bluuebunny/crossref_metadata_2025 huggingface dataset:
Volumetric Determinations of Cyanide, Thiocyanate, and Iodide Ions with Mercury(II) Ethylenediaminetetraacetate Using These Mixed-ligand Complexes as Indicators
Authors: Nomura Toshiaki
Published: July 2006

Mercury (II) complexes of EDTA, methylthymolblue, or cresolphthaleincomplexone form mixed-ligand complexes with cyanide, thiocyanate, or iodide ions. These anions can be determined with mercury(II) ethylenediaminetetraacetate, using the other mercury(II) complexes as indicators, because of the difference between the stability constant of the mixed-ligand complex of EDTA and that of the other complexes. The previously reported methods, however, require a calibration curve. The determination was simplified by Titer methods, using these mixed-ligand complexes as indicators. To the anion-sample solutions adjusted to a given pH value with a buffer solution, 5 ml portions of 1×10−4m mercury(II), an organic reagent, and anion solutions were added, these mixtures were then titrated with a 1×10−2m standard mercury (II) ethylenediaminetetraacetate solution. These solutions change in color from pale pink (PC) or yellow (MTB) to red-violet (PC) or blue (MTB) by the end point. The Titer values were determined by the use known of standard anion solutions.
Optimum Geometric Position for Radioactivation by Fast Neutron with a Neutron Generator
Authors: Kishikawa Toshiaki , Shinomiya Chiro
Published: July 2006

With a 14MeV neutrol generator the optimum irradiation position of disk or square samples of appropriate numbers are given as a function of the configuration of the sample relative to the source. Calculated values are compared with experimental data.
Circular Dichroism of Chromium(III) Complexes. II. Correlation between Behavior in the Spin-forbidden Absorption Band Region and Absolute Configurations
Authors: Kaizaki Sumio , Hidaka Jinsai , Shimura Yoichi
Published: July 2006

The absorption and circular dichroism (CD) spectra of twelve optically active chromium (III) complexes containing three bidentate ligands have been measured in the near-infrared to ultraviolet region. CD spectra in the spin-forbidden d-d absorption band region have been considered mainly in relation to the CD bands in the first spin-allowed d-d absorption band region. It has been concluded that the absolute configurations of chromium (III) complexes can be determined on the basis of the signs of the CD bands in the spin-forbidden band region. The splitting components of the CD bands in the spin-forbidden band region have been discussed considering the crystal field treatment by Macfarlane.
Telomerization of Vinyl Chloride with Carbon Tetrachloride Using Amine-Cupric Chloride. Effects of Amines and Solvents
Authors: Asahara Teruz\={o} , Sen\={o} Manabu , Wu Cheng-Ching
Published: July 2006

Telomerization of vinyl chloride with carbon tetrachloride was investigated in reaction systems containing amines and cupric chloride. The yield of telomers CCl3(CH2CHCl)nCl and the content of the telomer with n=1 were high when aliphatic amines with relatively long chains were used. An increase in basicity of amines raised the yield of telomers. When bifunctional amines such as diamines and alkanolamines were used, the yield of telomers was low and the content of higher telomers was high. The effect of added solvents on the yield of telomers was not so remarkable and an increase in the dielectric constant of solvents decreased the yields. The results were examined on the basis of Asscher-Vofsi mechanism, but could not be explained satisfactorily. A partly modified scheme was proposed for the radical addition in the cage complex stabilized with amine.
Aromatic Arylation with Aryl Radicals. I. A Novel Method for Generating Aryl Free Radical
Authors: Kobayashi Michio , Minato Hiroshi , Kobori Nobumasa , Yamada Eiichi
Published: July 2006

Benzenediazonium tetrafluoroborate in DMSO decomposed instantaneously with evolution of nitrogen upon addition of a DMSO solution of sodium nitrite. Orientations and partial rate factors for phenylation of substituted benzenes indicated that not phenyl cation but phenyl radical was produced as an intermediate. Hammett’s plots of partial rate factors of meta and para positions yielded good straight lines with ρm=0.46 and ρp=1.67. Plausible mechanisms were discussed. From m-dinitrobenzene 2,6- and 2,4-dinitrobiphenyl were produced in 47 and 23% yields, respectively, and the synthetic value of this method was pointed out.
Studies on the Baudisch Reaction. III. A Possible Intermediate in the Reaction
Authors: Tanimoto Iwao
Published: July 2006

The Baudisch reaction was applied to 1- and 2-naphthols, and 2-nitroso-1-naphthol was obtained as the sole product in both reactions. In a reinvestigation of the products obtained from phenols, it was also found that in some cases the nitroso group replaced the hydroxy group and a hydroxy group was newly introduced into the position ortho to the nitroso group. These results indicate that a copper(II)-hydroxylamine-catechol complex will be a possible intermediate of the reaction of phenol. The product studies on the reaction of catechols support the assumption. Kinetically, the formation of the complex seems to be the rate-determining step in the reaction of phenols.
Mechanism of Isotopic Exchange of Trisacetylacetonatoaluminum with Acetylacetone-14C in Organic Solvents
Authors: Saito Kazuo , Masuda Kazuyo
Published: July 2006

The kinetic study concerning isotopic exchange of acetylacetone (acacH) and trisacetylacetonatoaluminum [Al(acac)3] (Bull. Chem. Soc. Jap., 41, 384 (1968)) has been extended to solutions in various organic solvents. Similar catalytic actions of water and acid were observed, and the concentration of acacH did not affect the rate, so that the kinetic formula is expressed by

R=[complex](k_1+k_2[H_2O]+k_1’[acid]+k_2’[acid][H_2O])

