bluuebunny/crossref_metadata_2025 huggingface dataset:
Aminosugars. XIX. On the Structure of 2-Deoxy-2-guanidino-d-glucose
Authors: Yoshimura Juji , Sekiya Tetsuo , Iida Takao
Published: July 2006

It was found that 2-deoxy-2-guanidino-d-glucose prepared by guanidination of 2-amino-2-deoxy-d-glucose with cyanamide exists mainly as α-d-glucofurano[1′,2′;4,5]-2-imino-imidazolidine (5) which is easily converted into 2-imino-4-(d)-arabino-tetrahydroxybutyl)imidazoline-4 (6) under alkaline conditions. Acetylation of 5 and 6 gave the corresponding hexa- and heptaacetate (7 and 8), respectively. Warming of 7 in alcohols gave addition compounds of alcohols to the imino double bond, and deacetylation with sodium alcoholate at a room temperature yielded 2-acetamido-4-(d-arabino-tetrahydroxybutyl)imidazole (10). Similar treatment of 8 in ethanol at elevated temperature gave an unknown addition compound in which two N-acetyl groups were eliminated, and deacetylation with a small amount of sodium methylate yielded a mixture of (2R,S)-2-acetamido-2-methoxy-4-(d-arabino-tetraacetoxybutyl)imidazoline-4 and tetra-O-acetyl derivative of 10 which was also obtained by acetylation of 10.
The Isomerization of Propylene Oxide on Metal Phosphate Catalysts
Authors: Imanaka Toshinobu , Okamoto Yasuaki , Teranishi Shiichiro
Published: July 2006

The isomerization of propylene oxide was carried out on metal phosphate catalysts. The main products were allyl alcohol, propionaldehyde, acetone, and 1-propanol. It was found that allyl alcohol is produced by acid-base bifunctional catalysts, acetone, by basic-site catalysts only, and propionaldehyde, by acid-site catalysts. 1-Propanol may be produced by the hydrogen-transfer reaction of allyl alcohol. The conversion to propionaldehyde is proportional to the acidity of the catalyst, the strength of which is stronger than H0=+4.8. The sum of the conversions to allyl alcohol, acetone, and 1-propanol correlate linearly with the observed basicity (H0≥+7.2) of the catalyst. The selectivity and activity are determined by the basic and acidic properties of the catalyst. The mechanisms of the propylene oxide isomerization are also discussed.
The Crystal and Molecular Structure of Bis(l-prolinamidato)-nickel(II) Dihydrate
Authors: Tsukihara Tomitake , Katsube Yukiteru , Fujimori Kumiko , Ishimura Yoshihisa
Published: July 2006

The crystal structure of bis(l-prolinamidato)nickel(II) dihydrate has been determined by three dimensional X-ray analysis. The crystals are vermilion needles and belong to the space group P21. The unit cell has dimensions a=10.915, b=7.319, c=9.445 Å, β=112.6° and contains two structure units. The structure has been solved using Patterson synthesis, minimum function and Fourier synthesis and refined by diagonal and blockdiagonal least-squares methods on 1115 independent reflections. The final R value was 0.054. The nickel atom exhibits square planar coordination. Two proline-amide molecules are approximately related to each other by a two fold axis and these two ligand molecules coordinate to the central nickel atom in trans form. The oxygen atom of water does not coordinate to the nickel atom.
The Nitration of Nickel(II)-, and Copper(II)-complexes of Bis(salicylaldehyde)ethylenediimine
Authors: Tamaki Motonori , Masuda Isao , Shinra Koichiro
Published: July 2006

