bluuebunny/crossref_metadata_2025 huggingface dataset:
The Crystal Structure of Copper Yunainate Trihydrate, Cu(C5H8O3NS)2·3H2O
Authors: Furusaki Akio , Tomiie Yujiro
Published: July 2006

The crystal structure of copper yunainate trihydrate, Cu(C5H8O3NS)2·3H2O, has been studied by means of three-dimensional X-ray analysis. The crystal is monoclinic, with two formula units in a unit cell of the dimensions: a=15.94, b=6.33, c=8.60 Å, and β=95.6°; the space group is P21. The intensities were measured visually from equi-inclination integrating Weissenberg photographs taken with CuKα radiation around the b and c axes. The structure was elucidated by Sim’s method, and refined by the block-diagonal-matrix least-squares method, assuming anisotropic thermal motions for all the atoms. The final R factor is 9.2%. The copper atom is coordinated by imino nitrogen and carboxyl oxygen atoms of two yunainate groups, and a water oxygen atom. The first four atoms lie almost on a plane and make a square configuration of the trans type. The last one is bonded to the copper atom nearly in the direction of the normal of the plane. Thus, the coordination number of copper is five in the present crystal. Of the three sorts of water of crystallization, one is connected with the copper atom, as has already been mentioned, and the remaining two are lattice water, forming a hydrogen-bonded spiral chain around the screw axis. Further, these water molecules connect complex molecules to one another by their hydrogen bonds, forming a threedimensional hydrogen-bonded structure.
Kinetics of the Ligand Substitution Reaction of the Cobalt(II)-(Ethylene glycol)bis(2-aminoethyl ether)-N,N,N′,N′-tetraacetate Complex with 4-(2-Pyridylazo)resorcinol
Authors: Funahashi Shigenobu , Tanaka Motoharu
Published: July 2006

The kinetics of the ligand substitution reaction of the cobalt(II)-(ethylene glycol)bis(2-aminoethylether)-N,N,N′,N′-tetraacetate complex (Co(II)-EGTA) with4-(2-pyridylazo)resorcinol (PAR) have been studied photometrically in the pH range 8–9.4 at an ionic strength of 0.1 and at 25°C. The reaction proceeds simultaneously through two different reaction paths. Thus the rate law can be written as

\fracd[CoR_2^-]dt=k_1[CoY^2-][HR^-]+k_2[CoHY^-][HR^-]

where Y4− and R2− refer to tetravalent EGTA and divalent PAR respectively. Rate constants, k1 and k2 are 3.2m−1sec−1 and 2.1×104m−1sec−1. Possible mechanism for the substitution is discussed. The stability constants for mercury(II)-EGTA complexes and cobalt(II)-EGTA complexes are determined by the mercury electrode method at μ=0.1 and 25°C in order to analyze the substitution reaction: KHgY=1023.86±0.10, kHgHYH=103.06±0.10, KCoY=1012.3±0.1, KcoHyH=104.9±0.1, KCoH2YH=103.3±0.3.
Absorption Spectra of 2E States of Some Chromium(III) Complexes Revealed by Flash Method
Authors: Ohno Takeshi , Kato Shunji
Published: July 2006

Excited states of some chromium(III) complexes were studied by a flash technique at −196°C. Transient species with strong absorption bands in visible and near UV regions were observed to decay at the same rate as their phosphorescence for CrIII(acac)3, K3[CrIII(NCS)6], NH4[CrIII-(NCS)4(NH3)2], and CrIII(exan)3. They are therefore 2E states (phosphorescent states). A strong absorption band for CrIII(acac)3 is assigned to a charge transfer transition from 2E state based on the intensity and energy of the transition. A transition to localized excited states in ligand with a small extinction coefficient was observed in near infrared region for CrIII(acac)3.
Macro Chelate Rings. II. Syntheses and Properties of 2,7-Dimethyl-4,5-bis(salicylideneaminomethyl)xanthone as a Quadridentate Chelating Agent and Its Metal Complexes
Authors: Okawa Hisashi , Yoshino Tamotsu
Published: July 2006

2,7-Dimethyl-4,5-bis(salicylideneaminomethyl)xanthone, a new quadridentate chelating agent, was synthesized by a sequence of steps and subsequently characterized. Some divalent metal complexes of the ligand were isolated, and their properties were characterized on the basis of infrared spectra. The non-coplanar structure of the complex derived from the ligand was suggested by the resolution of a cobalt(II) complex into optical isomers.
Syntheses of Benzodiazepine Derivatives
Authors: Motoki Shinichi , Urakawa Chikahiro , Kano Akio , Fushimi Yukio , Hirano T\={o}ru , Murata Katsumi
Published: July 2006

This communication deals with the syntheses of the aza-analogues of benzoheptafulvene. Acetylacetone or benzoylacetone reacted with benzophenone chloride in the presence of sodium ethoxide to form 3-(α-phenylbenzylidene)pentane-2,4-dione (XIVa) or 1-phenyl-2-(α-phenylbenzylidene) butane-1,3-dione (XIVc) respectively. Treatment of o-phenylenediamine with XIVa in acetic acid - ethanol resulted in forming 2,4-dimethyl-3-(α-phenylbenzylidene)-3H-benzo[b]-1,5-diazepine (XVa) which has a 3,6-diaza-4,5-benzoheptafulvene ring skeleton. Similarly, substituted o-phenylenediamines reacted with XIVa to give 7-substituted 2,4-dimethyl-3-(α-phenylbenzylidene)-3H-benzo[b]-1,5-diazepines (XVb)—(XVd). Reaction of XIVa with hydrazine gave only the monohydrazone of XlVa. The ketene dimer reacted with o-phenylenediamines to give 4-methyl-2,3-dihydro-2-oxo-1H-benzo[b]-1,5-diazepines (Xa)—(Xc). However, the condensation of Xa with aldehyde gave an undesirable product.
Effects of Additives on the Alternating Copolymerization of Aziridines with Cyclic Imides
Authors: Kagiya Tsutomu , Adachi Teruho
Published: July 2006

