 group has a structure similar to that of the free molecule.
Topological Index and Thermodynamic Properties. I. Empirical Rules on the Boiling Point of Saturated Hydrocarbons
Authors: Hosoya Haruo , Kawasaki Keiko , Mizutani Kimiko
Published: July 2006

Empirical relations are proposed for the boiling point (bp) and the topological index (ZG) of a saturated hydrocarbon as

bp=alogZG+b

or bp=(alogZG+c)⁄\sqrtN+b,

where N is the number of the carbon atoms. A number of compounds with or without ring(s) are plotted for these relations. Correlation is generally better for cyclic compounds than for chain compounds. Sterically hindered paraffins deviate appreciably. Several empirical rules on the isomeric lowering of the boiling point of saturated hydrocarbons are presented and most of them are shown to be consistent with the above relations. Several empirical formulae for the boiling point of normal paraffins are compared and discussed.
On the Viscosities of Mixtures of Oligotrifluorochloroethylene and n-Heptadecane
Authors: Yoshida Naosato , Hamada Shuichi
Published: July 2006

The viscosities, ηm, of mixtures of oligotrifluorochloroethylene and n-heptadecane were expressed as follows: ηm=[(1−ΦR)−n(1−ΦR)]ηH+[ΦR+n(1−ΦR)]2⁄[ΦR⁄ηR+n(1−ΦR)ηH], where ΦR is the volume fraction of the oligotrifluorochloroethylene in the mixture; ηR and ηH, the viscosities of oligotrifluorochloroethylene and n-heptadecane respectively, and n, a parameter. The two components were considered to be comparatively well compatible with each other, because the parameter, n, was small (here about 0.1). The free-volume fractions, fT, of the mixed systems, as calculated from the WLF parameters, were larger than those calculated by assuming a simple additivity between those of the two components. This effect is considered to be caused by the mitigation of physical interactions among oligotrifluorochloroethylene molecules, which are dispersed by n-heptadecane as good compatibility is achieved between the two components.
Studies on Amino-hexoses. XVI. Synthesis of Deoxy-analogues of N-Acetyl-d-glucosamine
Authors: Arita Hitoshi , Fukukawa Kiyofumi , Matsushima Yoshio
Published: July 2006

For deoxy analogues of N-acetyl-d-glucosamine and three deoxy-analogues of phenyl N-acetyl-β-d-glucosaminide were synthesized by means of chlorination with sulfuryl chloride and reduction of the chlorides with tri-n-butyltin hydride. The free sugars thus obtained failed to crystallize except for 6-deoxy and 4,6-dideoxy compounds. Phenyl glycosides were mostly crystalline. The yield of chlorination and reduction was generally high.
Studies on Mixed Chelates. I. Mixed Copper(II) Chelates with N,N,N′,N′-Tetramethylenediamine and a Bidentate Ligand
Authors: Fukuda Yutaka , Sone Kozo
Published: July 2006

Six new mixed copper(II) chelates with N,N,N′,N′-tetramethylethylenediamine and a bidentate ligand, i.e., [Cu tmen en] (ClO4)2, [Cu tmen en] (NO3)2·H2O, [Cu tmen en](SO4)·4H2O, [Cu tmen gly](ClO4), [Cu-tmen ox] ·4H2O and [Cu tmen aca](ClO4) were prepared, and their visible absorption spectra were compared with those of the bis-chelate ions and molecules, [Cu en2]2+, [Cu gly2], [Cu ox2]2−, and [Cu aca2]. The results obtained indicate that steric factors play an important role in the formation and structure of these mixed chelates. The effects of various organic solvents on the electronic spectra of these chelates were also studied. (tmen=N,N,N′,N′-tetramethylethylenediamine, en=ethylenediamine, gly=glycinate ion, ox=oxalate ion, aca=acetylacetonate ion.)
The Structure of the Pteridine Glycoside from Aspergillus oryzae
Authors: Matsuura Sadao , Yamamoto Masaki , Kaneko Yasuyuki
Published: July 2006

