bluuebunny/crossref_metadata_2025 huggingface dataset:
Nuclear Quadrupole Resonances of 2,4,6-Trichlorobenzonitrile
Authors: Negita Hisao , Shibata Kaoru , Kubo Tsuneo
Published: July 2006

2,4,6-Trichlorobenzonitrile was examined by means of the nuclear quadrupole resonances (NQR) resulting from 14N and 35Cl nuclei. One 14N resonance line (the higher line of the pair) and three 35Cl resonance lines were observed. The Zeeman effect on a single crystal was studied in an attempt to predict the lower 14N line. Thus, |e2Qq|=3936.7 kHz and η=0.1298 were calculated for the nitrogen atom; the frequency of the lower line was estimated at 2824.8 kHz. On the other hand, (η=0.130; |e2Qq|=71.209 MHz), (0.128; 72.594), and (0.116; 73.720) were determined for the chlorine atoms in the order of increasing frequencies by studying the Zeeman effect of 35Cl NQR on the single crystal.
Polarographic Studies of Bis(2,2′,2″-terpyridine) Complexes of Manganese(II), Cobalt(II), Nickel(II) and Europium(III) in Acetonitrile
Authors: Aihara Makoto , Kishita Hirofumi , Misumi Seizo
Published: July 2006

The reduction mechanism of bis 2,2′,2″-terpyridine complexes of manganese(II), cobalt(II), nickel(II) and europium (III) were investigated in acetonitrile by means of DC and AC polarograph and Kalousek polarograph at DME and cyclic voltammetry at an HDME. It was found that univalent metal complex anions, such as [M-(terpy)2]− (M=manganese and nickel), were formed at the electrode surface in acetonitrile. For the europium(III) complex, the standard rate constant of the second reduction step was estimated.
Isomerization of Heptanes over a Palladium–Zeolite Catalyst
Authors: Sakai Tomoya , Goto Masafumi , Hatano Kei-ichiro , Kato Manjiro
Published: July 2006

The isomerization of heptane isomers, heptane, 2- and 3-methylhexane, 3-ethylpentane, and 2,3- and 2,4-dimethylpentane, was investigated kinetically over a palladium-zeolite catalyst in the presence of hydrogen at 280–350 °C. First-order rate constants of 11 reaction paths were given with their activation energies and pre-exponential factors. The reaction scheme network including 22 isomerization steps among 9 isomers was constructed through the detailed analysis of primary and secondary reaction products from the individual isomers. Finally, the several proposed isomerization mechanisms were examined on the basis of the present experimental results.
Estimation of Structures and Electronic States of Radicals Using INDO-SCFMO Method. II. Alkylperoxyl Radicals
Authors: Ohkubo Katsutoshi , Kitagawa Futoshi
Published: July 2006

The energetically most stable CH3OO and CH3CH2OO radicals have been found to have the following geometric values: r(Oα–Oβ)=1.12 Å, r(Oα–C)=1.38 Å for the former and 1.39 Å for the latter, ∠COαOβ=112° for the former and 115° for the latter, and r(C–C)=1.47 Å for the latter.
Substitution Reaction of Ethylenediaminetetraacetatoaluminate(III) with Indium(III) in Aqueous Solutions
Authors: Tsuchimoto Michiko
Published: July 2006

The kinetics of substitution reaction between the aluminium(III) EDTA complex and the indium(III) ion has been studied in aqueous solutions of pH 2–10; the aluminium(III) complex is more labile than the gallium(III) and the indium(III) complex.
The Synthesis of 24-Norfriedel-4-en-3-one
Authors: Kakisawa Hiroshi , Horie Tsuneyuki , Kusumi Takenori
Published: July 2006

The lead tetraacetate oxidation of 24-hydroxyfriedel-3-ene, prepared from friedelin, afforded a 3-acetoxy-24-norfriedel-4-ene, which was then convered into the title compound.
On the Mechanism of the Diels-Alder Reaction between 1,3-Cyclopentadiene and 1,3-Cyclohexadiene
Authors: Maeda Terunobu , Hamanaka Sawako , Ogawa Masaya
Published: July 2006

The reaction of 1,3-cyclopentadiene with 1,3-cyclohexadiene, when carried out at 94–118 °C for 5–7 hr, gave tricyclo[4.4.0.12,5]undeca-3,7-diene rather than tricyclo[5.2.2.02,6]undeca-3,8-diene.
Molecular Vibrations and Force Fields of Alkyl Sulfides. X. Skeletal Bending Vibrations of Several Simple Aliphatic Sulfides
Authors: Ohsaku Masaru
Published: July 2006

The skeletal bending vibrations of several normal alkyl sulfides were analysed. It is found that a heterogeneous system as this case can also be explained in the same manner as a homogeneous system.
Preparation of Tetramethylphthalimide
Authors: Chiba Koji , Endo Eiji , Yamaka Kyoji
Published: July 2006

Treatment of tetramethylphthalic anhydride (I) with 28% aqueous ammonia at room temperature afforded ammonium tetramethylphthalimide (IV) and and 2-cyano-3,4,5,6-tetramethylbenzoate (V). The amount of IV increased by heating at 100 °C, tetramethylphthalimide (VI) being precipitated. A plausible reaction path is proposed.
Molecular Structure of 7-Oxanorbornane as Studied by Gas Electron Diffraction
Authors: Oyanagi Kazuko , Fukuyama Tsutomu , Kuchitsu Kozo , Bohn Robert K , Li Shu-tung
Published: July 2006

The structure of 7-oxabicyclo[2.2.1]heptane (7-oxanorbornane) in the gas phase has been investigated by making joint use of the electron diffraction intensities measured in the present study and the rotational constants reported by Creswell. The thermal average bond lengths are: rg(C1–C2)=1.533±0.014 Å, rg(C2–C3)=1.571±0.015 Å, rg(C–O)=1.442±0.010 Å, and rg(C–H)=1.117±0.008 Å. The bond angles in the zero-point average structure (rav) are: ∠C–O–C=94.5±2.2°, θ (the dihedral angle between the C1–C2–C3–C4 and C4–C5–C–6–C1 planes)=113.5±0.8° and ∠H–C–H=105±5°. The uncertainties represent the estimated limits of experimental error. The C2–C3 bond is longer than the C1–C2 bond, and the latter distance is nearly equal to that of a normal C–C single bond. The C–O bond is about 0.02 Å longer, and the C–O–C bond angle is about 17° smaller than the corresponding parameters in dimethyl ether. These trends are analogous to those observed for norbornane and 7-thianorbornane.
An MO-theoretical Approach to the Aquation Mechanism of Carboxylatopentaammineruthenium(III) Complexes in Acid Solutions
Authors: Ohkubo Kastutoshi , Kitagawa Futoshi , Sakamoto Hiroyuki , Ohyoshi Akira
Published: July 2006