The effect of the addition of 2-methyl-2-oxazoline, which is an isomer of the growing chain end, was examined. The rate of the copolymerization of ethylenimine with succinimide increased upon the addition of 2-methyl-2-oxazoline. On the basis of this result and of the NMR spectrum of the copolymer, the mechanism of propagation via an activated state similar to oxazoline was proposed. The copolymerization was accelerated by the addition of sodium iodide, which is the catalyst of the isomerization of the growing chain end. The property of the copolymer obtained was different from that of the copolymer obtained without sodium iodide. Sodium iodide also affected the copolymerization of N-ethylethylenimine with succinimide, while it did not affect that of ethylenimine with N-ethylsuccinimide. The reduced viscosity of the copolymer increased with the reaction time. The reaction mechanism of the copolymerization in the presence of the catalyst was discussed on the basis of the facts mentioned above.
Spiro Compound Formation. IV. Acid-catalyzed Reactions of 2-Cyclohexylidenecyclohexanone Oxide
Authors: Nojima Masatomo , Hinoue Keniti , Tokura Niichiro
Published: July 2006

The reactions of 2-cyclohexylidenecyclohexanone oxide in the presence of (i) sulfuric acid, (ii) fluorosulfonic acid, (iii) boron trifluoride etherate, and (iv) antimony pentachloride have been studied. The products consisted of spiro[5.6]dodecane-7,12-dione, 2-(1-cyclohexenyl)-2-hydroxycyclohexanone, and 1,2,3,4,6,7,8,9-octahydrodibenzofuran. The ratio of the products was found to depend on the differences in the catalysts and solvents.
β-Ferrocenyl-α,β-unsaturated Ketones. II. The Reduction of β-Ferrocenyl-α,β-unsaturated Ketones and Their Relative Reactivities
Authors: Kono Hiromichi , Ishige Masayoshi , Sakai Koji , Shiga Mikio , Motoyama Izumi , Hata Kazuo
Published: July 2006

The catalytic reduction of several β-ferrocenyl-α,β-unsaturated ketones was investigated using Urushibara nickel A (U-Ni-A) or precipitated nickel (ppt-Ni) as the catalyst, and their relative reactivities toward the catalytic reduction were discussed in comparison with those of the phenyl analogs. Some anomalies observed in the NMR spectra of the reduction products was also discussed.
Studies of Diazosulfides. I. A Kinetic Study of the Reaction of Diaryldiazosulfides with β-Naphthol in Alkaline Ethanol
Authors: Yamada Takashi , Tanaka Nobuo , Morisawa Takao , Nishikuri Masao , Kaji Aritsune
Published: July 2006

It was found that diaryldiazosulfides (I) reacted at an appreciable rate with β-naphthol in alkaline ethanol to produce azo-dyes. This is contrary to Hantzsch’s observation. The initialrate constants of the reaction were determined at various temperatures. The electron-donating substituents accelerated the rate when they were in the N-aryl part of I (substituent X) but retarded when in the S-aryl part of I (substituent Y). A set of ρ-values which have opposite signs, ρx=−2.96 and ρY=3.93, suggested that the rate-determining step in this reaction is the heterolytic rupture of the N-S bond of I. This was supported by the negative values of the entropy of activation and by such a solvent effect as that the rate was significantly increased when the polarity of the solvent increased. As the change in the concentration of β-naphthol affected the rate, the possibility of the participation of the transition state or of the intermediate including β-naphthol was also discussed.
Hydrogenation and Hydrogenolysis. XII. The Hydrogenation of Isomeric Dimethoxybenzenes with Platinum Metal Catalysts
Authors: Takagi Yuzuru , Ishii Sadayoshi , Nishimura Shigeo
Published: July 2006

The catalytic hydrogenation and hydrogenolysis of isomeric dimethoxybenzenes over six platinum metals have been investigated at elevated temperature and pressure. The hydrogenolysis of methoxyl group occurred more extensively over Group VIII3 metals than over Group VIII2metals. The meta isomer hydrogenolyzed to greater extent and gave smaller cis/trans ratio of dimethoxycyclohexane, than the ortho and para isomers. The greater tendency of the meta isomer toward hydrogenolysis supports the previously proposed explanation according to which the electron-releasing group at meta position would promote hydrogenolysis.
Activity Coefficient of Sodium in Dilute Sodium and Gold Alloy at 1400°K
Authors: Hirota Kazushi , Katsura Takashi
Published: July 2006

The equilibria between the molten Na2CO3 and the Au-Na alloys were determined at 1400°K under CO+CO2 gaseous mixtures. The activity coefficient of Na in the Au-Na alloys was constantly 0.0392±0.0028 at concentrations ranging from 0.2 to 0.02 wt% Na.
Statistical Thermodynamics of Binary Liquid Mixtures
Authors: Arakawa Kiyoshi , Kiyohara Osamu
Published: July 2006

By means of the cell method and using the Sutherland type potential function for pair interactions between molecules, a statistical theory was formulated for binary liquid mixtures consisting of rigid spherical molecules differing in size. A formula was derived for cohesive energy as a function of the volume of liquid, and studied in combination with the radial distribution function. The applicability of the square-well type potential function within a cell was also examined. Formulas for excess thermodynamic functions were derived and their applicability investigated. For 22 binary systems consisting of nearly spherical molecules, excess thermodynamic functions were calculated and compared with data in literature. The results show that the theory is applicable to the mixtures.
The Crystal Structure of Quinolinium 2-Dicyanomethylene-1,1,3,3-tetracyanopropanediide, [2(C9NH8)+·(C10N6)2−]
Authors: Sakanoue Seiki , Yasuoka Noritake , Kasai Nobutami , Kakudo Masao
Published: July 2006

[2(C9NH8)+·(C10N6)2−] crystallizes in the form of the space group of Pbcn, with four formula units in the unit cell, and the following unit-cell dimensions: a=13.18, b=15.40, and c=11.56 Å. The structure was determined by obtaining phases directly from the structure-factor magnitudes by means of the symbolic addition procedure. For 1580 non-zero reflections, the final R is 0.147. The crystal structure shows that the packing unit is an “ion-pair” consisting of one di-valent anion and two mono-valent cations. The anion is sandwiched by two cations with weak charge-transfer interaction between them; the closest atomic contact is 2.99 Å. These units stack infinitely, forming a column, along the a axis. Between these stacking columns, there exists a hydrogen bond (N–H···N, 2.84 Å) along the b axis. The (C10N6)2− anion has a C2-2 symmetry; cyano-substituents are tilted out of the plane formed by four central carbon atoms, and the anion takes a propeller shape. The one arm is rotated 13° from the completely planar conformation, while the other two are rotated 24°. On the other hand, the (C9NH8)+ cation seems not to be planar.
Salt and Medium Effects on H− Indicators
Authors: Chattanathan N , Kalidas C
Published: July 2006