The rate constants and activation parameters are listed in Table 1. The k1 values are zero in non-polar solvents such as toluene and xylenes, whereas the k2 values are greater in these solvents than in polar solvents such as tetrahydrofuran and ethylacetate. The activation enthalpy is practically constant in these solvents, regardless of the participation of catalysts. The third and the fourth term seem to represent acid-catalysed reaction paths involving different proton carriers. The whole result appears to support our previous tentative conclusions that the exchange proceeds via an intermediate in which one of the acetylacetonate ligands is present as unidentate, and that the ease with which the free end recombines with the aluminum ion is responsible in determining the reaction rates.
Hot-Atom Chemistry of Bromine. IV. Chemical Effects of 81Br(n,γ)82gBr, 81Br(n,γ)82mBr and 82mBr(I. T.)82Br Excitation in Antimony Tribromide and Benzene System
Authors: Kishikawa Toshiaki , Aratono Yasuyuki , Shinomiya Chiro
Published: July 2006

Antimony tribromide and a molecular compound between antimony tribromide and benzene (2:1) have been irradiated to provide 82mBr sources. The results obtained by the dissolution of the irradiated molecular compound, by means of which technique the chemical effects of 81Br(n,γ)82gBr and 82mBr(I.T.)82Br were determined separately, had shown very low organic yields from either (n,γ) or (I.T.) excitation. The reaction of 82mBr(I.T.)82Br in benzene showed a growth in the organic yields. Moreover, the organic yield of 82Br was lower when the system was frozen than when it was stored as a liquid. These results are explained by assuming that, in the frozen system, the antimony tribromide (82mBr) forms a molecular compound with the benzene. The higher organic yields in the frozen systems than those in the molecular compound itself must be due to the formation of free bromine (82mBr), which turns out to be an organic radiobromide. The hydrolytic behavior of the irradiated antimony tribromide and the molecular compound supports the idea of the presence of free bromine (82mBr) at the end of the irradiation.
Mass Spectra of Diaryl Disulfides, Diaryl Thiolsulfinates and Diaryl Thiolsulfonates
Authors: Kozuka Seizi , Takahashi Hideo , Oae Shigeru
Published: July 2006

The mass spectra of diaryl disulfides, diaryl thiolsulfinates and diaryl thiolsulfonates have been studied by analyzing metastable peaks and mass numbers. The main fragmentation observed for the disulfides was the cleavage of the S–S bond while the fragmentation of thiolsulfinates was similar to that of disulfides after elimination of oxygen. In the case of thiosulfonates, however, no such deoxygenation was observed, formation of sulfonium ion and one oxygen migration from the sulfone sulfur to the thiol sulfur were observed. Formation of thiabenzonium ion was observed in the mass spectra of sulfinates and sulfonates.
The Reactions of 80Br Activated by Isomeric Transition in the Gaseous Phase. The Isotopic Variation between CH4 and CD4
Authors: Tachikawa Enzo , Kahara Toshiki
Published: July 2006

The roles of the excess kinetic energy and the thermal ionic processes in the reaction of the 80Br from the isomeric transition of 80mBr in gaseous CH4 and CD4 were investigated using a rare gas additive. A possible isotope effect has appeared on the substitution reaction of the energetic Br atom to form CH380Br or CD380Br, but not on the thermal processes to form CH380Br and CH280BrBr or their isotopic alternatives. At a zero mole fraction of moderator, the CH380Br/CD380Br ratio for the energetic process was found to be 2.7±0.3. This is consistent with the moderator and/or probability integral isotope effects. However, in a highly moderated system the results indicated that the former effect is more important than the latter. Furthermore it can be inferred from the total pressure effects on the energetic reaction products that the excited primary products are able to decompose unimolecularly due to internal excitation.
Syntheses of Benzo[e]-1,3,4-triazepine Derivatives from 2-Aminobenzophenones
Authors: Ishiwaka Takumi , Sano Mitsuru , Isagawa Kakuzo , Fushizaki Yasaburo
Published: July 2006

2-Aminobenzophenone semicarbazones (II) or 2-aminobenzophenone phenylhydrazones (III) were cyclized to 3,7-disubstituted 5-phenyl-2,3-dihydro-1H-benzo[e]-1,3,4-triazepines (IV) by treating them with paraformaldehyde. On the other hand, 3,7-disubstituted 2-oxo-5-phenyl-2,3-dihydro-1H-benzo[e]-1,3,4-triazepines (V) were prepared by the fusion of II at 190–195°C or by the treatment of III with phosgene. In the latter reactions, 1-carboxy derivatives (VI) of V were obtained by using two equimolar amounts of phosgene. Vf was treated with sodium ethoxide to give a ring-cleavage product, 5-chloro-2-ethoxycarbonylaminobenzophenone phenylhydrazone (VIIIf), which was then fused to afford 6-chloro-1,2-dihydro-2-oxo-4-phenylquinazoline (VIIb).
The Chemical Behavior of Low Valence Sulfur Compounds. III. Production of Ammonium Sulfamate by the Oxidation of Ammonium Thiosulfate
Authors: Naito Kunishige , Yoshida Masahiro , Shieh Mu-Chang , Okabe Taijiro
Published: July 2006

The oxidation of ammonium thiosulfate with compressed oxygen in aqueous ammonia solution was examined. It was found that ammonium sulfamate and ammonium sulfate are mainly produced and a small amount of nitrite and imidodisulfonate obtained in the final solution. The most suitable conditions to produce ammonium sulfamate from ammonium thiosulfate industrially are as follows: reaction temperature 100°C, oxygen pressure 50 kg/cm2, concentration of ammonia 16 mol/l, concentration of cupric ion 0.1–0.2 mol/l. The electrolytic oxidation, hydrogen peroxide oxidation and ozone oxidation of ammonium thiosulfate were also examined.
Studies of the Behavior of Trivalent Uranium in an Aqueous Solution. III. Extraction from a Hydrochloric Acid Solution by Bis(n-butyl) Orthophosphoric Acid and by Bis-(2-ethylhexyl) Orthophosphoric Acid
Authors: Sat\={o} Akiko , Suzuki Shin
Published: July 2006