The aquation mechanism of carboxylatopentaammineruthenium(III) complexes, (NH3)5RuO2CR2+, where R=H, CH3, C2H5, (CH3)2CH, and CH2OH, has been investigated with the Wolfsberg-Helmholz-LCAO-MO extended Hückel method augmented by metal d-orbitals. The very weak Ru–O coordination linkage (bond population=0.085–0.092) formed mainly by the antibonding dz2pz-σ and pzpz-σ orbitals facilitates the heterolytic bond-breaking of the Ru–O(dissociation energy=4.61–9.22 kcal/mol), and the order of the bond populations of the Ru–O is well reflected in that of the overall aquation rates.The preferable structure of the protonated complex is (NH3)5RuOHG(=O)R2+, produced by the interaction between the H+ catalyst and the non-bonding lonepair orbital of the neighboring oxygen atom attached to the metal.The H2O solvent was found to play an important role in the bond dissociation of the metal-oxygen linkage from a linear dependence between the reactivity index (1/2Nz2LU) of the protonated complex to such nucleophiles as H2O and the activation energy for the SN2 aquation reaction. The proposed tetragonal pyramidal intermediate of (NH3)5Ru3+ combines easily the Ru–O through the lowest unoccupied dz2 Ru-orbital, forming an aquo-complex with the binding energy of with H2O linkage, 30.25 kcal/mol
Apparent Molal Volumes and Adiabatic Compressibilities of n-Alkanols and α,ω-Alkane Diols in Dilute Aqueous Solutions at 5, 25, and 45°C. I. Apparent Molal Volumes
Authors: Nakajima Toshio , Komatsu Tsuyoshi , Nakagawa Tsurutaro
Published: July 2006

Density measurements have been carried out on a series of dilute aqueous solutions of n-alkanols and α,ω-alkane diols. The apparent molal volumes, φV, have been derived, and the φ°V values (V°2) at an infinite dilution have been estimated. The \barV°2, the ∂2\barV°2⁄∂T, and the ∂2\barV°2⁄∂T2 of the CH2, the CH3, and the CH2OH groups were obtained from the dependence of the \barV°2 and its temperature behavior upon the alkyl-chain length. It was found that the ∂2\barV°2⁄∂T2 value well reflects the structural effect.
Photochromism of 2-Hydroxytriphenylmethanol and Its Derivatives
Authors: Hamai Sanyo , Kokubun Hiroshi
Published: July 2006

2-Hydroxytriphenylmethanol (HM) shows photochromism in air-saturated acetonitrile and other solvents and also in the crystalline state. The colored form has been deduced to be o-fuchsone, produced by photochemical dehydration of HM. The photochromism mechanism is entirely different from that of other triarylmethane derivatives. The colored form is the same species as in thermochromism. The reactive state of HM was found to be the excited singlet state from the results of quenching experiments. The quantum yield of the photochemical reaction was determined to be 0.62 in acetonitrile by a method based on the equilibrium between the photochemical and thermal bleaching reactions. Photochromism occurs also at 77 K. At this temperature, HM radical is produced beside the colored form. The ratio of the concentration of HM radical to the colored form increases with irradiation time. Several HM derivatives show photochromism similar to HM.
The Syntheses of Ripariochromene A and Methylripariochromene A
Authors: Tsukayama Masao
Published: July 2006

7,8-Dimethoxy-2,2-dimethylchroman was obtained from pyrogallol trimethyl ether and β,β-dimethylacrylyl chloride via the corresponding chroman-4-one. The Friedel-Crafts reaction of the chroman with acetyl chloride yielded 6-acetyl-7-hydroxy-8-methoxy-2,2-dimethylchroman. The dehydrogenation of the acetylchroman with DDQ in anhydrous benzene afforded ripariochromene A. Ripariochromene A was converted into methylripariochromene A
The Magnetic Properties of Verdazyl Free Radicals. IX. The Crystal Structure of 1,3,5-Triphenyl-6-methylverdazyl Radical
Authors: Azuma Nagao , Deguchi Yasuo , Marumo Fumiyuki , Saito Yoshihiko
Published: July 2006

The crystal structure of 1,3,5-triphenyl-6-methylverdazyl has been determined by X-ray diffraction. The crystals are orthorhombic, with the space group of Pnma and with a=18.25(1), b=16.65(1), c=5.776(2) Å, and Z=4. The structure was deduced from the sharpened Patterson synthesis and was refined by the block-diagonal least-squares method to the final R value of 0.055 for 960 non-zero reflections collected on an automated four-circle diffractometer. The sym-tetrazinyl ring has an asymmetrical boat form, as has been observed in both 1,3,5-triphenylverdazyl and 1,3,5-tri-p-tolylverdazyl. The complete intermolecular overlap was observed in a tilted face-to-face array along the c-axis; this accounts for a fairly strong antiferromagnetic exchange interaction between the unpaired electrons.
Interfacial Capacity between a Silver Bromide Solid Electrolyte and a Blocking Electrode
Authors: Kimura Noriyoshi , Osaki Takahisa , Toshima Shinobu
Published: July 2006

The interfacial capacity between a silver bromide single crystal and graphite and platinum blocking electrodes was measured using an AC bridge in the potential range 0.05–0.55 V vs. Ag/AgBr at 200–400 °C. The observed capacity-potential curves were compared with the calculated values from the space charge layer capacity. In the case of the graphite electrode, the capacity had a minimum value at 0.15–0.20 V vs. Ag/AgBr, whereas for the platinum electrode, the capacity was considerably larger and the differential capacity-potential curves were complicated. It is concluded that the space charge layer capacity predominates for the graphite electrode, but for the platinum electrode, its interaction with silver ion must be taken into account.
Lanthanide-Induced Nuclear Magnetic Resonance Shifts and Molecular Structure of l-Azetidine-2-Carboxylic Acid. I. Evaluation of the Shifts Intrinsic to the Lanthanide-Substrate 1:1 Complex
Authors: Inagaki Fuyuhiko , Takahashi Seizo , Tasumi Mitsuo , Miyazawa Tatsuo
Published: July 2006