The activity coefficients of the molecular forms of a few nitrodiphenylamine indicators were determined by a solubility method in basic solutions of ethylene and propylene glycols. The medium effects on the ions of these indicators were also obtained by determination of the medium effects of their molecular forms separately by solubility measurements. Variation of the activity coefficients and the medium effects on the ions of the indicators are discussed.
The Spectroscopic Observation of the Selective Volatilization of Metal Solid Samples in a Nitrogen Plasma Flame
Authors: Oku Masaoki , Hirokawa Kichinosuke
Published: July 2006

Some metal solid samples were burned in a nitrogen plasma flame, and the spectrum intensity-time curves were spectrographically observed. The curves indicated that the fractional distillation of alloying elements was caused by the reactions of the solid-alloy sample and nitrogen gas. The fractional distillation was explained in terms of the difference in the stabilities of the metal nitrides. The distribution of the emission species and the temperature of the flame suggested that there were few chemical reactions in the flame or that the chemical reactions in the flame had little effect on the spectrum intensities. In an appendix, the method of line-pair selections for obtaining the correct temperature is considered.
Photon-Activation Analysis for Zirconium with Molybdenum Used as the Internal-Reference Element
Authors: Pung Tong-Chuin , Kato Toyoaki , Oka Yoshinaga
Published: July 2006

A method for the determination of zirconium has been studied by activation analysis with bremsstrahlung photons, with molybdenum used as the internal-reference element. This method is based on the γ-ray spectrometric measurement of the 89Zr activity produced by the 90Zr(γ,n) reaction and on the comparison of this activity with the 88Zr activity formed by the (γ,α) reaction on molybdenum. The reaction products and their rates of production in zirconium and in molybdenum have also been examined as functions of bremsstrahlung maximum energies up to 60 MeV, and the best conditions for the determination of zirconium are proposed. When the maximum energy was set at 20 MeV, no interfering reactions occurred; under the present experimental conditions, a zirconium content down to about 18 μg can be determined accurately. The reliability and the versatility of this method are demonstrated.
Studies of Ethylenediamine-N,N′-diacetatocobalt(III) Complexes. I. The Preparation and Some Properties of Ethylenediamine-N,N′-diacetatocobalt(III) Complexes, with Chloride, Water, Ammonia, Ethylenediamine, 1,10-Phenanthroline, and 2,2′-Dipyridyl as the Additional Ligands
Authors: Kuroda Kashiro , Watanabe Kiyokatsu
Published: July 2006

A series of cobalt(III) complexes containing the tetradentate ethylenediamine-N,N′-diacetate anion (EDDA) and chloride, water, ammonia, ethylenediamine, 1,10-phenanthroline, and 2,2′-dipyridyl as the ligands occupying the residual coordination positions have been prepared, and some of their physical and chemical properties have been examined. Two isomers have been isolated in the cases of the phenanthroline and dipyridyl complexes; they have been inferred to be the α-cis(pink) and the β-cis(red) isomers on the basis of their electronic absorption spectra. A new convenient route for the preparation of the series has been presented, a route which passes through the dichloro, chloroaquo, and diaquo complexes.
Synthesis and Properties of Two α-Phenylazostilbenes. A New Method for the Elimination of Water and p-Toluensulphonate Ion from Substituted Phenylhydrazones
Authors: Caglioti Luciano , Giumanini Angelo G
Published: July 2006

The synthesis of a linear azoalkene, α-phenylazostilbene (1), not conjugated to strong electron withdrawing groups is reported. α-(p-Methoxyphenylazo)stilbene (3) was prepared by a direct method. The mass spectra of 1 and 3 showed a rearrangement yielding positive ions of benzonitrile and benzaldehyde anils (7).
Anodic Reaction of 5-Alkyl-2-furoic Acids in Protic Solvents
Authors: Torii Sigeru , Tanaka Hideo , Ogo Hitosi , Yamasita Siro
Published: July 2006

Anodic oxidation of 5-alkyl-2-furoic acids (4 and 10) in protic solvents has been studied. The major products were 1-butenolides (12, 13, 16, and 17) and γ-keto esters (11 and 15) and their acids (14 and 18). Methyl 5-n-hexyl-2,5-dimethoxy-2,5-dihydro-2-furoate 19 was converted into γ-keto ester 11 and its acid 14 by hydrolysis with alkali and into 1-butenolide 12 by electrolysis of the alkaline solution. A possible mechanism of the anodic oxidation of 5-alkyl-2-furoic acids has been discussed.
Photochemical Reduction of Nitrobenzene and Its Reduction Intermediates. IX. The Photochemical Reduction of 4-Nitropyridine in a Hydrochloric Acid-Isopropyl Alcohol Solution
Authors: Hashimoto Shizunobu , Kano Koji , Ueda Kazuo
Published: July 2006

The photochemical reduction of 4-nitropyridine has been investigated in hydrochloric acid-isopropyl alcohol solutions. 4-Nitropyridine was not photoreduced in isopropyl alcohol, whereas when the photolysis was carried out in hydrochloric acid-isopropyl alcohol solutions, the photoreduction of 4-nitropyridine proceeded from its n,π* triplet state to give 4-hydroxylaminopyridine in a quantitative yield. The quantum yields for the disappearance of 4-nitropyridine in hydrochloric acid-isopropyl alcohol solutions increased with the concentration of hydrochloric acid up to 3.6×10−2 mol l−1 (Φ=0.27–0.94). These results suggest that the hydrogen abstraction of photoexcited 4-nitropyridine proceeds electrophilically because of the decrease in the electron density of the nitro group, in decrease resulting from the protonation of heterocyclic nitrogen and the n,π* excitation of the nitro group.
Oligomerization of Isoprene by Vanadium Catalysts
Authors: Uchida Yasuzo , Furuhata Ken-ichi , Ishiwatari Hisayasu
Published: July 2006

