bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electron-transfer Reactions of Multidentate Ligand Cobalt(III) Complexes. IV. The Reductions of Cobalt(III) Complexes of Amino Acids by Iron(II) in Aqueous and Water-methanol Solutions
Authors: Ohashi Kousaburo , Yamamoto Katsumi , Hirako Ichiro , Kurimura Yoshimi 
Published: July 2006

Abstract
The kinetics of the Fe(II) reductions of trans(O,Cl)-Co(dien)(am)Cl+ (am=glycine, α-alanine, β-alanine, leucine, and proline) and trans(N)-Co(am)2(ox)− (am=glycine, α-alanine, β-alanine, ox=oxalate, and dien= diethylenetriamine) have been made spectrophotometrically in an aqueous solution. Except for the β-alanine complex, the reactivities of the Co(III) complexes are not very different when the amino acid is replaced by the other one. The greater reactivities of the β-alanine complexes may be due to the steric strain on the six-membered β-alanine chelate ring. The rates of the reductions of cis(N)-Co(α-ala)2(ox)− and cis(N)-Co(β-ala)2(ox)− by Fe(II) are greatly affected by the addition of methanol to the aqueous solutions; the rate increases with an increase in the mol fraction of methanol. The replacement of water molecules in the solvation sphere of the reductant by the methanol molecules is considered to be one of the reasons for the greater rate in water-methanol solutions.
Ionic Equilibria in Mixed Solvents. VII. Hydrolysis of Copper(II) Ion in Dioxane-Water Mixtures containing 3 m (Li)ClO4 as an Ionic Medium
Authors: Ohtaki Hitoshi , Kawai Takayoshi 
Published: July 2006

Abstract
The hydrolytic reactions of copper(II) ion were studied at 25°C in water, in 0.1 and 0.5 mole fraction dioxane-water mixtures, each containing 3 m (Li) ClO4 as an ionic medium. Emf measurements were carried out in the range of the total copper(II) concentration of 0.01125–0.07106 m (in water), 0.01548–0.1356 m (in the 0.1 mole fraction dioxane-water mixture), and 0.02257–0.1231 m (in the 0.5 mole fraction dioxane-water mixture), respectively. Species formed and their formation constants determined (log*βp,q) are: CuOH (−7.54±0.02), Cu2OH (−6.22±0.02), Cu2(OH)2 (−11.12±0.05), and Cu3(OH)2 (−10.36±0.05) in water; CuOH (−7.44±0.02), Cu2OH (−6.22±0.02), Cu2(OH)2 (−11.35±0.05), and Cu3(OH)2 (−10.12±0.08) in the 0.1 mole fraction dioxane-water mixture; CuOH (−7.74±0.02), and Cu2OH (−6.40±0.02) in the 0.5 mole fraction dioxane-water mixture.
Chemical Constituents of Alnus sieboldiana (BETULACEAE). III. The Synthesis and Stereochemistry of Yashabushiketols
Authors: Asakawa Yoshinori 
Published: July 2006

Abstract
Dihydroyashabushiketol (2), isolated previously from the male flower of Alnus sieboldiana, has been synthesized by the condensation of benzaldehyde with acetylacetone, followed by hydrogenation. The absolute configuration at C5 of yashabushiketol (1) and 2 has been identified as S. The geometry between the trans double bond and the carbonyl group in 1 was established to be s-cis. Eleven more minor components of a known aromatic compound were identified at the same time.
The Synthesis of 3,6-Anhydro-5-O-methyl-d-galactose
Authors: Hirase Susumu , Watanabe Kyoko 
Published: July 2006

Abstract
3,6-Anhydro-5-O-methyl-d-galactose has been synthesized for the first time through a series of reactions composed of blocking the hydroxyl groups at C2 and C4 of methyl 3,6-anhydro-α-d-galactopyranoside with the phenylcarbamoyl groups, converting the resulting derivative of the methyl glycoside into the corresponding dimethyl acetal, methylating the newly formed hydroxyl group at C5, removing the blocking substituents, and finally hydrolysing the dimethyl acetal. The partially methylated anhydro-sugar obtained was uncrystallizable, and was characterized by its crystalline dimethyl acetal and crystalline aldonamide.
The Synthesis and Asymmetric Adsorption of an Optically-active Basic Polymer Starting from l-Proline
Authors: Yamashita Tetsushi 
Published: July 2006