The distribution of U(III) between hydrochloric acid solutions and benzene solutions of bis(n-butyl) orthophosphoric acid or cyclohexane solutions of bis(2-ethylhexyl) orthophosphoric acid has been investigated by using the uranium-237 isotope as a tracer. It has been found that the log-log plot of the distribution ratio vs. the concentration of dimeric organophosphoric acids, and that of the distribution ratio vs. the hydrogen ion concentration, always show a good linearity, with a slope of 3. This indicates that the complex-forming reaction is as follows:

U^3++3(HA)_2\ightleftarrowsU(HA_2)_3+3H^+

where (HA)2 represents the dimeric solvent, (HDBP)2 or (HDEHP)2. The above results are in agreement with the conclusions reached in the cases of other trivalent actinide and lanthanide elements by other investigators.
Mass Spectra of Phenyl p-Toluenesulfonates. Substituent Effect in Fragmentation
Authors: Kozuka Seizi , Takahashi Hideo , Tamagaki Seizo , Oae Shigeru
Published: July 2006

Mass spectra of substituted phenyl p-toluenesulfonates were analyzed with the aid of metastable peaks. Three steps in fragmentation were suggested as the main processes for these compounds i.e., the initial S–O bond cleavage giving sulfonylcation, the second desulfonylation and the final loss of acetylene. Effect of substituent on the rate of the decomposition was observed in these three steps. The results are discussed in terms of various internal energies of the initial fragment ions. Apparently, the rates of the initial decomposition depend on the nature of the substituents.
Reaction of Sulfoxides with Acylating Reagents. III. Mechanism of the Reactions of Phenyl Methyl Sulf oxide with Acetic Anhydride
Authors: Kise Masahiro , Oae Shigeru
Published: July 2006

The Pummerer reaction, viz., the reaction of sulfoxides having at least one methyl or methylene group with carboxylic acid anhydride gives α-acyloxy derivatives of the corresponding sulfide. Earlier, we suggested on the basis of 18O tracer experiments with 18O-labeled acetic anhydride that the Pummerer reaction of dimethyl sulfoxide with acetic anhydride proceeds through an intermolecular nucleophilic attack of acetoxy group on the methylene carbon of the ylide-ylene intermediate. Noticeable acetoxy interchange has been found to take place during a similar Pummerer reaction of aryl methyl sulfoxide. However, the Pummerer reaction is the main path when the reaction with acetic anhydride is performed at around 120°C. In the Pummerer reaction of aryl methyl sulfoxides, the substituent effect is large (ρ=−1.6) and the kinetic isotope effect (kH/kD) is also substantial, i.e., 2.9. The reaction is assumed to involve the initial acetylation and the subsequent slow proton removal steps. Addition of sodium perchlorate or acetic acid accelerates the acetoxy exchange reaction rather than the Pummerer reaction.
Anionic Copolymerization of Butadiene and 1,1-Diphenylethylene
Authors: Yuki Heimei , Okamoto Yoshio
Published: July 2006

The anionic copolymerization of butadiene (M1) and 1,1-diphenylethylene was investigated in tetrahydrofuran (THF) and benzene, using n-butyllithium (n-BuLi), Na-naphthalene, and Na-and K-dispersions as initiators. An alternating copolymer was formed in THF, where the reaction proceeded without termination and chain-transfer reactions. The monomer reactivity ratios, r1 were 0.13 (Li+), 0.09 (Na+), and 0.09 (K+) in THF at 0°C. The r1 values in benzene at 40°C were 54 (Li+), 0.71 (Na+), and 0.10 (K+). The order of rate constants in THF was k12>k11>k21; the last of these was 0.27m−1 sec−1, with n-BuLi at 0°C.
Studies on Hydrogenolysis. LVI. The Effect of Solvent and Additive on the Stereochemistry of Catalytic Hydrogenolysis of 2-Methyl-2-phenylaziridine Derivatives
Authors: Sugi Yoshihiro , Mitsui Sekio
Published: July 2006

In order to assess the effects of solvent and additive on the stereochemical course of the catalytic hydrogenolysis of styrene imine derivatives, the hydrogenolysis of optically active 2-methyl-2-phenylaziridine (Ia), 1,2-dimethyl-2-phenylaziridine (Ib), and l-acetyl-2-methyl-2-phenylaziridine (Ic) was carried out under various conditions. The hydrogenolysis of la and Ib over palladium hydroxide occurred preferentially with an inversion of the configuration in ethanol, but with a retention in benzene. Moreover, Ia was hydrogenolysed with a predominant inversion of the configuration in n-hexane, and the inverted product increased with a decrease in the adsorption strength of the hydrocarbon solvent. The hydrogenolysis of Ic, however, occurred with a significant inversion of the configuration in both ethanol and benzene. The addition of sodium hydroxide to the reaction mixture strongly promoted a retention of the configuration in the hydrogenolysis of Ia over palladium hydroxide, and finally Ia was hydrogenolysed with a stereospecific retention. In contrast, no such variations could be observed in the cases of Ib and Ic. The stereoselectivity was not affected significantly by the addition of sodium hydroxide in the Raney nickel-catalyzed hydrogenolysis of Ia. However, the addition of sodium hydroxide prompted a retention of the configuration in the case of Ib. These results can be explained consistently by the previously-proposed mechanism.
Reaction of Cobalt Hydrotetracarbonyl with Acetylene
Authors: Iwashita Yuji , Tamura Fumihide , Wakamatsu Hachiro
Published: July 2006

The reaction of cobalt hydrotetracarbonyl with acetylene was carried out in methanol as a model of the carboxylation of acetylene. The complexes formed in this reaction were identified by means of IR, NMR, EA and molecular weight measurement. The main product was acetylene dicobalt hexacarbonyl. From the decomposition reaction of this complex in ethanol, ethyl acrylate, ethyl propionate and diethyl succinate were obtained. The yield of ethyl acrylate increased in the presence of carbon monoxide. The reaction course from acetylene to acrylate was examined.
Magnetic Susceptibilities of Chloroform Mixtures
Authors: Gopalakrishnan R
Published: July 2006