Oligomerization of isoprene by the catalyst system consisting of VO(OEt)3 and organoaluminum compounds was studied. Isoprene was oligomerized to a mixture of dimers, trimers and higher oligomers by VO(OEt)3–Et2AlCl catalyst system. 2,6-Dimethyl-1,trans-3,6-octatriene was the main dimer of isoprene in this reaction. The addition of tetrahydrofuran, dioxane, triphenylphosphine, bis-diphenylphosphinoethane, triethylamine or tetramethylethylenediamine to this catalyst system raised the reaction rate and the selectivity for the dimer at lower donor/VO(OEt)3 molar ratios but suppressed the reaction at higher molar ratios. By VO(OEt)3–Et3Al catalyst system, isoprene was converted to a liquid polymer and by VO(OEt)3–EtAlCl2 catalyst system, it was cyclopolymerized to an insoluble polymer. Structures of two new oligomers of isoprene were also reported.
The Reactions of Dihalogenoalkanes with Dimethyltin Bis-(N,N-dimethyldithiocarbamate) and Related Compounds
Authors: Tanaka Toshio , Tanaka Koji , Yoshimitsu Tokio
Published: July 2006

Dimethyltin-bis(N,N-dimethyldithiocarbamate), (CH3)2Sn[S2CN(CH3)2]2, reacts with dihalogenoalkanes to give 1,3-dithiacycloalkyl-2-dimethylimminium dimethyltin halides, (Remark: Graphics omitted.) (n=1 or 2; m=2, 3, or 4; X=Cl, Br, or I). On the other hand, the reactions between dimethyltin bis(N-methyl-N-phenyldithiocarbamate), (CH3)2Sn[S2CN(CH3)(C6H5)]2, and dihalogenoalkanes yield preferentially alkylene bis(N-methyl-N-phenyldithiocarbamate). The difference in reactivity between the two types of complexes is discussed. The infrared and NMR spectra indicate that the positive charge on the dithiacycloalkylimminium ions is more delocalized in the higher homologues. The configurations of dimethyltin trihalide and tetrahalide anions in the solid state and in solution are also presented on the basis of the infrared spectra; the results suggest that, in solution, dimethyltin trihalide anions are more likely to be formed than are dimethyltin tetrahalides.
The Pyrolysis of Halocyclopropanes at High Temperatures
Authors: Asahara Teruzo , Ono Katsumichi , Tanaka Kazuki
Published: July 2006

The pyrolysis reactions of dihalocyclopropanes and monohalocyclopropanes were carried out at 200–400°C. Bromo-substituted cyclopropanes were readily decomposed in this temperature range. In all cases, the pyrolysis products were ring-opened olefinic hydrocarbons. As for the monohalocyclopropanes, the reactions proceed in a stereospecific manner. The possible mechanism was discussed in terms of the requirements of the electrocyclic ring opening.
A Theoretical Study of the Possible Interaction between Sulfonium Salts and Molecular Oxygen
Authors: Ohkubo Katsutoshi , Yamabe Tokio
Published: July 2006

The interaction between sulfonium salts and molecular oxygen was studied by the ASMO SCF method. Firstly, the results of the ASMO SCF calculation of trimethylsulfonium chloride suggested that the bond between the sulfonium cation and the anion was constituted mainly of the bonding (d-p)π-type overlaps (made by 3dyz-(or 3dxz-) of S and 3py (or 3px) of Cl) and of the antibonding (d-p)σ-type overlaps (made by 3dz2 (or 3pz) of S and 3pz (or 3dz2) of Cl). Secondly, the sulfonium salt interacts with molecular oxygen mainly through a (d-p)σ-type overlap between the 3dyz-(or 3dxz-)orbital of the former and the (1πg)z-orbital of the latter. Thirdly, a maximum overlap formed between 3d-sulfur orbitals and 1πg-orbitals of O2 is established at the O2-rotation angle of π/4 to the direction of the d-orbital expansion. Finally, the change in the energy state of O2 caused by the sulfonium-salt interaction was discussed.
Kinetics and Mechanism of Aquation and Anation of Some Amino Acid Pentamminecobalt(III) Complexes in Acid Aqueous Solutions
Authors: Murakami Tasuku , Ogino Kazuko , Kobayashi Hiromi , Yamazaki Hiroshi , Saito Kazuo
Published: July 2006

Kinetics of aquation has been studied with pentamminecobalt(III) complexes containing aliphatic amino acids (γ-aminobutyric acid, ε-aminocaproic acid, α-amino-isobutyric acid, ornithine, and proline), aromatic acids (benzoate, anthranilic, and p-aminobenzoic acid), and α-substituted acetates (monochloroacetate and glycolate). Anation rate constants were obtained for glycine, β-alanine, and ε-aminocaproic acid, and equilibrium constants between [CoH2O(NH3)5]3+ and [Co(NH3)5amH]3+ (amH=amino acid), Keq were calculated. The free energy plot logkaq  vs. logKeq gave a straight line with a gradient 0.6. This value has been discussed in terms of two possible mechanisms. The dependence of acid catalysed aquation rate constant, kH+ on pKa of carboxylate group of the amino acid is written as logkH+=0.5 pKa+ const., while that for α-substituted acetates log kH+=pKa+ const. Such a difference in the slope is interpreted as due to the electrostatic influence of–NH3+ group of coordinated amino acid.
Ultrasonic and Thermodynamic Study on Solute-Solvent Interaction. Binary Mixtures of t-Butyl Chloride, t-Butyl Bromide and 1,1,1-Trichloroethane with Carbon Tetrachloride, Benzene and p-Xylene
Authors: Kiyohara Osamu , Arakawa Kiyoshi
Published: July 2006