The lanthanide-induced PMR shifts (LIS) were observed in D2O solution of l-azetidine-2-carboxylic acid using europium, nitrate as shift reagent. Two series of measurements were carried out with the successive dilution and the incremental dilution methods. The analysis of observed data shows that the formation of 1: 2 complex between the lanthanide ion and the substrate molecule should be taken into account in addition to 1:1 complex. The LIS’s intrinsic to 1: 1 and 1:2 complexes were evaluated. An experimental method appropriate for obtaining the ratio of the LIS’s intrinsic to 1: 1 complex is proposed.
Profiles of the Distribution of Atoms in the Nitrous Oxide–acetylene Flame
Authors: Fujiwara Kitao , Haraguchi Hiroki , Fuwa Keiichiro
Published: July 2006

The distributions of neutral atoms in the nitrous oxide–acetylene flame have been measured by nebulizing aquo ions of the following sixteen elements into the flame; cadmium, nickel, zinc, copper, lead, cobalt, manganese, iron, chromium, molybdenum, calcium, tin, gallium, indium, titanium, and boron. The distributions have been figured on the response surfaces on which the changes in distribution are expressed as functions of the flame height and the acetylene flow rate. The response surfaces for the temperature and the OH radical were also investigated. The response surfaces for the atomic absorptions of the elements can be related to the thermodynamic properties of the oxides of the elements. The results have then been used for the discussion of the atomization processes of the elements in the flame. In addition, the sensitivities of absorption spectrometry in the nitrous oxide–acetylene flame have been compared to those in the air–acetylene flame.
The Chelation of 3-(p-Hydroxybenzylidene)-2,4-pentanedione with the Thallous Ion
Authors: Kawato Toshio , Kanatomi Hajime , Demura Yoichi , Murase Ichiro
Published: July 2006

A thallous compound of 3-(p-hydroxybenzylidene)-2,4-pentanedione was synthesized and its structure was determined by means of the infrared and proton magnetic resonance spectra. This compound was regarded as a thallous phenolate derivative; however, the effect of chelation by the 2,4-pentanedionate moiety due to a longrange anionotropy was observed. The acetyl proton exchange of the Tl(I) compound in D2O was observed by a PMR investigation. It was found that the methyl-proton exchange was inhibited by chelation.
Structure of Polyvanadotungstates. I. The Crystal Structure of α-(CN3H6)4V2W4O19
Authors: Nishikawa Keiko , Kobayashi Akiko , Sasaki Yukiyoshi
Published: July 2006

Crystals of α-(CN3H6)4V2W4O19 are monoclinic, space group P21 with the cell dimensions, a=14.85(2), b=19.48(2), c=9.48(1) Å, β=92.6(2)°. The X-ray structure determination showed that V2W4O194− anion has the hexaniobate-type structure consisting of 6 edge-shared MO6 octahedra. Each M position is randomly occupied by vanadium and tungsten atoms with a 2: 4 probability. This randomness makes it impossible to determine whether V2W4O194− anion has the cis or trans configuration or both. The final R value was 0.086 with anisotropic temperature factors for metals and isotropic factors for other lighter atoms.
The Extraction of Bis(8-picolylideneaminoquinoline)iron(II) Perchlorate into Nitrobenzene
Authors: Otomo Makoto , Kodama Kazunobu
Published: July 2006

The green chelate cation of bis(8-picolylideneaminoquinoline)iron(II) can be extracted into nitrobenzene as the form of the ion-pair with various univalent anions. The extractability with these anions is decreased in the order of B(C6H5)4−≈ClO4−>SCN−>I>>NO3−>Br−>Cl−>>CH3COO−. The extractive reaction with perchlorate ions has been applied to the spectrophotometric determination of minute amounts of iron(II). The nitrobenzene extract gives two characteristic charge-transfer (d→π*) bands at 663 and 569 nm. Under the optimum conditions of pH, ligand concentration and shaking time, Beer’s law is obeyed up to 1.2×10−4 M iron(II) in the organic phase. The molar absorptivity is 7.04×103 l·mol−1·cm−1 at 663 nm. The proposed method is selective and can be used for the determination of iron(II) in the presence of fairly large amounts of various ions, provided high concentrations of the ligand or suitable masking agents are used. A kinetic study made to obtain an information on the extraction mechanism of the ion-pair of this type showed that the rate equation can be represented as

-\fracd[Fe^2+]dt=k_0[Fe^2+][8-PAQ]_org^2(1+k_1[ClO_4^-])

where k0 and k1 are respectively the rate constant and a constant.
Syntheses and Properties of 2′-Aminobiphenyl-2-ol and Its Copper(II) Complexes
Authors: Mori Iwao
Published: July 2006

A new bidentate ligand, 2′-aminobiphenyl-2-ol(Habp), was synthesized. An examination of its behavior toward metal ions proved that, depending on the reaction conditions, the ligand gave mononuclear or polynuclear copper (II) complexes with seven-membered chelate rings. The complexes of the following compositions were thus characterized: Cu(abp)2, Cu(abp)2·H2O, Cu(abp)2·C6H6, Cu(abp)2·CH3COOC2H5, and Cu5(abp)8(OH)2·3H2O.
Photo-ethoxycarbonylation of Anisole, Dimethylaniline and Thiophene in Carbon Tetrachloride–Ethanol Solutions
Authors: Akiyama Takeo , Ikarashi Osamu , Iwasaki Koji , Sugimori Akira
Published: July 2006

UV-Irradiation of anisole, dimethylaniline and thiophene with carbon tetrachloride in ethanol produced ethoxycarbonylated compounds. In general, this photo-ethoxycarbonylation proceeds effectively when a charge transfer complex between aromatic compound and carbon tetrachloride is excited. Attack of tnchloromethyl radicals formed by the sensitized decomposition of carbon tetrachloride also occurs in parallel with the charge transfer mechanism.
Bitter Principles of Aquifoliaceae. III. The Structures and Stereochemistry of Three Aglycones Obtained by the Hydrolysis of Latifoloside A, a Bitter Glycoside from Ilex latifolia Thunb.
Authors: Ochi Masamitsu , Ochiai Katsumi , Nagao Kosho , Kubota Takashi
Published: July 2006