The structures of two blue-fluorescent substances, asperopterfn-A and -B, isolated from Aspergillus oryzae were investigated. Asperopterin-B was identified as 2-amino-3,4,7,8-tetrahydro-6-hydroxymethyl-8-methyl-4,7-dioxopteridine (7) by studying its chemical degradation, pKα values, and UV spectra; the structure was confirmed by synthesis. Asperopterin-A was shown to be the β-d-ribofuranoside of 7, 2-amino-3,4,7,8-tetrahydro-8-methyl-4,7-dioxo-6-pteridinylmethyl β-d-ribofuranoside (10).
The Photochemical Decomposition of Benzotriazoles
Authors: Tsujimoto Kazuo , Ohashi Mamoru , Yonezawa Teijiro
Published: July 2006

The photochemical decomposition of several 1-substituted benzotriazoles was investigated. It was observed that in contrast to the thermolytic decompositions of 1-benzyl and 1-benzoylbenzotriazole, the intermediates produced by the loss of nitrogen from these compounds upon irradiation react with hydrogen-donating solvents to yield either reduced or substituted products. The possibility of the presence of an antiaromatic benzoazacyclopropene as an intermediate can be excluded on the basis of the fact that the photolysis of 4′,5-dichloro-l-phenylbenzotriazole gave 3,6-dichlorocarbazole as the sole product. The acetone-sensitized photolysis of 1-benzoylbenzotriazole causes a Wolff rearrangement giving a cyclopentadiene derivative. On the basis of extended Hückel molecular orbital calculations on the intermediates, it is concluded that the photochemical loss of nitrogen from benzotriazoles gives excited-state 1,3-diradicals, while the thermolytic decompositions afford ground-state ones.
Gas-Phase Charge-Transfer Complexation of Carbonyl Cyanide as Acceptor
Authors: Fueno Takayuki , Yonezawa Yoshiro
Published: July 2006

Charge-transfer complexations of carbonyl cyanide with furan, tetrahydrofuran, diethyl ether, and their sulfur homologs have been investigated in gaseous phase at temperatures 22–82°C. Thermodynamic data showed that the complexations are enthalpy-controlled in the temperature range studied and that the complexes formed from n-donors are fairly strongly bound. Both the transition and bonding energies could be interpreted in terms of the usual two-state resonance model. It has been deduced that the spatial arrangements of the components do not greatly differ for the various donors studied, despite the difference in precise nature of the bondings involved.
Butadiene Formation from Ethanol over Silica-Magnesia Catalysts
Authors: Niiyama Hiroo , Morii Saburo , Echigoya Etsuro
Published: July 2006

Butadiene formation reaction from ethanol over various kinds of silica-magnesia having different MgO contents were studied from the standpoint of its acid-base catalysis. Maximum acidity was obtained at 50% MgO, while basicity increased with the MgO content. Silica-magnesia (85% MgO) having adequate acidity and basicity gave the maximum activity. The reaction mechanism and the roles of acidic and basic sites are discussed. The rate controlling step is the acetaldehyde formation catalyzed by basic sites.
Polarographic Studies on Substituted 2,2′-Bipyridyl N-Oxides
Authors: Katiyar S S , Lalithambika M , Shukla R P
Published: July 2006

The polarographic behavior of 4-methoxy-2,2′-bipyridyl 1-oxide has been investigated in 20% dioxane-water solution. Two well defined reduction waves appear in the pH range 0.76–8.8, a third wave in pH 9.3–10.4, but only one wave in more alkaline solutions. The variation of E1⁄2 with pH followed the relations (E1⁄2)1=−0.37–0.10 pH and (E1⁄2)2=0.84−0.065 pH for waves 1 and 2, respectively. The diffusion current constant for the second wave decrease with increasing pH whereas for the first wave it remains constant upto pH 7.0 and decreases afterwards. Variation of diffusion current with temperature and reservoir height indicates the diffusion controlled nature. Wave 1 is produced by the 2 electron reduction of protonated N-oxide to 4-methoxy-2, 2′-bipyridyl. This intermediate is further reduced, at more negative potentials, to 1,4′-dihydro-4-methoxy-2,2′-bipyridyl by consuming two more electrons and two hydrogen ions simultaneously. The third wave is presumably due to catalytic hydrogen evolution.
The Electric Conductivity of the H2O-B2O3 Melt
Authors: Kodama Hiroshi , Yokokawa Toshio , Niwa Kichizo
Published: July 2006