Magnetic susceptibilities of nine typical liquid mixtures were determined as a function of concentration. Deviations from an additive law were observed for these mixtures of chloroform with triethylamine, aniline, pyridine, α-picoline, 2,4-lutidine, diphenyl ether, toluene, nitrobenzene and chlorobenzene. The observed deviations are explained on the basis of hydrogen bond formation.
Photo-Ionization of Molecules in Solutions. VI. Studies on the Photo-current Arising from the Flash-Excitation of Aromatics in Solutions
Authors: Imura Takeshi , Yamamoto Naoto , Tsubomura Hiroshi
Published: July 2006

A technique is described for the study of the photocurrent due to the transient ionic species produced by the flash photolysis of aromatics in solutions at room temperature. The technique has proved to give valuable information in a way complementary to conventional flash spectrometry. The photo-ionization of N,N,N′,N′-tetramethyl-p-phenylenediamine was studied by this method in polar and non-polar solvents. The photocurrents of the solutions of some electron donor-acceptor systems were also measured, and the results were compared with that obtained from flash spectrometry. The recombination rate constants of the ionic species were estimated from the decay of transient photocurrents.
Macro Chelate Rings. III. Syntheses and Configurations of Complexes of New Ligands, 4,4′-Dimethyl-2,2′-bis(salicylideneaminomethyl)-diphenyl Ether and 4,4′-Dimethyl-2,2′-bis(salicylideneaminomethyl)diphenylamine
Authors: Okawa Hisashi , Koyama Hiroyuki , Inazu Takahiko , Yoshino Tamotsu
Published: July 2006

Two quadridentate chelating agents, 4,4′-dimethyl-2,2′-bis(salicylideneaminomethyl)diphenyl ether and 4,4′-dimethyl-2,2′-bis(salicylideneaminoinethyl)diphenylarnine, which may form a metal complex with a ten-membered chelate ring, were synthesized by a sequence of steps. The cobalt(II), nickel(II), copper(II), and zinc(II) complexes could be derived from the ligands. Their configurations around the central divalent metal ion were explored on the basis of the absorption in the ligand field in a solution. A tetrahedral configuration for cobalt(II) complexes as well as the zinc(II) complexes, and a pseudo-tetrahedral configuration for the nickel(II) and copper(II) complexes, were concluded.
Chlorofluorination of Carbon Disulfide and Sulfur
Authors: Abe Takashi , Nagase Shunji , Kodaira Kazuo , Baba Hajime
Published: July 2006

Chlorofluoromethanes and sulfur hexafluoride were obtained in good yields by the electrochemical fluorination of carbon disulfide in the presence of chlorine. The yields and compositions of the products were altered by the amount of chlorine fed in during electrolysis and also by the concentration of sulfur or carbon tetrachloride dissolved in carbon disulfide. Tetrafluoromethane, trifluoromethylsulfur pentafluoride, difluoromethylene bis-(sulfur pentafluoride), bistrifluoromethyl disulfide, and chlorodifluoromethylsulfur pentafluoride were also among the products. Further, the electrochemical fluorination of elementary sulfur was accomplished by the application of the technique of chlorofluorination, and sulfur hexafluoride was obtained in a reasonable yield. The chlorofluorinations of methyl sulfide and methyl disulfide were also attempted, but they afforded only chlorotrifluoromethane in poor yields.
On the Mechanism of the Vinyl Transetherification Reaction Catalyzed by Mercuric Acetate
Authors: Yuki Heimei , Hatada Koichi , Nagata Kazuhiko
Published: July 2006

The vinyl interchange reaction of methyl vinyl ether and methanol, methanol-d4, or ethanol catalyzed by mercuric acetate has been studied. Some organomercuric compounds have been isolated from the reaction mixture, and their catalytic activity for the interchange reaction has been examined. From these results, the mechanism proposed by Watanabe and Conlon (J. Amer. Chem. Soc., 79, 2828 (1957)) has been confirmed and further details of the reaction mechanism are discussed.
Reactions of Haloferrocenes. II. Kinetic Studies of the Reaction of Haloferrocene with Copper (I) Chloride - Pyridine Complex
Authors: Sato Masaru , Motoyama Izumi , Hata Kazuo
Published: July 2006

The reaction of bromoferrocene with copper(I) chloride - pyridine complex was found to be second-order, that is, first-order in each of bromoferrocene and copper(I) chloride-pyridine complex. The results obtained from the competitive reactions between bromoferrocene and bromobenzene indicated that bromoferrocene was 103 times more reactive than bromobenzene in the halogen-exchange reaction. The effects of the pyridine bases on the halogen-exchange reaction of bromoferrocene were examined, and the trend of the results was found to be different from that of bromobenzene. The reason for this was discussed on the basis of the reaction mechanism.
Tri(hetero)substituted Carbonium Ions. II. 2-Dialkylamino-1,3-dithiolanylium Ions. Reactions with Nucleophiles and Ambident Behaviors
Authors: Nakai Takeshi , Okawara Makoto
Published: July 2006

The reactions of 2-dialkylamino-1,3-dithiolanylium perchlorates with a variety of nucleophilic species including oxygen, sulfur and nitrogen nucleophiles have been investigated. Examination of the isolated products reveals that these trihetrosubstituted carbonium ions behave as ambident electrophiles toward nucleophiles with two reactive sites, i.e., the electron-deficient centered carbon (a) and the ring-methylene carbon atom (b), and that the nature of nucleophiles greatly affects the reaction course in a straightforward manner. The reaction course may be classified as follows. If the nucleophile is basic, the reaction at the site (a) (mode A) is favored, but if it has large sub-stituents, the initial proton abstraction reaction (mode C) is predominant, while if the nucleophile is polarizable, the reaction at the site (b) (mode B) is favored. The major factor deciding the reaction course is discussed in terms of the schematic energy profile of the overall reaction.
Synthetic Studies on Bacitracin. VII. Isomerization of Amino Acid Components of Thiazoline Peptides
Authors: Hirotsu Yoshihiro , Shiba Tetsuo , Kaneko Takeo
Published: July 2006