From the leaves of Ilex latifolia Thunb., two new bitter glycosides, latifoloside, A and B, have been isolated. The acid hydrolysis of A afforded three triterpenoid aglycones, which have been formulated by spectroscopic and chemical evidence as I, II, and III respectively.
Dehydrobromination of 16-Bromodihydroenmein-type Compounds
Authors: Isobe Takahiko , Kubota Takashi
Published: July 2006

16-Bromodihydroenmein diacetate (IV) obtained from dihydroenmein diacetate (III) by bromination with N-bromosuccinimide was dehydrobrominated with lithium chloride in dimethylformamide to give a product, the structure of which was elucidated as the intermolecular ether (VIII). The dimeric ether compound was also formed by similar reactions from the derivative of isodocarpin.
Tris(benzimidazo)-1,3,5-triazine from the Thermolysis of 2-Aryloxybenzimidazoles
Authors: Ishida Sadahiro , Fukushima Yoshiaki , Sekiguchi Shizen , Matsui Kohji
Published: July 2006

2-Aryloxybenzimidazoles gave tris(benzimidazo)-[1,2-a: 1′,2′-c: 1″,2″-e]-1,3,5-triazine and phenol in almost quantitative yields upon heating at 230–250 °C, while in the reaction in cumene small amounts of 2-aryloxy-1,2′-dibenzimidazole and dicumyl were obtained along with the major products. On the other hand, 2-phenylthiobenzimidazole gave diphenyl disulfide and 1,2′-dibenzimidazole, together with tris(benzimidazo)-1,3,5-triazine. The thermolysis is assumed to proceed by step-by-step radical processes involving the formation of such intermediates as 2-aryloxy-1,2′-dibenzimidazole and 2-aryloxy-1,2′-1′,2″-trisbenzimidazole.
The Acid-Catalyzed Cyclization of 2,3-Dimethyl-2-phenethyl-3-cyclohexen-1-one
Authors: Kusumi Takenori , Ohno Nobuo , Kakisawa Hiroshi
Published: July 2006

The cyclization of 2,3-dimethyl-2-phenethyl-3-cyclohexen-1-one 6a with aluminum chloride gave 4a,cis-10a-dimethyl-3,4,4a,9,10,10a-hexahydro-1 (2H)-phenanthrone 8a. The stereochemistry of the latter was established by synthesizing 4a,cis-10a-dimethyl-1,2,3,4,4a,9,10,10a-octahydrophenanthrene 10 through Diels-Alder reaction of 3-formyl-4a,cis-8a-dimethyl-4a,5,6,7,8,8a-hexahydro-2(1H)-naphthalenone 20 with butadiene.
Asymmetric Induction in Friedel-Crafts Reaction with (+)-1,2-Epoxybutane and (−)-2-Chloro-1-butanol
Authors: Nakajima Tadashi , Nakamoto Yoshiaki , Suga Sohei
Published: July 2006

The alkylation of benzene with (+)-1,2-epoxybutane in the presence of Lewis acid gave a mixture of optically active 2-phenyl-1-butanol (I) and 3-phenyl-1-butanol (II) together with a mixture of optically active 2-chloro-1-butanol (III), 3-chloro-1-butanol (IV) and 1-chloro-2-butanol (V). The formation of (−)-I and (−)-III suggests that the ring opening of the epoxide proceeds with an inversion of configuration, while that of optically active II and IV suggests an asymmetric induction at the carbon adjacent to the terminal methyl group of the epoxide. The reactions with aluminum chloride at 20 °C and with stannic chloride at −20 °C gave (+)-II in 10% and (−)-IV in 56% optical yield, respectively. In the reaction of (−)-III with benzene, such an asymmetric induction was also found to give (+)-II in 21–24% optical yield. The probable mechanism of this induction was discussed on the basis of the stability of the transition state conformations.
The Viscosity of Gaseous Sulfur Dioxide
Authors: Iwasaki Hiroji , Takahashi Mitsuo
Published: July 2006

The viscosity of sulfur dioxide was measured in the range from 25 to 160 °C over the pressure range from 1 atm to near the saturation pressure at 25–150 °C and up to 80 atm at 160 °C by means of the oscillating-disk method. The accuracy of the measurement is, at worst, ±0.25%, except that the accuracy is ±0.3% for the range above 66 atm at 160 °C. It is found that, at temperatures from 25 to 75 °C, the viscosity of sulfur dioxide shows a steady decrease with the pressure (or density) and that at 100 and 125 °C it passes through a minimum. On the contrary, the isotherms at 150 and 160 °C show a steady increase with the pressure (or density). The data were fitted to the polynomials of the density at each temperature investigated. The coefficient of the first-order density term in the equation, which indicates the degree of the initial density dependence, changes its sign from negative to positive at a temperature of about 135 °C.
Adsorption of Neutral Organic Substances Evaluated from Electrocapillary Curves and Double Layer Capacities
Authors: Niki Katsumi
Published: July 2006

Adsorption of neutral organic substances on mercury electrode was evaluated from both electrocapillary curves and differential capacities of the double layer. The results were compared for the adsorption of n-aliphatic alcohols, phenol, and o-cresol in 0.5 M H2SO4. There was some evidence that the electrode potential was more favorable than the charge on the electrode as an electrical variable in the adsorption of the n-aliphatic alcohols. However, the values deduced from the Frumkin model were generally larger than the θ’s obtained from the electrocapillary curves. This discrepancy is probably due to the deviation from the two-condensers-in-parallel model, because, the two condensers were not independent in an actual system. Neither the two-condensers-in-parallel model nor the three-condensers-in-parallel model were applicable to the adsorption of aromatic compounds.
The Inner-Sphere Mechanism Interpreted by the Hydrogen Ion Effect on the Fe2+ Reduction Rate of Oxalato-, Malonato-, Glycolato-, and Chloro-Cobalt(III) Complexes in Aqueous Solution
Authors: Ohashi Kousaburo
Published: July 2006