Electric conductivity was measured over the whole composition range of H2O–B2O3 in the liquid state. A peculiar conductivity-temperature relation was observed in a low B2O3-to-intermediate composition. The equivalent conductance of H3BO3 increases with its content in this range. Both the concentration of proton and its mobility through the proton-jump mechanism seem to change with the composition. The comparison of the results in the B2O3-rich range with those of alkali borates indicates a low extent of the dissociation of the –B–O–H group.
Chemical Studies of Minerals Containing Rarer Elements from the Far East District. LXV. Pollucite from Nagatare, Fukuoka Prefecture, Japan
Authors: Sakurai Kin-ichi , Kato Akira , Kuwano Noriyuki , Nagashima Kozo
Published: July 2006

The chemical analysis of pollucite found in a granite pegmatite at Nagatare, Fukuoka Prefecture, gave SiO2 46.03, Al2O3 17.76, Fe2O3 0.02, MnO 0.01, CaO 0.03, Li2O 0.16, Na2O 2.08, K2O 1.81, Rb2O 0.61, Cs2O 28.88, and H2O 2.74; total 100.13%; recalculated as (Cs,Rb)0.573(Na,K,Li,Mn,Ca)0.316(Al,Fe)0.943Si2.071O6·0.411 H2O as O=6, thus satisfying the crystallochemical formula advocated by Beger. X-ray single crystal and powder studies have shown it to be cubic, the space group is Ia3d; a0=13.674±0.005 Å. It is optically isotropic or very faintly birefringent, with n=1.520±0.002.
The Photochemical Reaction of α-Diketones
Authors: Maruyama Kazuhiro , Ono Keiichi , Osugi Jiro
Published: July 2006

The relative photochemical reactivity of α-diketones, in particular, 9,10-phenanthraquinone, 1,2-naphthoquinone, acenaphthoquinone, benzil, 4,4′-dimethylbenzil, 2,4,6-trimethylbenzil, 2,5,2′,5′-tetramethylbenzil, 2,3,5,6-tetramethylbenzil, 2,4,6,2′,4′,6′-hexamethylbenzil, phenylglyoxal, 2,5-dimethylphenylglyoxal, and 2,4,6-trimethylphenylglyoxal was investigated in hydrogen donating solvents. Type of the product and relative reactivity differ widely according to the structure of α-dike tones. Whereas 9,10-phenanthraquinone gives 1,4-adduct (V) in a hydrogen donating solvent (THF), 2,5,2′,5′-tetramethylbenzil gives 2-hydroxy-2-(2′,5′-dimethylphenyl)indanone (VII) via intramolecular hydrogen abstraction in nearly quantitative yield. No photochemical reaction of 2,4,6-trimethylbenzil or 2,3,5,6-tetramethylbenzil could be observed in the same solvent even under a long irradiation.
The Photochemical Reduction of Nitrobenzene and Its Reduction Intermediates. XI. The Photochemical Reduction of Azobenzene in Isopropyl Alcohol
Authors: Hashimoto Shizunobu , Kano Koji
Published: July 2006

The photochemical reduction of azobenzene in isopropyl alcohol has been investigated. The n-π* transition of azobenzene caused only the cis-trans photoisomerization, while the n-π* transition caused both photoisomerization and photoreduction. The reduction product was hydrazobenzene. The photoreduction was accelerated by a small amount of oxygen and was quenched by 1,3-pentadiene. The photoreduction was sensitized by fluorene and the aromatic carbonyl compounds (benzophenone, benzaldehyde, and acetophenone). These results suggest that the π,π* excited triplet state (T2) of azobenzene abstracts a hydrogen atom.
Viscous Properties of Liquid Oligotrifluorochloroethylene
Authors: Yoshida Naosato , Hamada Shuichi
Published: July 2006

The viscosities of fractionated liquid oligotrifluorochloroethylene were measured in the molecular-weight range from 820 to 2100 at temperatures ranging from 40 to 120°C. While the relationships between logη and logMn were regarded as being approximately linear in the molecular-weight range smaller than 1090, and their slopes were much larger than unity, a considerable deviation from the approximately linear relationship was observed in the molecular-weight range larger than 1090. The temperature dependence of the viscosities was well explained in terms of the WLF equation under the present experimental conditions. The large slope in the range of the linear relationship may be caused because the reciprocals of the free-volume fractions, 1/f, increase remarkably with an increase in the molecular-weight. The free-volume per cubic centimeter, F, contributed by chain-ends increased abruptly with an increase in the molecular-weight in the range smaller than about 1200.
Vibrational Analysis of Electronic Transition Bands of Coronene
Authors: Ohno Koichi , Kajiwara Takashi , Inokuchi Hiroo
Published: July 2006