Sound velocity and density of binary mixtures of t-butyl chloride (tBC), t-butyl bromide (tBB), and 1,1,1-trichloroethane (TCE) with carbon tetrachloride (CT), benzene (B), and p-xylene (pX) were measured at temperatures, 25 and 35°C. The excess molar volume and excess compressibility of these systems were calculated. The temperature dependency of excess volume was negative for aromatic solutions and positive for CT solutions. The temperature coefficients of excess compressibility were negative for all systems. The relation between thermodynamic properties and intermolecular interactions in these systems were discussed. Two systems, B-TCE and CT-TCE, were found to be nearly ideal. The solute-solvent interactions in CT-tBC and tBC-TCE systems were found to be more attractive than in other systems.
The Crystal Structure of cis-Ammonium Disulfitotetramminecobaltate(III) Trihydrate, NH4[Co(SO3)2(NH3)4]·3H2O
Authors: Nomura Teruo , Nakahara Masayoshi
Published: July 2006

The structure of NH4[Co(So3)2(NH3)4]·3H2O has been determined by the heavy-atom method and refined to R=0.12 by a least-squares analysis based on 874 three-dimensional visual data. The compound crystallizes in the orthorhombic space group P212121 with unit cell dimensions of a=10.995, b=17.563, c=6.834 Å, and Z=4. The two sulfito groups in the complex anion are coordinated to the central cobalt atom in cis positions through their sulfur atoms, with Co-S distances of 2.23 Å (mean). The cis-configuration of brown sodium salt, with an absorption spectrum similar to that of the trihydrate of ammonium salt, has also been established.
The Surface Properties of the Silica-Titania System Prepared by the Hydrolysis of Metal Alkoxides
Authors: Hosaka Hiroshi , Meguro Kenjiro
Published: July 2006

The surface and bulk properties of silica-titania systems, prepared by the co-hydrolysis of silicon ethoxide and titanium tetrabutoxide, were investigated by measuring the heat of immersion, the adsorption of nitrogen, water, and ammonia, the X-ray diffraction, the DTA, and the TGA. It was found that the addition of silica to titania has a large suppressive effect on the crystal growth of anatase and on the transformation of anatase to rutile. The heat of immersion, the surface hydrophilicity (the surface area by water adsorption/the surface area by nitrogen adsorption) and the amount of ammonia adsorbed gave inverted sigmoid curves when the titania content was varied. Especially, the shape of the curve of the change in the heat of immersion coincides approximately with that of the surface hydrophilicity.
Photochemical Reaction of 9-Cl-Acridine in Aerated and Deaerated Ethanol. I
Authors: Nakamaru Katsumi , Niizuma Shigeya , Koizumi Masao
Published: July 2006

It was established that upon irradiation, the degassed ethanol solution of 9-chloroacridine is quickly converted into 9,9′-biacridyl by the reaction 2 (9-Cl-acridine) \overset+2H\underset(hν)→ 9,9′-biacridyl+2HCl and that 9,9′-biacridyl produced is then reduced photochemically to 9,9′-biacriden as the main product. The reaction scheme completely denies the scheme previously proposed (V. Zanker and W. Flügel, Z. Naturforsch., 19(b), 376 (1964)) in which the primary photoproduct is a charge transfer complex between 9-Cl-acridine and its reduced form. 9,9′-biacridyl is photoreduced to an acridan-like compound even in the aerated solution perhaps via molecular mechanism in contrast to 9-Cl-acridine which yields acridone under similar conditions. ESR spectrum with hfs was detected in the acidic solution (degassed) containing 9,9′-biacriden produced photochemically. The mechanism of its production was discussed. Similar reactions using various solvents (aerated and deaerated) were examined and the general feature of the primary processes was described.
The Crystal and Molecular Structure of Pyromellitic Acid Dihydrate (Benzene-1,2,4,5-tetracarboxylic Acid Dihydrate)
Authors: Takusagawa Fusao , Hirotsu Ken , Shimada Akira
Published: July 2006

The crystal structure of pyromellitic acid dihydrate has been determined by the method of X-ray diffraction. The crystal is triclinic in the P\bar1 space group, with Z=1 and cell dimensions of a=10.05, b=6.45, c=5.45 Å, α=74.5°, β=112.2°, and γ=77.3°. The structure was derived from the three-dimensional Patterson function and was later refined by the least-squares method, using the anisotropic thermal parameters, to give a final R index of 7.4%. All the hydrogen atoms were located on the difference-synthesis map. The average C(ring)–C(ring) distance is 1.386 Å, while the average C(ring)–C(carboxyl) distance is 1.496 Å. One carboxyl group is twisted by 17.9°, and the other is twisted by 74.5°, out of the plane of the benzene ring. The C–O(H) and C=O distances differ significantly from each other, the average values being 1.302 and 1.211 Å respectively. Four types of hydrogen bonds, with an average O–H···O distance of 2.732 Å, form a three-dimensional network. Thus, each molecule is joined, through hydrogen bonds around the center of symmetry, to two other molecules, forming an endless chain in the [1 \bar1 1] direction. Water molecules are arranged on the plane parallel to (1 1 0) so as to hold the chains together by hydrogen bonds.
Photochemical Reactions of Uranyl Ions with Organic Compounds III. The Correlation between the Reaction Mode and the Pre-Equilibrium in the Photolysis of the Uranyl-lactate System
Authors: Sakuraba Shukichi , Matsushima Ryoka
Published: July 2006

On the basis of the assumed mechanism for the photolysis of the uranyl-lactate system, the equilibrium constant for the complex formation, K, was evaluated from the photo-kinetic data by using a monochromatic 4047 Å light; it was then compared with those obtained from the usual spectrophotomeric measurements. A comparison of the K values obtained by means of the photo-kinetic data (1.0–1.1×10−1) and by means of the analytical data (1.1–1.2×10−1) gave an excellent agreement; there was also a good agreement between the slope of the plot of the photo-kinetic data and that predicted from the assumed mechanism. The results supported the crude mechanism assumed earlier.
Stability Constants of Cu(II) Chelates with o-Phenylenediamine Derivatives
Authors: Kina Kenyu , Tôei Kyoji
Published: July 2006

The stability constants of copper(II) chelates with o-phenylenediamine derivatives have been determined by the pH titration method. The measurements have been carried out at 25.0±0.1°C and μ=0.10(by KNO3).