Abstract
N-Prolyl-p-aminostyrene was synthesized by the reaction of N-carboxy-l-proline anhydride with p-aminostyrene phosphate. This optically-active basic monomer was then copolymerized wtih N,N′-bis(p-viny]phenyl)-adipamide to give a basic polymer. Similar basic polymers were also obtained, starting from other α-amino acids, through this procedure. Of these polymers, the polymer involving l-proline was used for the chromatographic resolution of the phthalamidic acid derivatives of Dl-phenylalanine, Dl-valine, and Dl-phenylglycine. The polymer resolved partially Dl-N-(o-carboxybenzoyl)phenylalanine.
Aroyl Arenesulfonyl Peroxides. V. Mechanisms of the Reactions of Benzoyl p-Toluenesulfonyl Peroxide with Several Nucleophiles
Authors: Hisada Ryuki , Kobayashi Michio , Minato Hiroshi 
Published: July 2006

Abstract
Reactions of benzoyl p-toluenesulfonyl peroxide (BTP) with several nucleophiles were investigated. The reaction with triphenylphosphine gave benzoyl p-toluenesulfonate and triphenylphosphine oxide, that with diphenyl sulfide gave benzoyl p-toluenesulfonate and diphenyl sulfoxide, and that with p-tolylmagnesium bromide gave p-toluenesulfonate and benzoic acid. In the reaction of BTP[carbonyl-18O] with triphenylphosphine, 88% of carbonyl oxygen-18 was retained as the carbonyl oxygen of the benzoyl p-toluenesulfonate formed, whereas in the reaction of BTP[carbonyl-18O] with diphenyl sulfide only 58% of the label in the starting peroxide was found in the carbonyl oxygen of the benzoyl p-toluenesulfonate formed. In the reaction of BTP[sulfonyl-18O] with p-tolylmagnesium bromide, it was found that the two sulfonyl oxygens of BTP were completely retained in the two sulfonyl oxygens of the p-tolyl p-toluenesulfonate formed. Possible mechanisms of these reactions are discussed.
Light-scattering Studies of the Interaction between Bovine Serum Albumin and Guanidine Hydrochloride in Aqueous Solutions
Authors: Nakagaki Masayuki , Sano Yoh 
Published: July 2006

Abstract
The denaturation of bovine serum albumin (BSA) by guanidine hydrochloride (GuHCl) was studied by means of the light-scattering method. The Zimm plots were curved so that apparently imaginary values of the radius of gyration were obtained, but the modified Zimm plots, drawn by applying the correction factor for the optical anisotropy of segments, gave reasonable values of the weight-average molecular weight, the radius of gyration, and the second virial coefficient. The correction factor was calculated by using the experimental values of the scattering ratio at 90° of the scattering angle. The analysis of the intrinsic viscosity showed that the BSA molecules were elongated. According to these results, it has been concluded that the BSA molecules are streched by the denaturation the more as the GuHCl concentration is higher, and that the denatured BSA molecules, at first, form dimers by the side-by-side aggregation of two molecules, but that the intermolecular bindings, too, are broken with the further addition of GuHGl. The length reached at 5m GuHGl was about 1/5 of the fully stretched length. This suggests the possibility that the denatured BSA molecules can keep their local natural conformations.
Ternary Lamellar Compounds of Graphite with Aluminum Bromide and Bromine
Authors: Sasa Tadashi , Takahashi Yoichi , Mukaibo Takashi 
Published: July 2006

Abstract
Graphite was allowed to react with binary reactants of aluminum bromide and bromine. The formation of ternary lamellar compounds was observed. A change in the activity of the reactants in the system gave three compounds I, II, and III with different contents of aluminum bromide and bromine. Compound I, obtained as the reaction product of graphite with the solution of bromine saturated with aluminum bromide, has a composition of C9AlBr3·Br2, and a lamellar structure of the first stage with Ic of 10.24 Å. Compound II, which has the lowest bromine content, has a composition of C24AlBr3·Br0.3 and a lamellar structure of the second stage with Ic of 13.35 Å. Compound III, obtained at a bromine activity higher than that for compound I, has a non-stoichiometric composition of about C5–6Br(AlBr3)0.2, and a structure of the second stage with Ic from 13.58 to 13.72 Å. The phase diagram of the ternary system was derived. Compounds I and III have higher bromine contents than C8Br, which is the saturation compound of graphite-bromine system. This is supposed to be due to the stabilization of bromine by the coexistence of aluminum bromide.
The Formation of High-boiling By-products in the Isomerization and Disproportionation of m-Xylene over a Silica-alumina Catalyst under Pressure
Authors: Takaya Haruo , Todo Naoyuki , Hosoya Tadasuke , Oshio Hideki , Minegishi Toshio 
Published: July 2006