The fluorescence and absorption spectra of coronene dissolved in organic solvents were measured at room temperature. Their vibrational structures were analyzed by reference to the Raman lines of crystalline coronene measured by means of a He-Ne gas laser, and the observed transition energies were compared with the calculated ones. It was suggested that the p-band of the absorption spectrum of coronene (23000–27000 cm−1) is composed of more than one electronic transition, in contrast with the case of benzene. The fluorescence and phosphorescence spectra of coronene in n-octane were also measured at 77°K, and their vibrational structures were successfully analyzed with some perturbing vibrations and a few totally-symmetric ones.
The Polarized Phosphorescence Spectra of Phenazine in a Phenanthrene Crystal
Authors: Ikegami Kasumi , Mikami Naohiko , Ito Mitsuo
Published: July 2006

The polarized phosphorescence spectra of phenazine in phenanthrene was observed at 4.2 K. From the assignments of vibrations that were made on the basis of the results of polarized Raman spectra measurements for the single crystal, it was concluded that the possible mechanisms for the appearance of the vibronically-induced part of the spectrum are the following:

(Remark: Graphics omitted.)

Furthermore, it has been found that the vibrational modes which give rise to the more intense in-plane polarized bands are out-of-plane ring modes. These results seem to support the regularity found by Lim et al.
Vibration-Rotation Interaction Constants, l-Type Doubling Constants and Cubic Force Constants of CH3I and CD3I
Authors: Matsuura Hiroatsu , Overend John
Published: July 2006

The harmonic parts of the vibration-rotation interaction constants and the l-type doubling constants were calculated for CH3I and CD3I from the harmonic force field. The harmonic parts were subtracted from the experimental values to obtain the anharmonic parts which give relations among the cubic normal-coordinate force constants. Some of the individual values for the cubic force constants associated with the bending modes were obtained by using the derived relations and the previously estimated values for the stretch-stretch-stretch cubic force constants of the methyl group.
Studies on Reactions of the N-Phosphonium Salts of Pyridines. I. A New Method for the Activation of Carboxylic Acids via the N-Phosphonium Salts by Means of the Oxidation of Tri- and Di-esters of Phosphorous Acid in the Presence of Tertiary Amines
Authors: Yamazaki Noboru , Higashi Fukuji
Published: July 2006

Carboxylic acids were found to be activated by an oxidation mixture prepared from tri- and di-esters of phosphorous acid and mercuric chloride in a pyridine solution; they yielded the corresponding anilides upon treatment with aniline, together with a nearly quantitative yield of metallic mercury. The yield of the anilides was affected by the alkyl groups in the esters and by the tertiary amines. Only a small effect of the steric factor of carboxylic acids upon the reaction was seen in the cases of the diesters, and none at all was observed in the triesters. The reaction was proposed to proceed via the N-phosphonium salts of pyridines, which were not purely isolated, but which were assumed on the basis of the IR spectra.
Adsorption and Inhibition Effect of Triton X at the Mercury/Solution Interface
Authors: Ohsaka Tetsuya , Yamamoto Hajime , Yoshida Tadashi
Published: July 2006

The time dependence of differential capacity and that of polarographic current were observed to elucidate the adsorption behavior of Triton X. The adsorption showed a relatively ideal system of the diffusion-controlled type in which semi-infinite linear diffusion was assumed. The results from the two different observations agreed approximately. The Koryta equation was applied to obtain the maximum surface concentration Γm of Triton X in the adsorption of the monolayer. logΓm decreased linearly with increasing log\barM (mean molecular weight), the slope being ca. −1. In the case of high bulk concentration, the adsorption showed unusual phenomena considered to be caused by the formation of a multi-layer which tended to become marked with the decrease of \barM. The inhibition effect of Triton X on reduction current revealed approximately the same tendency regardless of cations Cd2+ and Cu2+. Though the dependence of inhibitive action on \barM was relatively small, the degree of inhibition became somewhat small with increasing \barM in contrast to the cases of PVP and PEG. The shape of instantaneous i vs. t curve was approximately elucidated by Matsuda’s treatment of the system where the limiting current was depressed by diffusion-controlled adsorption. The i-t curve revealed that the degree of inhibition scarcely increases until attainment of a certain high coverage when a sharp increase takes place.
ESR Studies of the Negative Ions of Biphenyl Derivatives. IV. Conformation of 4,4′-Polymethylenebiphenyl Anion Radicals
Authors: Ishizu Kazuhiko , Nemoto Fujito , Hasegawa Hideo , Yamamoto Koji , Nakazaki Masao
Published: July 2006