The hydrogen ion effect on the rate of the Fe2+ reduction of oxalato-, glycolato-, and chloro-cobalt(III) complexes was investigated kinetically. It was found that the rates of the Fe2+ reduction of cobalt(III) complexes such as trans(N)-Co(ox)(β-ala)2−, trans(N)-Co(ox)(gly)2−, trans(N)-Co(ox)(gly)(en), Co(ox)33−, and trans-(O,Cl)-Co(Cl)(am)(dien)+ (am=glycinate, α-alaninate or β-alaninate ions) increase with an increase in the hydrogen ion concentration. This result can be explained by accounting for the protonation of the oxygen atom of the carbonyl group of the nonbridging ligand. The inner-sphere mechanism can be deduced for the Fe2+ reductions of these complexes due to the hydrogen-ion effect. Moreover, a kinetic study of the Fe2+ reduction reaction of Co(Hmalo)(NH3)52+ and Co(malo)(NH3)5+ was carried out. An inner-sphere mechanism for these reactions is proposed from an analysis of the kinetic data. Discussion of the structure of the precursor complex and of the rate determining step for the Fe2+ reduction reactions of cobalt(III) complexes are also made.
Copper(II) Chelates with Some Photographic Color Intermediates. Structure-Stability Relationships
Authors: Shawali Ahmad S , El-Hilaly Ahmad E , El-Ezaby Mohammad S
Published: July 2006

Acid dissociation constants, pK1 of a series of benzoylacetanilides (Ia–i) have been determined potentiometrically in 50 vol% ethanol–water media at 30 °C. The stability constants, logβ1, of their copper(II) chelates have also been determined. The effects of substituents on the anilide moiety of the ligand on the equilibria are discussed. The data were correlated by the equations: pK1=9.39–0.916 σ; logβ1=1.34pK1−5.42; and logβ1=7.20–1.44 σ. These results were taken to imply that the stabilization by dative metal-to-ligand π-bonding is not significant in copper(II)–benzoylacetanilide complexes.
Non-isothermal Studies of Adduct Molecules of Metallic Halides with Oxo Compounds in Solid State. II
Authors: Chaudhuri N Ray , Mitra S
Published: July 2006

Non-isothermal studies of several adduct molecules of metallic halides with oxo-compounds as the type MX2(THF)y, in solid state were carried out with a Derivatograph, where M is Mn(II), Co(II), Ni(II), Cu(II) or Cd(II), X is Cl− or Br−, THF is the abbreviated form of tetrahydrofuran and y is 0.25–2.00. These adduct molecules lost tetrahydrofuran in single or multiple steps upon heating. Thermally stable intermediate products were isolated and characterised by elemental analysis and IR spectral measurement. The activation energy for each step of decomposition of the adducts was evaluated from the analysis of TG, DTG, and DTA curves of the respective derivatograms. Enthalpy change was evaluated from DTA peak area and order of reaction was found to be unity for each step of decomposition. Thermal parameters for the above adducts were compared with those of the adducts of dioxane.
Studies of Tritylated Pentoses and Methyl Pentoses. I. The O-Tritylation of Methyl α-d-Fucopyranoside
Authors: Otake Toshiki , Sonobe Toru
Published: July 2006

Two trityl derivatives of fucose, methyl 2-O- (II) and 3-O-trityl α-d-fucopyranoside (III), were obtained in good yields by the reaction of methyl α-d-fucopyranoside (I) and trityl chloride in pyridine. The ratio of II and III in the reaction mixture was about 3 : 2. The structures were mainly established by NMR with appropriate derivatives. The gas chromatography-mass spectrometry of the partial methyl ethers of I was also discussed.
Solvent Effects on Stereo and Regioselectivities of Ring-opening Reaction of Epoxide with Aluminum Chloride
Authors: Inoue Masashi , Sugita Toshio , Kiso Yoshiaki , Ichikawa Katsuhiko
Published: July 2006

The ring-opening of 2,3-epoxybutane with aluminum chloride yielding 3-chloro-2-butanol was carried out in several different solvents. The reaction proceeds with 94% retention of configuration in a nitromethane solvent. The retentive ring-opening was observed to variable extents when nitro compounds, ethers, and aromatics were utilized as the solvents, but a complete inversion resulted in the other solvents. The regioselectivity was examined using 1,2-epoxypropane. The composition of the 1-chloro-2-propanol and 2-chloro-1-propanol thus produced was also strongly affected by the solvent. The latter was exclusively produced in nitromethane, though the former predominated in several other solvents. The structure of aluminum chloride in various solvents is discussed, and aluminum chloride-solvent 1 : 1 addition compounds in solution are concluded to be important for retentive and abnormal ring-opening.
Steroids. I. The bromination of 1α-Methyl and 1α-Phenyl-3-keto Steroids
Authors: Takahashi T Tomoyoshi , Satoh J Yasuo
Published: July 2006

1α-Phenyl-5α-cholestan-3-one was prepared from 5α-cholestan-1-en-3-one by treatment with the Grignard reagent in the presence of copper (I) chloride. In the mono- and dibromination of 1α-methyl-3-keto steroids, it was found that the position and configuration of bromine were the same as in the case of the 1-nonsubstituted 3-keto steroid. The A-ring conformations of these bromoketones were studied by means of NMR and ORD.
Aminocyclitols. 33. Synthesis of Diaminocyclopentanetriols
Authors: Tadano Kinnichi , Emori Yasufumi , Ayabe Mitsukuni , Suami Tetsuo
Published: July 2006

Three hitherto unknown 2,5-diamino-1,3,4-cyclopentanetriols have been prepared. Their structures were established by chemical evidence.
Effects of Alkali Metal Cation, Solvent, and Alkylating Agent on the Alkylation of Alkali Metal Enolates of Ethyl Acetoacetate
Authors: Hara Yoshinori , Matsuda Minoru
Published: July 2006

Alkylation of Li+, Na+, and K+ enolates of ethyl acetoacetate by dimethyl sulfite in dimethyl sulfoxide, hexamethylphosphoric triamide, and N,N-dimethylformamide at 50 °C has been studied. The ratio of O/(C+C,C)-alkylation is considerably dependent on the size of the counter cation and the solvent. The tightness of the ion pair is responsible for determining the ratio. The structure of alkylating agents has also influence upon the alkylation ratio. Dimethyl sulfite gives a higher O/(C+C,C)-alkylation ratio than methyl halides which may be ascribed to the hard methyl sulfite anion as leaving group.
The Enzyme-like Reaction Catalyzed by Flavin-Reduced Keratin Systems
Authors: Takahashi Fujio , Ogasa Tatsuo , Hirano Morio , Suzuki Shuichi
Published: July 2006