Abstract
Continuous liquid-phase isomerization and disproportionation reactions over silica-alumina catalysts were carried out using m-xylene with varying concentration of water. The reactions were conducted at 290°C and 400°C under a pressure of 300 kg/cm2. The results showed that the concentration of water required to attain a maximum activity for the isomerization was higher than that needed for the disproportionation reaction. The high-boiling by-products produced at 400°C comprized 2–5 per-cent of the weight of the total products, and the main component, polymethyldiphenylmethane, amounted to 70–80 per-cent of the by-products. The yield of polymethyldiphenylmethane was linearly correlated with that of toluene. This result appears to suggest that the disproportionation reaction and the polymethyldiphenylmethane formation proceed at a common active site and through the same intermediate.
Vibrational Spectra of trans-trans Diacetamide and Its C-and N-Deuterated Compounds
Authors: Kuroda Yoshihiro , Saito Yutaka , Machida Katsunosuke , Uno Toyozo 
Published: July 2006

Abstract
The infrared spectra of CH3CONHCOCH3, CD3CONHCOCH3, CD3CONHCOCD3, and their N-deuterated compounds have been recorded for the unstable crystalline modification in which the molecules are in the trans-trans conformation (form B). The Raman spectra of CH3CONHCOCH3 in the form B crystal and in the complex with KI have also been recorded. Vibrational assignments have been given by referring to the characteristic group frequencies of related compounds, the infrared dichroic measurement for CH3CONHCOCH3 and the isotopic frequency shifts. The normal coordinates analysis has been made by assuning the planar trans-trans conformation of the –CONHCO– (–CONDCO–) group. The calculated frequencies fit to the observed satisfactorily.
An NMR Study of Metal Complexes Containing Acetylacetone and Related Compounds. III. The Preparation and Determination of the Configurations of Cobalt(III) Complexes Containing N,N′-Ethylenebis(acetylacetonimine) and N,N′-Ethylenebis(salicylideneimine)
Authors: Fujii Yuki , Osawa Akio , Furukawa Yoichiro , Ebina Fujio , Takahashi Sozo 
Published: July 2006

Abstract
A series of cis-β-form cobalt(III) complexes containing N,N′-ethylenebis(acetylacetonimine) dianion (baen) or N,N′-ethylenebis(salicylideneimine) dianion (salen) were prepared—cis-β-[Co(X)(Y)] and cis-β-[Co(X)(Z)]ClO4(where X=baen or salen, Y=anions of acetylacetone, benzoylacetone, 8-hydroxyquinoline, and Z= ethylenediamine, 1,10-dipyridyl, 1,10-phenanthroline). The synthetic methods and characterization data are given. Also prepared were a series of trans-form cobalt(III)-bean complexes—trans-[Co(X)(A)2]ClO4 and trans-K[Co(X)(NO2)2] where X=baen, and A=ammonia, methylamine, pyridine, aniline). The isolation of only cis-β-form complexes in reactions between [Co(X)(H2O)2] and the bidentate ligands contrasts with the isolation of only trans-form ones in those between [Co(X)(H2O)2] and the monodentate ligands. This result was explained in terms of the relative stabilities of the three configurations of the coordinated baen and salen. On the basis of the configurational analysis, the relative stabilities of the three configurations were determined to be trans-planar form &gt; cis-β form &gt; cis-α form.
The 9-Barbaralyl Cation
Authors: Hoffmann Roald , Stohrer W-D , Goldstein M J 
Published: July 2006