The electron spin resonance has been observed for anion radicals of 4,4′-polymethylene bridged biphenyls which have various lengths of the polymethylene chain, from the carbon number of n=11 to that of n=16. The relation between the chain length of the methylene bridge and the ring-proton splitting were studied in order to see how the polymethylene span brings on a strain in the biphenyl ring. The geometrical structures of the sp3-hybrid bond of the β-carbons were investigated on the basis of the observed values of the β-proton splitting in each derivative. In the cases of both pentadeca and hexadeca derivatives, the magnitude of both the ortho- and the meta-ring proton splitting are comparable with those of the 4,4′-diethylbiphenyl anion radical, the open-chain model of the present derivatives. A rotation of the β-methylene sp3-bond is forbidden in this case, however, and the coupling constants of the β-methylene protons no longer exhibit an equivalent value; that is, two of these C–H bonds are placed on a coplanar biphenyl plane, but the others are twisted out by about 30° from the 2pz axis of the ring-carbon atom. When the number of the methylene groups is reduced from thirteen to twelve, the magnitude of the ortho-ring proton coupling constant is greatly reduced. The HMO calculations of the spin density were carried out. The observed tendency of the ring-proton splitting can be qualitatively understood on the assumption that the coplanar biphenyl ring may be modified by twisting the phenyl groups about the central 1-1′ bond rather than by slanting them together against the original aromatic plane. A strong beam of the polymethylene chain also causes a modification of the geometrical structure of the β-methylene sp3 bond and results in a reduction of the β-proton coupling constant to a large extent.
Transference of Water to the Nitrobenzene Phase for the Extraction of Tris(1,10-phenanthroline)iron (II) and Tris(2,2′-bipyridine)iron(II) Chelate Salts
Authors: Yamamoto Yuroku , Tarumoto Tsunehiko , Tarui Takao
Published: July 2006

The amount of water transferred to the nitrobenzene phase was determined for the extraction of ion pairs of tris(1,10-phenanthroline)iron(II) and tris(2,2′-bipyridine) iron(II) with halide and pseudohalide anions. For both chelate systems the smaller the anion, the greater the amount of water transported, very similar results being obtained for a common anion. The results were discussed in relation to water of crystallization, extractability and temperature effect.
Intramolecular Participation of Sulfide Linkage in the Reactivity of Carbene and Diazoalkanes. I. Alkylcarbenes and Diazoalkanes Bearing Alkylthio, Arylthio, and Allylthio Groups on a-Carbon
Authors: Ojima Iwao , Kondo Kiyosi
Published: July 2006

α-Alkyl- and α-arylthioalkylcarbenes were thermally or photochemically generated from the corresponding ketones according to a modification of the Bamford-Stevens method. The carbenes thus generated were found to form labile episulfonium ylides, which then rearranged to vinyl sulfides. The episulfonium ylides were trapped with diethyl maleate and dimethyl fumarate. An α-allylthioalkylcarbene was generated by the photolysis of α-allylthioacetophenone tosylhydrazone in the presence of sodium methoxide at −70°C; this afforded α-allylthiostyrene exclusively. A smooth thio-Claisen rearrangement of the resulting α-allylthiostyrene was also observed. 3-Thiabicyclo[3.1.0]hexane was obtained when α-allylthioacetophenone tosylhydrazone was decomposed thermally at 150°C, or photochemically at 10°C in the presence of bases. The mechanisms of these new reactions are also discussed.
A Kinetic Study of the Mutarotation of d-Xylose by the Polarographic Method
Authors: Ikeda Tokuji , Senda Mitsugi
Published: July 2006