Ethyl 2-(1-benzyloxycarbonylaminoethyl)-R-Δ2-thiazoline-4-carboxylate (III), ethyl 2-(1-benzyloxycarbonylamino-2-methyl-n-butyl)-R-Δ2-thiazoline-4-carboxylate (VI) and their acid amide derivatives (V, VII and VIII) were prepared by either the iminoether coupling method or the dehydration method. As a general character of thiazoline peptide, it was found that the amino acid residue connected to thiazoline ring at N-terminal side is completely racemized at the stage of thiazoline ring formation, and further epimerized, in the case of isoleucine, by treatment with the basic reagent.
The Molecular Structure of Tin Tetrachloride as Determined by Gas-electron Diffraction
Authors: Fujii Hideji , Kimura Masao
Published: July 2006

The molecular structure of tin tetrachloride was determined by the sector-microphotometer method of gas-electron diffraction. By taking into account the phase-shift for the Sn-Cl pair, the following results were obtained: the tetrahedral structure with rg(Sn–Cl)=2.2808±0.0037 Å, l(Sn–Cl)=0.0499±0.0033 Å, and l(Cl···Cl)=0.1086±0.0050 Å. These values, especially that of the mean amplitude, l(Sn–Cl), are different from those previously reported by other workers. This is because the effect of the phase shift was neglected in the previous investigations.
Variational Calculation of Atoms and Molecules by a Modified Hassé Method Using Hulthén Functions. I. Hydrogen and Helium Atoms
Authors: Yamabe Tokio , Ishimaru Shingo , Fukui Kenichi
Published: July 2006

A modification of the Hassé method is presented in an attempt to describe perturbed systems. This method resolves divergence difficulties which are often encountered when the simple Kirkwood-Hassé method or Unsöld approximation is used for the coulombic perturbation problems. The procedure is illustrated for the perturbed hydrogen atom; energy values which are close to the exact ones are thus obtained. The method is also applied to the case of the ground-state helium atom; a closed-form expression of the energy is thus derived. The optimized value is −2.8983 a. u. Some other discussions are given in connection with the perturbation theory.
Oxidation of Vanadium(II) by Nitrate Ion
Authors: Tanaka Kazuyoshi
Published: July 2006

The oxidation rates of vanadium(II) to vanadium(III) by nitrate ion were determined from the time dependence of the polarographic diffusion currents. As supporting electrolytes sodium perchlorate and sodium sulfate were used. The oxidation rates were linearly dependent on hydrogen ion concentration in strongly acidic solutions (pH<2) and independent in weakly acidic solutions (pH<2). Polarographic half-wave potentials, reversibility and diffusion currents indicated that vanadium(II) in sulfate medium formed a sulfato-complex or an ion-paired species which was oxidized faster than V2+ (hydrated) in perchlorate medium. The oxidation in sulfate medium proceeded mainly by a single two-electron oxidation, and further reaction between vanadium(II) and vanadium(IV) yielded a stable dimer of vanadium(III) detected by absorption experiments. The rates measured in various halide solutions, except fluoride, gave almost the same rate constants in perchlorate medium. The gaseous products from nitrate ion were identified as NO and N2O by infrared spectrum measurements. The overall oxidation was proposed;

8V(II)+2NO_3^-+10H^+→8V(III)+N_2O(g)+5H_2O
Pyrolysis-Gas Chromatographic Analysis of Vinylchloride-Vinylacetate Copolymer
Authors: Okumoto Tadaoki , Takeuchi Tsugio , Tsuge Shin
Published: July 2006

Pyrolysis-gas chromatography was applied to rapid and precise determination of vinylchloride-vinylacetate copolymer by use of the yields of acetic acid and of benzene. The separation column was filled with packing of polymer beads (porapak Q) which are free from deterioration by hydrogen chloride evolved during the thermal degradation of copolymers. Relative yields of acetic acid, which originated from the side chains of the polymer and corresponded to vinylacetate content, and of benzene, formed mainly from successive vinylchloride units, were calculated from the relative peak area appearing on the pyrogram by making relative sensitivity correction for the flame ionization detector. By this method the composition of copolymer can be determined using 0.5–2.0 mg of sample with mean absolute deviation 0.5–0.4 wt%, with the yields of acetic acid and of benzene.
Application of the AC Polarographic Method to the Microdetermination of the Sulfide Ion by the Methylene Blue Procedure
Authors: Hasebe Kiyoshi , Kambara Tomihito
Published: July 2006

A new AC polarographic method utilizing the methylene-blue procedure was used for the determination of the sulfide ion. By means of dimethyl-p-phenylenediamine sulfate and iron(III) alum, the sulfide ion is converted quantitatively into methylene blue in the sulfuric-acid milieu. The methylene blue thus formed shows a prominent and reproducible AC peak, which can be suitably utilized for the indirect microdetermination of the sulfide ion. Halide ions interfere with the determination, however.
Reactions of Some Olefins with N-Chlorourea in the Presence of Acetonitrile
Authors: Wada Yasuo , Oda Ryohei
Published: July 2006