Abstract
We find that the 9-barbaralyl cation assumes a structure with 3-fold symmetry in which there is an interesting orbital pattern caused by strong conjugative interaction of the central p orbitals with the cyclopropane rings. We think this symmetrical cation is identical with the transition state for the Cope rearrangement of 9-barbaralyl cation.
Syntheses of Substituted Phenyl-2-thienyliodonium Halides and Their Pyrolysis Reactions
Authors: Yamada Yorinobu , Okawara Makoto 
Published: July 2006

Abstract
Various substituted phenyl-2-thienyliodonium halides were prepared by the reaction of thiophene with substituted phenyliodoso acetates in acetic anhydride–concentrated sulfuric acid. In the pyrolysis reaction of substituted phenyl-2-thienyliodonium chlorides it was found that the chloride ion selectively attacked the 1-carbon of the phenyl group. The product ratios in the pyrolysis reaction of substituted phenyl-2-thienyliodonium bromides can be explained on the basis of a bimolecular aromatic nucleophilic substitution except for p-chlorophenyl-2-thienyliodonium bromide. In the case of p-chloro substituted derivative an interesting effect of p-chloro group was observed. The pyrolysis reaction of substituted phenyl-2-thienyliodonium iodides gave substituted phenyl iodides and 2-iodothiophene. The solution reaction of phenyl-2-thienyliodonium halides in N,N-dimethylformamide gave halobenzene and 2-iodothiophene. These results suggest that the reaction proceeds via an interaction between the halide ion and the phenyl group in a trigonal-bipyramidal structure.
The Reaction of Dicarbonyl Compounds with Potassium in the Presence of Trimethylsilyl Chloride
Authors: Murakawa Takashi , Fujii Koji , Murai Shinji , Tsutsumi Shigeru 
Published: July 2006

Abstract
The reaction of dicarbonyl compounds with potassium in the presence of trimethylsilyl chloride was studied. The carbonyl compounds were benzil (II), 9,10-phenanthroquinone (III), p-benzoquinone (IV), disodium salt of tetrahydroxy-p-benzoquinone (V), and trans-dibenzoylethylene (VI), as well as benzophenone (I). I and II gave bistrimethylsiloxy compounds in good yields, but III did not react under the same conditions. 1,4-Bistrimethylsiloxybenzene and 1,4-diphenyl-1,4-bistrimethylsiloxybutadiene were obtained from IV and VI respectively. A similar conjugate reductive silylation was successful with V affording hexakistrimethylsiloxybenzene in 35% yield.
Products from the Reaction of Dinitrotetramethylbenzenes with Fuming Nitric Acid. A New Route to Some Polynitro Carbonyl Compounds
Authors: Suzuki Hitomi , Nakamura Kiyomi 
Published: July 2006

Abstract
Reaction of dinitrotetramethylbenzenes with fuming nitric acid has been investigated. 5,6-Dinitro-1,2,3,4-tetramethylbenzene undergoes a slow oxidation to give 2,3,4,5-tetranitro-2,3,6,6-tetramethylcyclohex-4-enone in 82–87% yield, which is thermally unstable and upon heating readily converted into 4,5-dinitro-2,3,6,6-tetramethylcyclohexa-2,4-dienone losing two molecules of nitrogen dioxide. 4,6-Dinitro-1,2,3,5-tetramethylbenzene reacts readily with cold fuming nitric acid, giving 2,6-dinitro-3,4,5-trimethylbenzaldehyde in 76–84% yield, together with small amounts of 2,6-dinitro-3,4,5-trimethylphenylnitromethane, 2,6-dinitro-3,4,5-trimethylbenzoic acid, and 2,6-dinitro-3,4,5-trimethylbenzyl alcohol. 3,6-Dinitro-1,2,4,5-tetramethylbenzene is stable towards the action of fuming nitric acid, but is slowly converted into 3,6-dinitro-2,4,5-trimethylbenzyl nitrate on being heated with mixed acid at 40–50°C. The mode of formation of unusual products is briefly discussed.
Total Syntheses of Carbohydrates, IV. 2-Deoxy-Dl-, l- and d-erythro-pentoses and Related Sugars
Authors: Nakaminami Gen , Shioi Sachiko , Sugiyama Yoko , Isemura Satoko , Shibuya Mikio , Nakagawa Masazumi 
Published: July 2006