The reduced keratin (RK), which was obtained by the reductive cleavage of human hair, was found to act as an apoenzyme and to furnish the reaction field for flavin adenine dinucleotide (FAD): the absorbance of the succinic acid–FAD–RK system in solution increased in the region of 200–250 nm with the lapse of time. From this system fumaric acid was isolated. FAD was found to form a complex with RK and the FAD–RK complex exhibited a catalytic activity for the dehydrogenation reaction of succinic acid to fumaric acid. FAD was reduced in this reaction and the reduced FAD was oxidized by oxygen. It was found that the process of the dehydrogenation reaction obeyed the Michaelis-Menten kinetics; the equilibrium constants of the complex formation between FAD and RK were determined by measuring the initial velocities of the dehydrogenation reaction. The binding site of FAD and RK in the complex was discussed.
Primary Photochemical Process of Sulfur in Solution
Authors: Nishijima Chiho , Kanamaru Nobuaki , Kimura Katsumi
Published: July 2006

A photochemical intermediate possibly attributed to linear S8 has been found with a flash-photolysis technique and a rigid-glass technique. The decay behavior of transient in ethanol at room temperature between 10 and 100 ms may be interpreted in terms of the dimerization and polymerization of the linear S8.
The Infrared Frequency Shift and Half Width of the Hydrogen-Bonded Band in Some Phenol–Nitrile Systems
Authors: Jawed Inam
Published: July 2006

The relationship between the infrared frequency shift and half width of the hydrogen bonded band for a number of phenol-nitrile systems has been studied. A linear relationship, (Δν1⁄2)bonded=0.31Δν+21.7 cm−1, has been obtained. It seems that in such plots the intercept is about the magnitude of the half width of the free or unbonded ν(XH) band; i.e., at zero value of the frequency shift, the half width of the bonded band equals that of the free band.
The Structure and Reactivity of [Zn(OMe)2·(EtZnOMe)6]
Authors: Ishimori Michihiro , Hagiwara Tokio , Tsuruta Teiji , Kai Yasushi , Yasuoka Noritake , Kasai Nobutami
Published: July 2006

The molecular structure of [Zn(OMe)2·(EtZnOMe)6], an enantiomorphic catalyst for the polymerisation of methyloxirane, has been determined.
Branched-chain Sugars. VI. Reaction of Methylene Dimagnesium Bromide with Uloses
Authors: Yoshimura Juji , Sato Ken-ichi , Wakai Hiroo , Funabashi Masuo
Published: July 2006

Application of methylene dimagnesium bromide, instead of the Wittig reagent, to several uloses gave the corresponding methylene derivatives in nearly equal yields, when the hydroxyl groups vicinal to the carbonyl function are protected with alkaline-stable groups.
The Inclusion Effects of Cyclodextrins on the Photolysis of p-Benzoquinone in Aqueous Solution
Authors: Yamada Kazutoshi , Kohmoto Shigeo , Iida Hirotada
Published: July 2006

The additive effects of cyclodextrins on the photolysis of p-benzoquinone in water were investigated spectrophotometrically. By applying Michaelis-Menten keinetics, the dissociation constant of the inclusion complex was determined. The quantum yield for the formation of hydroquinone from the complex increased, while that of 2-hydroxy-1,4-benzoquinone decreased.
Olefination of Aldehydes by Methylenedicalcium Diiodide
Authors: Kawabata Nariyoshi , Naka Michiharu , Komazawa Takao , Yamashita Shinzo
Published: July 2006

Reaction of diiodomethane with calcium in tetrahydrofuran gave methylenedicalcium diiodide in 17% yield. Reaction of the calcium compound with aldehydes was shown to give the corresponding olefins in estimated yields of 53–94%.
Studies of Spontaneous Emulsification. II. The Effect of Nonionic Surfactants
Authors: Ogino Keizo , Ota Motoki
Published: July 2006

At the oil/water interface, spontaneous emulsification occurs when oil containing certain oil-soluble substances such as cholesterol is allowed to stand in contact with aqueous nonionic surfactant solutions. In this study, the interfacial tension between oil and water phases was measured in the presence of various oil-soluble substances, such as cholesterol, 1-dodecanol, and cis-9-octadecene-1-ol, added as ingredients in oil and various nonionic and anionic surfactants added in water, this study ascertained their effects on the emulsification.
Studies of MoO3–Al2O3 Catalyst in Ethylene Polymerization. III. The Nature of Mo(V) and Its Relation with Activity
Authors: Hashimoto Keizi , Watanabe Shozi , Tarama Kimio
Published: July 2006

In order to determine the active center of ethylene polymerization over MoO3–Al2O3, the g-tensor and the amount of molybdenum(V) in each chemical state were determined by means of ESR measurement. The anisotropy of the g-tensor revealed the strength of the crystal field in the state; the decreasing order of the strengths was as follows: state(S)>state(M)>state(W)>MoO3–SiO2\fallingdotseqfree MoO3. In the state(S) molybdenum oxide is insoluble in aq.10M–NH3, in the state(M) it is soluble in aq. NH3 but insoluble in water, and in the state(W) it is soluble in water. The amount of molybdenum(V) in the state(W) was studied in connection with the activity, because only the state(W) was suitable for polymerization. The behavior of the activity was in fair agreement with that of the molybdenum(V) content in the state(W) and this content depedned on the amount of supported MoO3 and on the extent of reduction. The amount of molybdenum(V) in the state(W) corresponded to the amount of chemisorbed hydrogen, which was a polymerization initiator. The chemisorption of oxygen on the catalyst caused a complete disappearance of both the activity and the molybdenum(V) content in the state(W). Therefore, it was concluded that the active center of the polymerization was molybdenum(V) in the state(W).
Analytical Application of Catalytic Polarographic Current of Nickel(II) in Acidified Thiocyanate Solutions Containing Cobalt(II)
Authors: Itabashi Eiki , Yusa Ikuko
Published: July 2006