A new three-component reaction of N-chlorourea, olefins and acetonitrile is reported. Styrene gives N-(1-ureidoethylidene)-2-choro-1-phenylethylamine, N-(2-chloro-1-phenylethyl)acetamide and 4-phenyl-2-oxazolidone. Addition proceeds in a Markovnikov manner as shown by structural evidence. Cyclohexene gives N-(1-ureiodoethylidene)-2-chlorocyclohexylamine and N-(2-chlorocyclohexyl)acetamide. The stereochemistry of the reaction has been shown to be trans as demonstrated by chemical and physical evidence. Mechanisms for the reaction are proposed.
Application of the Continuous Variation Method to the Conductometric Determination of Formation Constants–Hexamminecobalt(III) Chloride - Sodium Sulfate and Tris(ethylenediamine) cobalt(III) Chloride - Sodium Sulfate Systems
Authors: Katayama Shunzo , Tamamushi Reita
Published: July 2006

The conductance behavior of mixtures was investigated with the following systems in aqueous solutions of various ionic strengths at 25°C; NaCl - KCl, NaCl - NaClO4, NaCl - Na2SO4, [CO-(NH3)6] Cl3 - Na2SO4 and [CO(en)3]Cl3 - Na2SO4. Appreciable deviations of the measured conductivities from additivity were observed in the last two systems involving the cobalt(III) complexes. The deviation was attributed to the ion-pair formation of the complex cations with sulfate ions; the ion-pair formation constants at various ionic strengths were determined by means of computer analysis of the deviation without relying on the Onsager conductance equation. The thermodynamic ion-pair formation constants at 25°C were as follows: logK=3.53 for [CO(NH3)3+·SO42− and logK=3.60 for [CO(NH3]3+·SO42−. The analysis of conductance behavior of mixtures was proved to be a useful method of studying ion-pair formation particularly at relatively high ionic strengths.
Electronic Absorption Spectra and Electronic Structures of Some Würster’s Blue Salts
Authors: Sakata Tadayoshi , Nagakura Saburo
Published: July 2006

Electronic absorption spectra were measured at various temperatures for Würster’s blue iodide, bromide, and chloride. The charge-transfer bands were found to be strongly dependent upon temperature. Concerning the iodide, the temperature dependency can be explained quantitatively, or at least semiquantitatively, by the aid of the linear Ising model in relation to the local ordering of the electron spins of Würster’s blue cation radicals. This model gives the exchange energy of 99±23 cm−1 for the iodide. For the bromide and the chloride, the dimer model was successfully applied to the analysis of the temperature dependence of the charge-transfer bands, giving singlet-triplet energy separations of 248±30 cm−1 and 255±30 cm−1 for the bromide and the chloride, respectively. The electronic structure and the intermolecular interaction were discussed for these radical salts, their electronic absorption spectra being compared with one another.
Metal Chelates of Some β,δ-Triketone Homologues. Copper(II) Chelates of 2,6-Diacetyl-4-methylphenol, 2,2′-Dihydroxybenzophenone, 2-Acetoacetylphenol and 2-Acetyl-1,8 -dihydroxynaphthalene
Authors: Taguchi Yoshio , Sagara Fumio , Kobayashi Hiroshi , Ueno Keihei
Published: July 2006

Copper(II) chelates of 2,6-diacetyl-4-methylphenol, 2,2′-dihydroxybenzophenone, 2-acetoacetylphenol and 2-acetyl-1,8-dihydroxynaphthalene were synthesized. The first and last ligands give only a mononuclear chelate of type CuL2 respectively, whereas the second and third ones give a binuclear complex of type Cu2L2 in addition to the mononuclear complex. In the cases of the latter ligands two types of complexes are interconvertible and in a solution phase there exists an equilibrium between them. Higher temperature favors a binuclear form and lower temperature another form. Structures of the complexes are assigned with spectroscopic and thermogravimetric data.
Studies of Thin-layer Chromatography of Inorganic Salts. IV. Chromatographic Behavior of Square Planar Complexes in Comparison with that of Octahedral Complexes
Authors: Baba Tetsuo , Yoneda Hayami
Published: July 2006

The chromatography of copper(II) and platinum(II) complexes on silica gel was investigated in comparison with that of cobalt(III) and nickel(II) complexes. Each complex showed various Rf values from zero to unity, when it was developed with aqueous solutions of various salts. This was interpreted to be due to different degrees of anionic association with the complex. The pattern of deversity of Rf values in copper(II) and platinum(II) complexes was found to be definitely different from that in cobalt(III) and nickel(II) complexes. Thus, different association mechanisms were proposed for both cases. In copper(II) and platinum(II) complexes, association occurs through the direct coordination of the anion to the metal ion, while, in cobalt(III) and nickel(II) complexes, association takes place at the outer-sphere of the complex.
The Codimerization of Styrene with Ethylene Catalyzed by Olefin-palladium(II) Chloride Complexes
Authors: Kawamoto Keiji , Imanaka Toshinobu , Teranishi Shiichiro
Published: July 2006

The codimerization of styrene with ethylene catalyzed by the olefin-palladium chloride complexes was investigated in a homogeneous system under mild conditions; di-μ-chloro-dichlorobis-(styrene)dipalladium(II), (Pd(C6H5CH=CH2)Cl2)2, was found to be an effective catalyst. When ethylene was bubbled into a styrene solution containing the styrene-palladium complex at 50°C for 6 hr, codimers including trans-1-phenyl-1-butene, cis-1-phenyl-1-butene, and trans-1-phenyl-2-butene were obtained in 1278, 57 and 170% yields respectively, based on palladium(II) used. However, the absence of ethylene resulted in the formation of a 70% yield of the dimer of styrene, trans-1,3-diphenyl-1-butene. The order of the solvent effect on the rate of the codimerization was as follows: nitrobenzene>nitromethane>acetic acid, phenol>dioxane>>benzene>>acetonitrile. A possible mechanism for this reaction was discussed on the basis of the present results.
Imidazole Catalyses in Aqueous Systems. IV. Bimolecular and Michaelis-Menten-Type Catalyses of a Phenyl Ester Hydrolysis by Some Hydrophobic Imidazole Derivatives
Authors: Kunitake Toyoki , Shinkai Seiji
Published: July 2006