The polarographic behavior of d-xylose in several buffer solutions was investigated. The rate constants, k1, k2, k−1, and k−2, of the mutarotation of α-d-xylose, assumed as α\oversetk1\undersetk−1\ightleftharpoonsγ\oversetk2\undersetk−2\ightleftharpoonsβ, were calculated by the use of Wiesner’s method, but with a modified equation for the polarographic current. The overall mutarotation rate constant, ko, which is denned by ko=(k1k−2+k−1k2)⁄(k−1+k−2), was also determined. The rate constants, ko, k1, and k2, were analyzed as a linear function of the buffer concentration. It was revealed that the catalytic effects of the buffer salts were mainly due to their basic components for all the buffer salts investigated. The Bronsted plots of k1 and k2 for all the basic components gave straight lines with the same slope of 0.42. The rate constants for several amines deviated from the slope; this deviation was ascribed to the steric hindrance caused by their large molecular sizes.
The Nucleophilic Photo-substitution Reaction of Anthraquinone Derivatives. I. The Photo-amination of Sodium 1-Amino-4-bromoanthraquinone-2-sulfonate
Authors: Inoue Haruo , Hida Mitsuhiko , Tuong Tran Dinh , Murata Takashi
Published: July 2006

The photo-amination reaction of sodium 1-amino-4-bromoanthraquinone-2-sulfonate (I) was studied. The experimental results may be summarized as follows: 1) The photo-reaction is evoked by the absorption of light corresponding to the first absorption band (490 nm) of (I); 2) no dark reaction is observed: 3) aromatic amines appeared not to photo-react with (I); 4) the larger the polarity of the solvents used, the greater the yield of the product; 5) in the absence of oxygen, the photo-reaction was stopped. The possible reaction schemes were discussed.
The Palladium-catalyzed Arylation of 4-Chromanone Enol Esters. A New Synthesis of Isoflavanones
Authors: Saito Ryu-ichi , Izumi Taeko , Kasahara Akira
Published: July 2006

Heck’s reaction of 4-chromanone enol esters with arylpalladium compounds in acetic acid afforded isoflavanones in a high yield. The structural elucidation of these products was accomplished by spectral inspections.
One-Electron Reduction of Carbonium Ions. III. The Effect of Added Anions on the Rate of Reduction of the Tropylium Ion with Cr(II)
Authors: Okamoto Kunio , Komatsu Koichi , Tsukada Susumu , Murai Osamu
Published: July 2006

The one-electron reduction of tropylium fluoroborate with Cr(II) was carried out in aqueous solution containing various anions (Cl−, Br−, SO42−, HSO4−, BF4− and ClO4−) which were added as proton acids or as sodium salts, and the reaction rate at 25°C was measured by the use of the flow method. It was found that Cl−, Br−, and SO42− exhibit the characteristic rate-accelerating effect, whereas BF4− and ClO4− show a slight rate-retarding effect. From the extrapolation of the anion concentration to zero, it was indicated that this reaction can proceed even in the absence of added anions. From these findings, together with the results of chemical and spectrophotometrical analyses of the Cr(III) species, it was concluded that the reduction of the tropylium ion with Cr(II) proceeds through an electron-transfer step where the anion (Cl−, Br−, or SO42−) or the water molecule acts as a weakly interacting electron-transfer bridge. This mechanism is essentially analogous to the “inner-sphere mechanism” known in the field of inorganic metal complex chemistry.
A Study on the Kinetics and Mechanism of the Oxidation of Carbon Monoxide over Zinc Oxide
Authors: Choi Jae Shi , Kim Bo Won
Published: July 2006

A kinetic study on the oxidation reaction of carbon monoxide has been carried out between 260 and 350°C by means of the static method using n-type ZnO semiconductor as a catalyst under various oxygen and carbon monoxide pressure. The order of reaction between 260 and 320°C was found to be 1.5, with dPCO2⁄dt=kPCO·PO21⁄2. The Roginsky-Zeldovitsch equation, dPCO2⁄dt=ke-ap, fits well at 350°C. The mechanism of the reaction can be explained by the n-type character of ZnO.
The Electron-scavenging Process in 3-Methylhexane Glass at 77 K Studied by ESR
Authors: Oka Koichi , Yamazaki Hideo , Shida Shoji
Published: July 2006