o-Phenylenediamine derivatives, which have a substituent group (CH3, CH3O, COOH, or Cl, etc.) at the 4 positions, were used as ligands. The overall stability constants of the copper chelates are of the order: CH3, CH3O, H, COO−, Cl, COOH; their values were 8.50, 8.42, 7.72, 7.06, 5.76, and 5.35 respectively. The effects of substituent groups on the stability constants have been studied. The plot of the overall stability constants against the sum of Hammett σm and σp values was found to be linear. The chelate stability and acid dissociation constants of the acido complexes of 3,4-diaminobenzoic acid were determined by the use of an augmented matrix.
The pH Dependence of Anion Exchange Chromatographic Separation of Tri- and Tetraphosphate Anions
Authors: Nakamura Terumasa , Kimura Mitsuyasu , Waki Hirohiko , Ohashi Shigeru
Published: July 2006

The anion-exchange distribution ratios of tri-, tetra-, and pentaphosphate were determined in a Dowex 1-X4-potassium chloride system at different pH by the batch method. The difference between the mean charges of the phosphates in resin phase and solution was explained in terms of a higher pH of resin phase than that of the solution. pH dependence of the separation factors for tri- and tetraphosphate and for tetra- and pentaphosphate was estimated from the batch equilibrium data, and the relative elution positions of these phosphates were confirmed by the practical chromatographic runs.
The Reaction of Acetylenecarboxylic Acid with Amines. XVI. Formation of Alkyl Isoxanthopterinacetates Possessing Imine Structure
Authors: Iwanami Yasuo
Published: July 2006

Methyl and ethyl isoxanthopterin-6-acetates and their 4-amino analogues have been prepared via a new route from acetylenedicarboxylate and 2,5,6-triamino-4-hydroxypyrimidine or 2,4,5,6-tetraaminopyrimidine. These compounds uniquely exist in the imine form as evidenced by NMR and IR spectral data. This is the only exceptional case so far examined, since a number of related compounds exist in enamine form. When dissolved in sulfuric acid, however, tautomerization of imine to enamine is observed. It was demonstrated by NMR inspection that the methylene hydrogen on the side chain is exchangeable with deuterium. The tautomerism in sulfuric acid is discussed.
Heterocycles Structurally Influenced by a Side Chain. I. 3-Phenacyl-2(1H)-quinoxalinones and 3-Phenacyl-2H-1,4-benzoxazin-2-ones
Authors: Iwanami Yasuo , Seki Taketsugu , Inagaki Takeshi
Published: July 2006

Seven phenacyl derivatives of 2(1H)-quinoxalinone and 2H-1,4-benzoxazin-2-one (IV and V) have been synthesized to introduce a common structural element –CH2–CO– into their 3-positions. Their structures are compared with those of the related compounds described previously. The main purpose of the present study was to see whether or not their ring double bonds ((Remark: Graphics omitted.)) have ever been displaced onto the side chains, constituting an enamine so as to form =CH–CO–, the carbonyl of which is hydrogen bonded with the secondary amino group of the rings thereby formed. Consequently, existence as the enamine form, facilitated by an intramolecular hydrogen bonding, has been evidenced by IR and NMR spectral data. It is, therefore, fitting to call them by the more practical expression “3-phenacylidene-3,4-dihydro-2(1H)-quinoxalinone” (IVa), and so on. Hydrolysis of IV gave the corresponding 3-methyl-2-(1H)-quinoxalinones (VI) and benzoic acid (VII), while that of V afforded the starting substances, o-aminophenols (III) and benzoylpyruvic acid (VIII) which had been partially decomposed into pyruvic acid (IX) and VII.
Asymmetric Hydrogenation of C=O Double Bond with Modified Raney Nickel. XX. The Effect of Additives on the Asymmetric Activity
Authors: Higashi Fukuji , Ninomiya Toshio , Izumi Yoshiharu
Published: July 2006

The effects of various additives in methyl acetoacetate were tested in the asymmetric hydrogenation reaction. Among them, water has a particular effect on the asymmetric activities of the catalysts; in the presence of a certain amount of water, the catalysts modified with l-Glu, l-Val, and l-Ala hydrogenated methyl acetoacetate to methyl ls(+)3-hydroxybutyrate, while, without the addition of water, the catalysts promoted the hydrogenation to yield methyl ds(−)3-hydroxybutyrate. The catalyst modified with l-Ala at pH 6.0 and the catalyst modified with l-Glu at pH 5.0 and 100°C were especially sensitive to water, and both catalysts showed (+) asymmetric activity when a trace of water was also present. Even in the hydrogenation without the addition of water, the recovered catalysts modified with l-Glu, l-Val, and l-Ala from the hydrogenation in the presence of water gave results similar to those in the hydrogenation in the presence of water. The effect of water as an additive was discussed, and it was concluded that the water affects the asymmetric site of the catalyst rather than the keto-enol equilibrium of the substrate.
Intramolecular Interaction between Hydroxyl Group and π-Electrons. XXIV. The Interaction Involving the Cyano Group
Authors: Oki Michinori , Yoshida Takashi
Published: July 2006

The infrared O–H stretching spectra of various 1- and 2-cyano alcohols have been measured, and the presence of intramolecular O–H···π interaction has been detected. Some discussion of the confirmation of such alcohols is given.
The Reaction of Ethyl Alkylchloropyruvate with Sodiomalonate and Sodioacetoacetate
Authors: Takeda Akira , Wada Satosi , Fujii Masatosi , Nakasima Isao , Hirata Shoiti
Published: July 2006

The reaction of alkylchloropyruvate (1) with sodiomalonate gave γ-alkyl-α,β-dialkoxycarbonyl-Δβ,γ-butenolide (2), which led to γ-ketocarboxylic acid (3). The reaction of 1 with sodioacetoacetate gave 2-alkyl-5-methylfuran-3,4-dicarboxylate (6) via the intermediate 2-alkyl-3-hydroxy-5-methyl-2,3-dihydrofuran-3,4-dicarboxylate (5). It has been shown unambiguously that the carbanions of both sodiomalonate and sodioacetoacetate attack the carbonyl carbon of 1 predominantly.
Kinetics of Liquid-phase Hydrogenation of Aliphatic α,β-Unsaturated Aldehyde over Raney Cobalt Catalyst
Authors: Hotta Kazuhiko , Kubomatsu Teruo
Published: July 2006