Simple and sensitive methods have been developed for the determination of nickel(II), based on the catalytic polarographic current in acidic thiocyanate solution in the presence and absence of cobalt(II). The basis of the methods and the effect of variables have been investigated and elucidated. In the absence of cobalt(II), thiocyanate solution containing large amounts of hydrogen ions serves a supporting electrolyte, while an acidic thiocyanate solution containing tetra-n-butylammonium salts is suitable for the determination of nickel(II) in the presence of cobalt(II). These methods are applicable to the determination 2×10−6 M nickel(II) in the presence and absence of 1×103 M cobalt(II).
An Investigation of the Triplet State Dynamics of p-Chloroaniline by Microwave Induced Changes in the Phosphorescence Intensity and by Triplet←Singlet Absorption
Authors: Nishi Nobuyuki , Kinoshita Minoru
Published: July 2006

The phosphorescent triplet state T1 of p-chloroaniline (PCA) in a p-xylene host, in a neat crystal (n-trap), and in a PCA crystal doped with p-dichlorobenzene (x-trap) has been studied with the aid of phosphorescence spectra, optically detected zero-field magnetic resonance, and T1←S0 absorption spectra at temperatures below 4.2 K. The dynamic properties, particularly the radiative properties, of the individual spin states of T1 are discussed in detail using the emission spectra for each spin state obtained with microwave techniques. For the x-trap system, the emissions from the Ty and Tz sublevels are found to be coincident in contrast to the other two systems. From this observation, it is suggested that the characters of the Ty and Tz states of normal PCA are mixed together in the x-trap.

The populating rates for the individual spin states were examined for the PCA crystal systems as a function of the excitation energy, when the excitation was induced by light having wavelengths in the T1←S0 absorption region. The relative populating rates thus obtained are dependent on the excitation energy. Therefore, it is concluded that the spin alignment produced by direct optical pumping from the ground state to the triplet manifold of the crystal is conserved during the vibrational relaxation and energy transfer processes. By using this unique wavelength dependence of the populating rates, the nature of the n- and x-traps is discussed and the vibrational structure of the T1←S0 spectrum is analyzed.
The Conformations of Oligosaccharides. III. The Crystal and Molecular Structure of Melibiose Monohydrate
Authors: Hirotsu Ken , Higuchi Taiichi
Published: July 2006

The crystal structure of α-melibiose monohydrate (C12H22O11·H2O) was determined by direct methods using two-dimensional cosine invariants. The space group is P212121, with Z=4 and unit cell dimensions of a=15.814(5), b=10.924(5), c=8.903(4) Å. The structure was refined to R=0.044 for 1439 reflections measured with MoKα radiation. Difference synthesis indicated the partial (15%) random substitution of α-melibiose molecules by the β-anomer. The molecular conformation of α-melibiose is almost the same as that previously found in the melibiose moiety of raffinose, although some of the bond lengths and angles are significantly different. The molecules are linked by complex hydrogen-bond systems which consist of six-link finite chains and five-membered closed loops.
Studies of the Ruthenium(III) Complexes. XII Kinetic Studies of the Deammonation-anation Reactions of Halogenopentaammineruthenium (III) Complexes in the Solid State
Authors: Ohyoshi Akira , Kohata Susumu , Nishimori Masanobu , Shimura Yoshiaki , Iwasaki Noriko
Published: July 2006

The kinetics of the thermal substitution reaction of chloro- and bromopentaammineruthenium(III) complexes has been studied in the solid state. The reaction rates and kinetic parameters were determined for these reactions: [RuX(NH3)5]Y2(s)→[RuXY(NH3)4]Y(s)+NH3(g), and (X=Cl, Br: Y=Cl, Br, I, NO3). The values of the rate constant (s−1), the activation energy (kcal mol−1), and the activation entropy (cal mol−1 K−1) were 1.70×10−5 (at 222 °C), 41.8, and 0.7 for [RuCl(NH3)5]Cl2; 1.02×10−4 (at 226 °C), 30.2, and −19.6 for [RuCl(NH3)5]Br2; 1.35×10−4 (at 208 °C), 25.3, and −26.6 for [RuCl(NH3)5]I2; 8.47×10−3 (at 162°C), 29.7, and −11.5 for [RuCl(NH3)5](NO3)2; 1.26×10−4 (at 219 °C), 21.8, and −35.1 for [RuBr(NH3)5]Cl2, and 1.17×10−3 (at 162 °C), 14.7, and −40.0 for [RuBr(NH3)5](NO3)2 respectively. The SN1-like mechanism is favorable for the deammonation-anation reaction of all the chloropentaamine series except for the iodide, while the SN2-like mechanism is more probable for the corresponding reaction of the bromopentaammine series. The reaction mechanism is predominantly controlled by the coordinating ability of the inner-sphere halide ion and secondarily by that of the outer-sphere anion.
The Complexing of the Thallium(I) Ion with Other Solvents in Acetonitrile. Investigation Using a Cationsensitive Glass Electrode
Authors: Nakamura Toshio
Published: July 2006

The complexing of the thallium(I) ion with other common solvents has been studied in acetonitrile by using a univalent cation-sensitive glass electrode. A method similar to that developed to study the complexing of sodium and lithium ions was employed. Mono-, di-, and tri-solvated species were formed with DMF, SDMF, DMA, pyridine, formamide, and DMSO. Tetra-solvated species were also formed with N-methylformamide and HMPA. The complex formation constants for the mono-solvated thallium(I) ion were 4.1 with DMF, 5.6 with SDMF, 6.9 with DMA, 11 with pyridine and formamide, 12 with N-methylformamide, 15 with DMSO, and 1.0×102 with HMPA. Prior to these experiments, the cation-sensitive glass electrode was confirmed to respond to the thallium-(I)-ion activity in different solvents by comparing its behavior with that of a thallium-amalgam electrode. When water was the complexing solvent the potential of the glass electrode was not stable, and therefore, a thallium-amalgam electrode was used instead of a glass electrode to obtain the hydration constants of the thallium(I) ion in acetonitrile. Mono- and di-solvated species were formed with water and the hydration constant for the mono-solvated species was 1.1. The amalgam electrode and the glass electrode were used to obtain the constants with DMSO.
Reactions of the Di-μ-oxo-bis[aquaoxalatooxomolybdate(V)] Ion
Authors: Komura Akitoshi , Ikeda Yasuzi , Imanaga Hiroto
Published: July 2006