Abstract
5-Bromo-2,5-dideoxy-threo-pentono-γ-lactone (III) could be obtained stereoselectively from 3-hydroxy-4-pentenoic acid (I) by the reaction with N-bromosuccinimide in water. On successive treatment with an aqueous potassium hydroxide and an acid type cation exchange resin, bromolactone (III) gave stereoselectively 2-deoxy-erythro-pentono-γ-lactone (IV). Reduction of IV by means of bis(1,2-dimethylpropyl)borane afforded 2-deoxy-erythro-pentose (V). 3-Hydroxy-4-pentenoic acid (I) could be optically resolved. The (+)-acid yielded 2-deoxy-d-erythro-pentose (d-V) and the (−)-acid could be converted to 2-deoxy-l-erythro-pentose (l-V). 2,5-Dideoxy-threo-pentose (VIII) and 5-bromo-2,5-dideoxy-threo-pentose (IX) were obtained from bromo-lactone (III). Diethyl mercaptal of IX gave azido-compound (XI) in a low yield by the reaction with sodium azide. The conformation of γ-lactones (III, IV, and VII) and the mechanistic aspects of stereoselective reactions are discussed.
Electron Spin Resonance Study of Adduct Formation by Bis(trifluoroacetylacetonato) copper(II) with Phosphorus Donor Ligands
Authors: Leh F , Chan K M 
Published: July 2006

Abstract
The study of the ESR spectra parameters of bis(trifluoroacetylacetonato)copper(II)-phosphorus complexes in chloroform solution at room temperature and 77°C shows that the g and hyperfine tensors change with the formation of 1 : 1 adduct. Such effect is more clearly exhibited by the parameters A|| and g||. A correlation is obtained between the spectral data and the basicity of the tertiary phosphine ligands.
Stable Paramagnetic Species in Natural Strontium Sulfate Crystals
Authors: Matsuzaki Toshio , Setaka Morio , Gromov V V , Kwan Takao 
Published: July 2006

Abstract
Natural strontium sulfate crystals were found to show complex ESR spectra without any special irradiation. The spectra were classified into three groups, A, B, and C; the thermal and photochemical behavior of each group was distinguished from that of the others. It was proposed that Group B originates from SO3- radicals, and Groups A and C were tentatively interpreted as due to lattice defects (F-center and V-center).
The Nuclear Magnetic Resonance Study of Several o-Disubstituted Benzenes
Authors: Kondo Michio 
Published: July 2006

Abstract
The nuclear magnetic resonance spectra of six o-disubstituted benzenes containing a carbonyl group have been analyzed. The chemical shifts of the proton-6, adjacent to the carbonyl group, show a solvent dependence, indicating changes in the intramolecular interactions between the two ortho substituents.
Polymerization of Vinyl Monomers in the Presence of Surface Active Agents. II. The Rate of Polymerization of Methyl Methacrylate
Authors: Asahara Teruzo , Sen\={o} Manabu , Shiraishi Shinsaku , Arita Yoshikazu 
Published: July 2006

Abstract
The polymerization of methyl methacrylate in the presence of sodium tetrapropylenebenzenesulfonate(ABS) in an aqueous system without any ordinary initiators was examined kinetically. The rate of polymerization of methyl methacrylate is dependent on the initial concentrations of methyl methacrylate and ABS, and expressed by the equation:
Rp∝[ABS]0.37[MMA]0.32
The apparent activation energy of the polymerization is about 3 kcal/mol. It was confirmed by electron microscopic observation that the number of polymer molecules is in the same order as that of the micelle particles in the polymerization system.
Oxidative Coupling of Aminonaphthols
Authors: Omote Yoshimori , Takizawa Yasuomi , Sugiyama Noboru 
Published: July 2006

Abstract
The oxidative coupling of three aminonaphthols by manganese (III) tris(acetylacetonate) was examined. The products from 5-amino-2-naphthol were enol-acetylacetonylidene-1-(6-hydroxynaphthyl)-inline (1) and 2,2′-dmydroxy-5,5′-diamino-1,1′-binaphthyl (2); those from 8-amino-2-naphthol were 4-(acetylacetone-3″-yl)-7,7′-dihydroxy-1,1′-azonaphthalene (3) and eno1-acetylacetonylidene-7-hydroxy-1-naphthylimine (4); the product from 5-amino-1-naphthol was enol-acetylacetonylidene-4-hydroxy-1-naphthylimine (5).
Study on Reverse Osmosis. The Permeation Behavior of Surfactant Solutions through Cellulose Acetate Membranes
Authors: Kamizawa Chiyoshi , Ishizaka Seiichi 
Published: July 2006