Kinetic studies on the hydrogenation of 2-methyl-2-pentenal (UD) over the Raney cobalt catalyst were performed at temperatures ranging from 10 to 40°C in n-hexane. The products were found to be 2-methylpentan-1-ol (SA), 2-methyl-2-penten-1-ol (UA) and 2-methylpentanal (SD). The initial rates of the formation of SA(rSA), SD(rSD), and UA(rUA) were determined in the concentrations of UD(CUD), 0.026–0.263 mol/l. It was found by kinetic analysis that (rSA+rSD) was represented by a Langmuir-type rate equation and rUA by another one. The rate equations which fitted the rate data are as follows.

r SA+rSD=\frac1.1×1010e−15200⁄RTCUD(1+4.4×105e−7500⁄RTCUD)2

r UA=\frac1.2×108e−13500⁄RTCUD(1+9.3×103e−5600⁄RTCUD)2

A mechanism in which the formation of SA and SD and that of UA proceed through different types of adsorbed UD was proposed. The adsorbed species in enol form and that in keto form were considered with respect to the formation of SA and SD. Activation energies for the formation of SA plus SD and of UA were determined to be 7.7 and 7.9 kcal/mol, respectively. The selectivity defined as the ratio of rSA to (rSA+rSD) was found to increase with the increase of the surface coverage of hydrogen.
Thiocyanoacetate. I. Reactions of Thiocyanoacetic Esters with Aldehydes
Authors: Kambe Satoshi , Hayashi Toshio , Yasuda Heinosuke , Midorikawa Hiroshi
Published: July 2006

Thiocyanoacetic esters (I) and aldehydes reacted in the presence of potassium fluoride or carbonate to give α,β-unsaturated ester as a major product and an unexpected solid product (II) as a minor one, which was determined to be N-carbamoyl-2-imino-5-substituted 1,3-oxathiolane-4-carboxylic esters.
Formation of Ketenimines by the Reaction of Thioamides with Diethyl Azodicarboxylate and Triphenylphosphine
Authors: Mitsunobu Oyo , Kato Koki , Wada Makoto
Published: July 2006

The reaction of diphenylacetothioanilide with diethyl azodicarboxylate and triphenylphosphine gave rise to the formation of diphenylketene(N-phenyl)imine. Similarly, the reaction of N-(p-tolyl)diphenylacetothioamide gave diphenylketene(N-p-tolyl)imine. On treatment with diethyl azodicarboxylate in the presence of sodium ethoxide, diphenylacetothioanilide afforded bis(N-phenylbenzalimidoyl) disulfide in a good yield. The intermediate of the formation of the ketenimines is also discussed.
The Reactions of Aroyl Peroxides with Grignard Reagents. III. On the Structure and the Reaction of the Complex Containing Benzoyl Peroxide
Authors: Okubo Masao , Maruyama Kazuhiro , Osugi Jir\={o}
Published: July 2006

The orange-colored complex which is formed in the reaction of benzoyl peroxide with Grignard reagent was studied by infrared spectra, and the reaction of the complex with Grignard reagent was also examined. In this complex, the structure of BPO was still maintained by coordinating with magnesium atom through the peroxidic as well as the carbonyl oxygen atoms. Reaction products of this complex with phenylmagnesium bromide were benzoic acid(as Mg-salts), phenyl benzoate, benzophenone, triphenylcarbionol, and bromobenzene. The heterolytic mechanism on the formation of bromobenzene was proposed. The molar ratio of products depended seriously upon the mode of addition of Grignard reagents. The exclusive formation of bromobenzene and Mg-salts of benzoic acid without phenyl benzoate under an experimental condition was explained by assuming the electron-transfer process through the coordinating bond in the complex.
Liquid Phase Chlorination of Olefins with Cupric Chloride. III. Effect of Additives and Kinetics
Authors: Koyano Takashi , Watanabe Osamu
Published: July 2006

Chlorination of 1-octene with cupric chloride has been investigated in methanol at 110–130°C. The yield of 1,2-dichlorooctane (I) increased by addition of lithium chloride in the reaction mixture, while that of 1-chloro-2-methoxyoctane (II) decreased. Addition of water and cuprous chloride markedly retarded the reaction. The initial rates of formation of I and II could be expressed as v=k[octene]0 [CuCl2]01.6 and v=k[octene]0 [CuCl2]0, respectively. These results can be explained as an initial formation of a complex between olefin and cupric chloride molecule, followed by competitive attack on the complex by chloride ion and methanol. In the less polar reaction media containing more octene, the ratio of I/II increased. This may be ascribed to the steric effect of cupric chloride in the intermediate.
Studies on Reactions of Isoprenoids. XIV. Facile Lactone Formations from 2-endo-Cyano-, 2-endo-Cyanomethyl-, and 2-endo-Carboxymethyl-5-norbornenes
Authors: Sasaki Tadashi , Eguchi Shoji , Sugimoto Michio
Published: July 2006

Treatment of 2-endo-cyano-5-norbornene (I) with polyphospholic acid (PPA) at 60°C afforded 6-endo-hydroxybicyclo[2.2.1]heptane-2-endo-carboxylic acid lactone (V) in 40–46% yields, while 2-endo-cyanomethyl-5-norbornene (IV) prepared from 2-endo-methoxycarbonyl-5-norbornene (II) via the corresponding alcohol (III) gave 3-exo-hydroxybicyclo[2.2.1]heptane-2-exo-acetic acid lactone (VIII) in 25% yield by a similar treatment with PPA. With sulfuric acid, IV gave only intractable polymeric materials. However, under milder conditions using a sulfuric acid-acetic acid mixture, IV afforded 2-exo-cyanomethyl- (VI) and 2-exo-carbamoylmethyl-6-exo-acetoxynorbornane (VII) in 69 and 2% yields, respectively. On the other hand, iodolactonization of the carboxylic acid (IX) derived from IV afforded 5-exo-iodo-6-endo-hydroxybicyclo[2.2.1]heptane-2-endo-acetic acid lactone (X) in 68% yield. The formation of VIII from IV was explained by the successive Wagner-Meerwein rearrangement, 3,2- and 6,2-hydride shifts, followed by cyclization.
A Modification of Red Blood Cells by Isocyanates
Authors: Kitajima Masao , Sekiguchi Wataru , Kondo Asaji
Published: July 2006