Reactions of the complex ion [Mo2O4(C2O4)2(H2O)2]2− (I) have been investigated. On acidification with perchloric acid and hydrochloric acid, complex (I) gave molybdenum(V) aqua-dimer ion [Mo2O4(H2O)6]2+, which was converted into the monomeric species [MoOCl5]2− in concentrated hydrochloric acid. The initial reaction of complex (I) with mercaptoacetic acid, giving a complex of stoichiometry 1 ligand: 1 Mo, was followed by a slower reaction which probably gave higher complexes. In the reactions with o-aminophenol and 2,2′-bipyridyl, complexes of stoichiometry 1 ligand: 1 Mo and 1 ligand: 2 Mo, respectively, were formed in solutions. The following complexes have been isolated: Mo2O4(dtc)2, Mo2O3(dtc)4 (dtc=diethyldithiocarbamate), MoOCl3. phen (phen=1,10-phenanthroline), and Mo2O3Cl4(bpy)2 (bpy=2,2′-bipyridyl). The infrared and electronic spectra of the complexes and their probable structures are given. The relative ease of replacement of ligands from complex (I) has been discussed.
Liquid Phase Disproportionation of Propylene over MoO3–Al2O3Catalyst in the Presence of Solvents
Authors: Ogata Eisuke , Sodesawa Toshiaki , Kamiya Yoshio
Published: July 2006

Liquid phase disproportionation of propylene using hydrocarbon solvents over MoO3–Al2O3 (atomic ratio: Mo/Al=1⁄25) catalyst was investigated at 80 °C at a pressure of 50 kg/cm2. The catalytic activity in heptane solution was preserved for a long time, because the small amount of polyolefins produced by polymerization reactions was entirely dissolved in the heptane and carried away from the catalyst surface. Selectivity for ethylene and butenes increased slightly in the heptane solvent. Benzene was not a suitable solvent because of poor solubility of the polymers and the formation of alkylbenzenes. A small amount of dissolved hydrogen also was found to be somewhat effective in lengthening the catalyst life. The polymers were found to be composed of larger amounts of ethylene than propylene and to have two molecular weight distribution maxima.
Cyanamide Derivatives. Part 99. Electrolytic Oxidation of Cyanamide
Authors: Kubo Koji , Nonaka Tsutomu , Odo Keijiro
Published: July 2006

Cyanamide was electrochemically oxidized with a platinum anode in aqueous potassium hydroxide. Electrolysis was carried out at 1.30 V vs. SCE of anode potential. Oxidation products consist of several unknown 1,2,3,5-tetrazine compounds and known linear cyano compounds.
Vinyl Polymerization. 341. A Proposal of a Mechanism for Radical Polymerization of Vinyl Monomers with Sodium Polymethallylsulfonate
Authors: Imoto Minoru , Nakamura Yoshiaki , Ouchi Tatsuro
Published: July 2006

In aqueous solution, sodium polymethallylsulfonate (PMAS-Na) can initiate a radical polymerization of vinyl monomer which has positively charged vinyl group. In the polymerization of MMA, Michaelis-Menten equation was applicable. From the results obtained, a bimolecular initiation mechanism, involving hydrogen atom transfer, was concluded to be reasonable. The relationships between pH of the aqueous layer and conversion and between polymerization temperature and conversion were of downward bell type. By Stewart model, it was found that PMAS-Na has a very rigid conformation. This structure can be compared with a rigid tertiary structure of enzyme, and the reaction appearances of enzyme and PMAS-Na can be considered to resemble very much each other.
The Reaction between Hydrocarbon and Hydrogen Chloride in Silent Electrical Discharge. I. The Reaction of Ethylene with Hydrogen Chloride
Authors: Kawamoto Kazuaki , Tamura Keiko , Hikasa Setsuko
Published: July 2006

Silent discharge was found to induce the reaction of ethylene and hydrogen chloride and to give mainly addition and telomerization products. Discharge on a mixture of ethylene and hydrogen chloride in an ozonizer under atmospheric pressure gave chloroethane, 1-chlorobutane, and 1,4-dichlorobutane as the main products. Besides these compounds, chloroethylene, 2-chlorobutane, 1,3-dichlorobutane, 2,3-dichlorobutane, 1,2-dichlorobutane, 1-chlorohexane, 1,2-dichloroethane, and gaseous products were also formed. The maximum yield of the liquid products was obtained when ethylene and hydrogen chloride were mixed in the ratio of approximately 1:1. The formation of telomers was favored by a low ratio of the hydrogen chloride to the ethylene concentration, and by a low temperature in the discharge reaction. On the other hand, gaseous products increased with the rise in the discharge temperature and with an increase in the ratio of ethylene to hydrogen chloride. Judging from the product distribution, the reaction may be explained in terms of radical reactions involving vinyl, ethyl, and chlorine radicals. Among the reactions between ethylene and HX, such as hydrogen cyanide, hydrogen sulfide, and hydrogen chloride, the highest conversion was obtained by using the hydrogen chloride as the reactant.
The Base-Catalyzed Condensation Reaction of o-Nitroisobutyrophenone in Liquid Ammonia
Authors: Yamaguchi Kimiko
Published: July 2006

The base-catalyzed condensation reaction of o-nitroisobutyrophenone (III) with sodium acetylide in liquid ammonia gave 1-ethynyl-2-methyl-1-(o-nitrophenyl)-1-propanol (G) as the main product and o,o′-azoxybenzamide (C), 2-carbamoyl-2′-carboxyazoxybenzene (C′), 2,2-dimethyl-3-indolinone (D), 1-hydroxy-2,2-dimethyl-3-indolinone (E), and 1-hydroxy-2,2-dimethyl-1,2-dihydro-4-quinazolone (F) as minor products. On the other hand, with sodium amide the ketone (III) gave Compounds C and C′ as the main products and Compounds D, E, and F as the minor products. These products were formed by the α-proton abstraction.
Transbutylation of Aromatic Hydrocarbons with Di-t-butylanisole
Authors: Shimada Keizo
Published: July 2006

The trans-t-butylation of aromatic hydrocarbons with di-t-butylanisole in the presence of aluminum chloride was studied. It was found that the t-butyl group substituted at the ortho position to the methoxy group transfered easily to the hydrocarbons, but the t-butyl group of the para position did not transfer to the hydrocarbons. The transbutylation products did not suffer further isomerization when the catalyst aluminum chloride was less than 1/2 mol of the di-t-butylanisole used. Competitive trans-t-butylation was carried out and kT⁄kB, km–X⁄kB, kO–X⁄kB, and kEB⁄kB were found to be 24, 2.2, 136, and 19, respectively.