Catalytic hydrolyses of p-acetoxybenzoic acid by several imidazole derivatives were conducted at 15–40°C in aqueous systems using a pH-stat. Imidazole compounds containing the naphthalene ring catalyzed the hydrolysis following the Michaelis-Menten kinetics as in enzymatic reactions, while catalysis by less hydrophobic imidazoles followed the second-order kinetics. Enhancement of the overall catalytic efficiency in the Michaelis-Menten pathway was estimated to be ten times at most as compared with the bimolecular pathway. The thermodynamic and activation parameters were obtained at 15–40°C for the Michaelis-Menten pathway. The binding of catalyst and substrate was characterized by small positive enthalpy changes (ΔH≅+3.5 kcal/ mol) and large positive entropy changes (ΔSu≅+28 eu), indicating that the complex formation was ascribable to hydrophobic interactions. The intra-complex product formation was characterized by not unreasonable ΔH≠ values and extraordinarily large negative ΔS≠ (≅−50 eu) values. The unexpectedly small rate enhancement in the Michaelis-Menten pathway was attributed to the unfavorable ΔS≠ term, which suggested that the structure of the Michaelis complex was quite different from that of the transition state of the product formation.
Kinetic Studies of Adsorbed Films of Tritium-labelled Sodium Stearate at the Air/Water Interface
Authors: Seimiya Tsutomu
Published: July 2006

The adsorption of tritium-labelled sodium stearate at the air/water interface was directly measured radiometrically using an ultra-thin-windowed Geiger-Müller tube for varying soap concentrations, pH values, and temperatures. The changes in the amount of adsorption and in the surface tension were simultaneously traced with the lapse of time. The pressure-area curve was then obtained by the successive plotting of the surface pressure against the area at the same aging; the curve at equilibrium was also obtained. Thus, the pressure-area relationship of the adsorbed monolayer was automatically measured during the course of adsorption approaching equilibrium. A close resemblance was observed between the monolayer of stearic acid on-neutral water and the adsorbed films on the stearate solution of pH values from 8.85 to 9.30 at 30°C. The amount of adsorption measured for an alkaline solution often exceeds the value to be expected from the saturation value for a completely-ionized stearate monolayer. The pressure-area characteristics suggested a transition from the condensed state of the adsorbed film at a higher surface concentration to an expanded state at a lower concentration. It was also confirmed, by measuring the amount of adsorption in the atmospheres of both nitrogen and air containing carbon dioxide, that the atmospheric carbon dioxide acts to increase the adsorption of stearic acid on the aqueous surface. The diffusion coefficient of the adsorbing solute, calculated from the initial rate of adsorption, showed a smaller value than that obtained by conductometric measurements.
Ionic Dissociation. II. An Extended Hückel Treatment of the Dissociation of Pseudo Acids
Authors: Yamabe Hiroko , Kato Hiroshi , Yonezawa Teijiro
Published: July 2006

The electronic structures of several pseudo acids are studied, in connection with their reactivity and stability, by the Extended Hückel method. The linear relationship between the observed pKa value and the change in the calculated electronic energy, ΔE, in the course of the dissociation of the pseudo acids is also observed. The order of the stability of the carbanion, referred to its parent acid, as estimated from our calculations, is; CH2NO2−>CH2COCH3−>CH2CN−. Di- or tri- substituted carbanions should be more stable. This order is parallel with that of the electron-attracting abilities of the groups adjacent to the methylene group. The highest-occupied MO of the carbanion is remarkably unstable, resembling a lone-pair level, and the atomic orbital population of that MO is large at the Pz AO of the carbon. This reflects the high reactivities of the carbanion as a reaction intermediate; the electrophilic addition probably takes place at the carbon atom.
Group Interactions in Polyelectrolytes. III. The Electrostatic Effect of Neighboring Groups on the Ionization of Polyelectrolytes
Authors: Kawabe Hiroshi , Yanagita Masaya
Published: July 2006

The two parameters in the modified Henderson-Hasselbach equation, pH=pKa−n′log-[(1−α)⁄α], where pKa and n′ are empirical constants and where α is a degree of the ionization of a polymeric acid, were evaluated on the assumption that the ionization of polyelectrolytes is electrostatically affected in the main by a few neighboring ionized groups and that the over-all ionization is composed of only a few elementary ionization. The titration curves of various polyelectrolytes in the absence of salt could be classified into two types: ΔpK′≥2 and ΔpK′<2, where ΔpK′ is the difference between the succeeding ionization constants. The maleic acid-styrene copolymer and polyvinyl amine belong to the former type, while polyacrylic acid and pectinic acid belong to the latter. In the former, a plot of pH against log[(1−α)⁄α] nearly falls on a line in only a limited range and n′ is substantially equal to the number of elementary ionizations. In the latter, both pKa and n′ are related to the distance between the groups. The titration curve of polyacrylic acid, drawn by means of the above equation with the parameters calculated on the basis of the kinetic data of the alkaline hydrolysis of polymethyl acrylate, was in good agreement with the observed titration curve. The titration data of other polyelectrolytes also fall nearly on their calculated titration curves.
A Theoretical Consideration of the Electron-scavenging Process in Liquid Hydrocarbons
Authors: Yamazaki Hideo , Shinsaka Kyoji
Published: July 2006

The electron-scavenging process by a scavenger and the random recombination between ions and electrons in a spur in the radiolysis of nonpolar hydrocarbons have been investigated theoretically on the basis of the extended type of Smoluchowski equation. To obtain the approximate solutions, a model of the distribution of charged species in which a positive ion core is surrounded by electrons is assumed; several approximations are also made during the calculation. The reaction rate of the electron scavenging is expressed by the overlapping integral between the concentration of the electrons and that of the scavenger. The rate of the recombination reaction is approximately expressed as the total flux of the electrons flowing into the core of parent ions. The G value of electron scavenging shows a Langmuir-type dependence on the concentration of the electron scavenger. The values of the slope of the sigmoidal curve at the mid point and of the corresponding scavenger concentration almost agree with the experimental value.
Polarography of Halides in Dimethylformamide. V. Bromine and the Tribromide Ion
Authors: Matsui Yoshihisa , Date Yoshio
Published: July 2006