Abstract
Transport phenomena of some surfactants were investigated with Loeb-type skinned membranes annealed at 60, 70, 75, and 80°C, with the following results. (1) The rejection of cationic and anionic surfactants is larger than that of nonionic surfactants, especially at concentrations below CMC. (2) In the case of nonionic surfactants, their fluxes decrease with the increase of molecular weight. (3) The effect of CMC on the transport of surfactants is great, particulary in the case of nonionic surfactants. (4) Concentration polarization on the surface of the membrane can be predicted by taking into account the difference between surfactant fluxes below and above CMC.
The Preparation of Divalent Cation Non-permselective Cation Exchange Membrane by Coating with Vinylon Film
Authors: Dohno Reizo , Azumi Takatugu , Takashima Shiro 
Published: July 2006

Abstract
The preparation of non-permselective membrane for the divalent cation was attempted by coating it with thin vinylon film on one side of a commercial cation-exchange membrane. When the coating surface of the cationexchange membrane was set on the concentration-compartment side (cathode side), the permselectivity coefficient of the calcium ion to the sodium ion was equal to that of untreated cation-exchange membrane and no effect of the selective treatment was recognized. However, when the coating sufrace was directed to the desalting-compartment side (anode side), an effect of the selective treatment was observed; in this case, the permeability of the calcium ion was more depressed, corresponding with the formalation degree of the selective-treatment membrane; for example, the permselectivity of the calcium ion for the membrane which was formalated for 180 min at 30°C decreased about one half compared with the untreated membrane. The electric resistance of the cation-exchange membrane increased upon the coating with the vinylon film, and especially the resistance of the calcium ionic-form membrane indicated a remarkable increase.
An NMR Study of Metal Complexes Containing Acetylacetone and Related Compounds. IV. The NMR Spectra and the Ligand-exchange Reaction of Cobalt(III) Complexes Containing N,N′-Ethylenebis(acetylacetonimine) and Amino Acid
Authors: Fujii Yuki 
Published: July 2006

Abstract
A series of mixed cobalt(III) complexes with the general formula of K[Co(baen) (amino acid anion)2]·nH2O (baen=dianion of N,N′-ethylenebis(acetylacetonimine); amino acid = glycine, β-alanine, l-alanine, d-alanine, d,l-alanine, l-valine, d-valine d,l-valine, l-leucine, l-isoleucine, and l-phenylalanine) were newly prepared from a reaction mixture of trans-N,N′-ethylenebis(acetylacetoniminato)diaquocobalt(II), [Co(baen)(H2O)2], and the amino acids. Also prepared were mixed cobalt(III) complexes having the general formula of [Co(baen)(X)2]-ClO4(X=glycine ethyl ester, l-alanine ethyl ester, l-leucine ethyl ester, l-phenylethylamine, d-phenylethylamine, and d,l-phenylethylamine). From the elemental analyses, and the IR and NMR spectra, the amino acid anions were found to coordinate as a unidentate ligand, and the structures of all the complexes were determined to be trans with respect to the two nitrogen atoms of the coordinated amino groups. The NMR spectral behavior of the complexes containing d,l-amino acid anions and d,l-phenylethylamine was well interpreted in terms of the existence of the following three species in a relative ratio of 1:2:1; [Co(baen)(l-form ligand)2]±n, [Co(baen)(l-form ligand)(d-form ligand)]±n, and [Co(baen)(d-form ligand)2]±n. A rapid intermolecular exchange reaction of the apical amino acid anion groups was newly found in water: [Co(baen)(A)2]−+[Co(baen)-(B)2]−\ightleftharpoons2[Co(baen (A)(B)]− (where A and B indicate the apical amino acid anions). Also found was a rapid exchange reaction of the apical amino acid anion groups between the complex and free amino acid anion. Strong support for the rapid inter molecular exchange reaction was obtained in a CD spectral study of them.