The effect of various additives, i.e., nitrous oxide, sulfur hexafluoride, methyl chloride, and sulfur dioxide, on the yield of the trapped electrons produced in the γ-irradiated 3-methylhexane (3MHX) glass at 77 K have been investigated by the ESR technique. The yields of the trapped electrons were reduced by the addition of all the solutes examined; the efficiency of electron scavenging was found to be in the order of SF6>CH3Cl>N2O>SO2. The concentration dependence of the electron scavengers showed that the efficiency of the electron scavenging in the glassy state had values intermediate between those in the gas and liquid phases. The high efficiency observed in the glassy state suggests that the non-solvated electrons before being trapped move about rapidly in the glassy matrix as the form of quasi-free electrons. The ESR-power saturation of the trapped electrons was considerably reduced by the addition of N2O; a possible mechanism of the relaxation of the ESR is proposed.
Metal Complexes Containing Six-membered Chelate Rings. III. Preparation and Structure of Mono- and Bis(2,4-Pentanediamine)cobalt(III) Complexes Containing Acetylacetonate or Oxalate Ion
Authors: Mizukami Fujio , Ito Haruko , Fujita Junnosuke , Saito Kazuo
Published: July 2006

New cobalt(III) complexes [Co(acac)2(2,4-ptn)]+, [Co(acac)(2,4-ptn)2]2+ and [Co(ox)(2,4-ptn)2]+ have been synthesized, resolved into optical isomers and their structures determined; 2,4-ptn=optically active (RR and SS) and meso (RS) 2,4-pentanediamine, acac=acetylacetonate ion, ox=oxalate ion. The patterns of circular dichroism spectra of these complexes in the first absorption band region are very similar to those of the corresponding α-diamine cobalt(III) complexes.
Heterocyclic Azomethine Compounds and Their Reduction Products as Analytical Reagents. I. Syntheses and Acid Dissociation Constants of Picolinaldehyde 2-Hydroxyanil and Its Derivatives and Their Reactions with Metal Ions
Authors: Otomo Makoto , Kodama Kazunobu
Published: July 2006

Picolinaldehyde 2-hydroxyanil and its methyl, chloro and nitro derivatives at the 5-position of benzene nucleus were synthesized for the purpose of investigating their applicability as an analytical reagent. The acid dissociation constants were determined by means of potentiometric titration in aqueous dioxane of various concentrations. It was found that the basicity of donor atoms of the parent compound increases with the introduction of a methyl group and decreases with that of a chloro or nitro group. The three compounds other than the nitro derivative are light-colored and react with many divalent metal ions in slightly basic media to form strongly colored chelates, which can be extracted into organic solvents such as partially halogenated hydrocarbons. The distribution coefficients of the three compounds between chloroform and water were also determined spectrophotometrically, that of the chloro derivative being the largest.
The Synthesis and The Configuration of 3-Aminotetrahydrothiophene-3-carboxylic Acids
Authors: Hatanaka Minoru , Ishimaru Toshiyasu
Published: July 2006

Several monomethylsubstituted 3-aminotetrahydrothiophene-3-carboxylic acids have been synthesized from the corresponding 3-ketotetrahydrothiophenes by the Strecker and the Bucherer-Bergs syntheses. In each case, the former synthesis leads to one stereoisomer, and the latter, to the opposite stereoisomer. The configurations of 3-amino-2-methyltetrahydrothiophene-3-carboxylic acids have been determined by a study of the NMR spectra; the others have been estimated on the basis of these results. The configurations do not contradict those first assigned to the alkyl substituted 1-amino-1-cyclohexanecarboxylic acids.
Kinetic Studies of Fast Reactions in Aqueous Solutions of Amylamine by Means of Ultrasonic Absorption
Authors: Nishikawa Sadakatsu , Yasunaga Tatsuya , Takahashi Kojiro
Published: July 2006

The ultrasonic absorptions in aqueous solutions of amylamine were measured in the frequency range of 3.5–220 MHz and in the concentration range of 0.01–3.06 M. Two kinds of relaxations were observed. One was attributed to the 5A–A5 reaction of non-ionized molecules of amylamine, and the rate constants were determined from the concentration dependence of the relaxation time at various temperatures. The thermodynamic parameters were determined from the temperature dependence of the rate and equilibrium constants. The other was attributed to hydrolysis, which is a diffusion-controlled reaction. In order to clarify the relation between the stability of the aggregate and the length of the hydrophobic group, the ultrasonic absorptions in aqueous solutions of propylamine were also measured. The excess absorption due to the association-dissociation reaction was not observed; only that due to hydrolysis was observed. It was deduced from this investigation that the aggregate formed by the hydrophobic bonding exists in the aqueous solutions of normal amines, the carbon numbers of which are more than 4.