The polarographic behavior of bromine and the tribromide ion at the dropping mercury electrode was investigated in dimethylformamide. A freshly-prepared solution of bromine gives two cathodic waves. When the solution is allowed to stand at 25°C in the dark, however, the first wave gradually becomes anodic, independently of the electrolysis. When the first wave is completely anodic, an equilibrium is established. The resulting polarogram coincides with that of hydrogen tribromide. The formation of hydrogen tribromide was ascribed to the chemical reduction of bromine by dimethylformamide. Diffuse sunlight accelerates the decomposition of bromine, which in turn yields hydrogen bromide. It was also suggested that, when the dropping mercury is used as an indicator electrode, bromine and the tribromide ion may react with the dropping mercury prior to being electrolyzed, forming mercuric bromide and the tribromomercurate ion respectively, which may in turn depolarize the indicator electrode.
The Syntheses and Properties of the Benzothiazole or Benzimidazole Derivative Adducts of Tin(II, IV) and Antimony(III) Halides
Authors: Ouchi Akira , Takeuchi Toshio , Taminaga Iwao
Published: July 2006

The benzothiazole, 2-amino-benzothiazole, benzimidazole-2-thiol, and benzothiazole-2-thiol adducts of tin(II, IV) chlorides, antimony(III) chloride, and antimony (III) bromide with the formulae of Mn+LmXn− (where L is the ligand and where X is Cl or Br) were synthesized. From their electronic and infrared spectra, it can be seen that the 2-amino-benzothiazole adducts are more stable than those of other ligands and that the metal-ligand bonds in the former remain, even in the ethanolic solution.
Ion-exchange Chromatographic Analysis on the Chain Length of Polyphosphate Products
Authors: Matsuura Niro , Lin Tsin-ko , Kobayashi Yoshimitsu
Published: July 2006

The ion-exchange chromatographic technique was used in order to find the average chain number of a polyphosphate product. For the assignment of the nth polymer in the obtained chromatogram, the dependence of the distribution coefficient, Kd, on the eluent concentration examined by the use of both 20-cm and 60-cm resin columns. A lower series of polyphosphate was included in a relatively large amount in order that the average chain number based on the chromatographic analysis could be duly appreciated only for the case of basic polymers with lower molecular weights. For a product “Graham Salt” with a number of phosphate links, the higher series of polyphosphate could not be desorbed entirely from the resin column; the accurate estimation of the average number was, then, improbable. The viscosity method is also not advisable to use the computation of a mean polymerization number in the polyphosphate with a low molecular weight. An attempt was made to improve the data on the average chain number by the viscosity measurements together with the chromatographic analysis of the polymer constituent.
Compounds Related to Acridine. VII. The Synthesis of 9-Ethynylacridine and Its Reaction with p-Nitrosodialkylaniline
Authors: Tsuge Otohiko , Torii Akiyoshi
Published: July 2006

The dehydrobromination of 9-(1,2-dibromoethyl)acridine, which had easily been obtained by the bromination of 9-vinylacridine, to 9-ethynylacridine was attempted by several methods, and it has been established that this transformation can be effected in a 55% yield by the use of methanolic potassium hydroxide in dioxane. It has been found that the reaction of 9-ethynylacridine with p-nitrosodialkylaniline under the influence of hydrochloric acid in ethanol leads to the formation of the corresponding 1-(9-acridinyl)-1,2-bis(p-dialkylaminophenylimino)ethane N1,N2-dioxide. In addition, the configuration of the dioxide has also been proposed on the basis of spectroscopic studies and an inspection of the Dreiding models.
The Constituents of Hops. IV. The Volatile Composition of Humulus Lupulus L. var. cordifolius Maxim.
Authors: Naya Yoko , Kotake Munio
Published: July 2006

The steam-volatile constituents of Humulus Lupulus L. var. cordifolius Maxim, have been studied, and 66 compounds of the oil have been identified. Besides the previously-reported principal hop components (myrcene, β-humulene, caryophyllene, β-selinene, δ- and γ-cadinenes), evidence was found for the presence in an abnormally high concentration of others: zingiberene, α-curcumene together with β-bisabolene, and β-sesquiphellandrene, selina-3,7(11)-diene, and selina-4(14),7(11)-diene. A number of oxygenated sesquiterpenoids were detected. The major one was found to be caryophyllene-oxide. The isolated components were identified by spectroscopic or chemical means.
Nucleation in Liquid Sulfur Droplets
Authors: Hamada Shuichi , Nakazawa Yoshihiro , Shirai Toshiaki
Published: July 2006

The freezing behavior of supercooled liquid sulfur droplets were studied by means of a microscopic method. The number fraction of the solidified droplets in the experiments of continuous cooling on well-purified sulfur was only about 15% over the temperature range from 120°C to −70°C at the cooling rate of 0.20°C/min, and no abruptly discontinuous nucleation was found in these supercooling temperatures. The number fractions of the solidified droplets were found to be related to their volumes below −20°C. The nucleations in the well-purified liquid surfur droplets were confirmed to be a homogeneous process under these conditions. The specific nucleation rates per unit of volume were estimated to be 0.450, 1.13, and 1.16 cm−3sec−1 at the specified temperatures of −20, −40, and −50°C respectively. The dependences of (lnI+ΔFA⁄kT) on 1⁄(ΔT)2T obeyed the theory of Turnbull and Fisher. The interfacial free energy of sulfur at the liquid-crystal surface was estimated to be 12.1 erg/cm2; this value was considered to be an appropriate one according to the Zadumkin consideration.