Modified red cells that have a reinforced membrane and hemoglobin which is difficult to denature are prepared by treating red cells with some isocyanates. These modified cells have the same shape as normal red cells, but they are not lysed by osmotic pressure or by the actions of any reagents except for some ionic surface-active agents. No agglutination was observed when they were mixed with the blood of foreign animals or with blood of different blood groups. The hemoglobin within the cell gave a reversible oxygenation curve and had a high oxygen affinity. Toluene-2,4-diisocyanate was found to be the most suitable reagent among the many isocyanates examined. A suspension reaction method which consists of the addition of an isocyanate emulsion to a red-cell suspension at 5°C is developed for the modification process.
The Synthesis of the Polymer Containing the Si-O-phenylene Bond, using Transition Metal Salts as Catalysts
Authors: Iwakura Yoshio , Uno Keikichi , Toda Fujio , Hattori Kenjiro , Abe Minoru
Published: July 2006

Various transition metals were found to be effective as catalysts in the dehydrocondensation of phenols and silanes.

R3SiH+PhOH\oversetmetal salt→R3SiOPh+H2

The effective species were PdCl2, H2PtCl6·6H2O, PtCl2, RhCl3, NiCl2, silane-treated NiCl2, Ptl2, PtS, Raney Ni, Pd-black, Pt-black, Au-black, FeCl3, ZnCl2, CuSO4, CuCl, Cu–Cr, Cu(CH3CO2)·CuO, the methyl ethyl ketoxime complex of Pd, Pt(OX)3, and Pd(OX)2. The ineffective species were metal mirrors of Pd, Au, Ag, Pt, and Cu, and the acetylacetonato complex of Ni, Co(II), Co(III), and Cu. The reaction was then extended to the preparation of polymers containing a Si–O–phenylene linkage in the main chain. Dihydricphenols, e.g., bisphenol A, hydroquinone, 4,4′-dihydroxydiphenyl gave high-molecular-weight polymers with an equimolar amount of a dihydro-silane, e.g., diphenylsilane, p-toluylmethylsilane and p-bisdimethylsilylphenylene, in bulk or in a solvent at temperatures above 150°C. The polymer obtained began to flow above 100°C.
Radikalische aromatische m-Nitrierung bei Umsetzung von Benzoylperoxyd mit Stickstoffdioxyd und bei Umsetzung von p-Chlorperoxybenzoesäure mit Stickstoffoxyd in Toluol
Authors: Suehiro Tadashi , Hirai Mikio , Kaneko Takehira
Published: July 2006

Die radikalische Nitrierung des Toluols findet bei der Umsetzung von Benzoylperoxyd mit Stickstoffdioxyd bei 60–100°C in 4–15% Ausbeute und bei der Umsetzung von p-Chlorperoxybenzoesäure mit Stickstoffoxyd bei 20–80°C in 30–50% Ausbeute statt. In beiden Umsetzungen waren die Isomeren-Verhältnisse der gebildeten Nitrotoluole o/m/p=6–25/75–91/0–3. Daß diese m-orientierende Nitrierung über das Zwischenprodukt, Aroyloxycyclohexadienyl-Radikal, abläuft, wurde sichergestellt aufgrund der Isomeren-Verhältnisse der Nitrotoluole im Vergleich zu denen der Benzoesäureester von Kresolen aus der konkurrierenden Benzoyloxylierung (o/m/p=40–54/13–16/33–45) und aufgrund der relativen Reaktivität des Toluols (2–4) gegenüber Benzol bei der Nitrierung und der Benzoyloxylierung.
The Synthetic Intermediate of Pyridoxine. II. The Thermal Cyclization of Ethyl α-Isocyanopropionate to 5-Ethoxy-4-methyloxazole
Authors: Maeda Itsutoshi , Togo Kazushi , Yoshida Ryonosuke
Published: July 2006

The thermal cyclization of ethyl α-isocyanopropionate (I) was performed to 5-ethoxy-4-methyloxazole (II) as an intermediate for the synthesis of pyridoxine. The similar reaction of several new alkyl esters of α-isocyanocarboxylic acid to the corresponding 5-alkoxy-4-substituted oxazole was also carried out. The reaction products of the thermal cyclization of I were investigated. When the cyclization was carried out at 180°C for 5 hr, the maximum yield of the main product, II, was 20%; unreacted I (30%), ethyl α-cyanopropionate(20%), and dimer of I (5%) were also obtained. The α-hydrogen of ethyl α-isocyanosuccinate (X) can be more easily removed than that of I, so X may be expected to be more readily converted to 5-ethoxy-4-ethoxycarbonylmethyloxazole (XI), which is also an intermediate of pyridoxine. The yield of XI from X did not exceed 30% because of the side reaction.
Studies on Intermolecular Complex Formation. I. Between Nucleotide Bases and Organic Compounds
Authors: Tamura Chihiro , Sakurai Noriko , Sato Sadao
Published: July 2006

The present investigation was focussed on a survey of the chemical compounds which are capable of binding with nucleotide bases. X-Ray powder patterns show that adenine and cytosine have a strong tendency to interact with many organic compounds having a carboxyl group and cyclic alternant CONH groups. A few compounds bind with thymine and uracil.
The Hybridization Effect on the Equilibrium Distance. III
Authors: Miyazaki Tomoo , Shigetani Tsunehisa , Shinoda Hiroyuki
Published: July 2006

In order to re-examine the unexpected conclusion previously reported that the hybridization effect is unimportant in determining the C–C single bond length, a more reliable calculation involving the configuration interaction treatment and more elabolate calculations by the NDDO and unrestricted INDO methods have been performed. The results of the INDO-CI and unrestricted INDO calculations were in good agreement with those which were obtained by the previous calculations. According to the NDDO calculations, however, the equilibrium distances of different kinds of C–C single bonds were found to increase with the decreased s character in hybrids, although this effect was not very significant. The effect of interaction between non-adjacent atomic orbitals in determining the bond length has been discussed in full detail.