The M(Salen) complexes (where M=NiII, CuII, CoII-NO, and VIVO, and where Salen=bis(salicylaldehyde)-ethylenediiminato dianio) were reacted with nitric oxide in organic solvents in the air. The free ligand can only form a compound with the formula of SalenH2·2HNO3, while the complexes with M=Ni or Cu gave NO2-substituted complexes, M(5,5′-dinitro-Salen), in almost quantitative yields. In the cases of Co(Salen)NO and VO-(Salen), no substitution reaction on the phenyl ring took place, but they formed a nitric acid adduct, Co(Salen)NO·nHNO3·nH2O(n=1 and 2) and VO(Salen)·HNO3·H2O. The reactions are thought to proceed by means of a process involving a nitric acid. The reactivity of the Ni- and Cu-Salen complexes is explained in terms of a π-electron localization at the 5- and 5′-positions of the phenyl rings resulting from dπ→pπ back bonding. A lack of a similar substitution reaction in Co(NO)- and VO-Salen complexes is explained as being due to the lower stability in the metal-Salen bonding.
Trace Analysis of Metals by ESR. III. Determination of Silver by Solvent Extraction with Tetraethylthiuram disulfide Silver(II) Complex
Authors: Yamamoto Daijiro , Ozeki Fumiaki
Published: July 2006

A new method was worked out for the determination of silver using ESR. Bivalent complex of silver with tetraethylthiuram disulfide extracted with carbon disulfide, benzene, carbon tetrachloride, xylene, ethylbenzene, toluene, chloroform, and organic solvents was stable. The complex in carbon disulfide gave a very strong ESR signal, the sensitivity being 0.1 ppb. The amount of solution required was 1 ml. Colorimetric method can also be applied. However, the sensitivity was lower than that of ESR method. Silver was determined photometrically at 620 nm as a complex with tetraethylthiuram disulfide. The absorption followed Beer’s law in the range 10–100 ppm of silver concentration at 620 nm. Bivalent silver complex could be selectively extracted in the presence of several ions, except copper(II) and mercury(II). Results of the continuous variation method indicate that the silver(II)-tetraethylthiuram disulfide ratio in the complex is 1 : 1.
The n-π* Absorption and Phosphorescnce of Terephthalaldehyde
Authors: Murakami Yoshio , Shimada Ryoichi , Kanda Yoshiya
Published: July 2006

The n→π* absorption spectrum of terephthalaldehyde (TPA) has been studied. The fn→π*-value observed in cyclohexane at room temperature was 1.3×10−3, which was 2.4 times that of benzaldehyde (BA). Vibrational analyses of the absorption and phosphorescence spectra of TPA indicate that the CHO-torsional, CHO-wagging, aldehyde H-wagging, and out-of-plane ring deformation vibrations are important in the vibronic perturbation between (n,π*) and (π,π*) states. The spectral structures and the results of CNDO computations of the fn→π*-values of the n→π* absorptions of TPA and BA suggest that the intensity enhancement in the TPA absorption is due to an increase in the vibronic perturbation between (n,π*) and (π,π*) states as well as to an increase in the electronically-allowed character in TPA in comparison with that in BA.
Mass Spectrometric Analysis of Water-insoluble Yellow Monoazo Pigments
Authors: Kobayashi Kousuke , Hirose Kazutoyo
Published: July 2006

Water-insoluble Yellow Monoazo Pigments were examined in order to establish a new analytical system using mass spectrometry. The characteristic ions observed were as follows: molecular ions, amine-component ions which are formed by the scission of the amide bond with hydrogen transfer and which are the most intense ones, ions at m⁄e: 43, and, in some cases, further-decomposed ions from the amine-component ions. A new analytical system was established on the basis of the analysis of the mass fragmentations of 27 samples, and applied to three unknown samples. The structure of these pigments can be deduced from the low-resolution mass spectra for those derived from substituted anilines, and from the high-resolution spectra for those derived from other amines.
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

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

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

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

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

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

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

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

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

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

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

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 > cis-β form > cis-α form.
The 9-Barbaralyl Cation
Authors: Hoffmann Roald , Stohrer W-D , Goldstein M J
Published: July 2006

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

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

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

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

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

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

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

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

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

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

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

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

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.
Kinetics of Liquid-phase Hydrogenation of Aliphatic α,β-Unsaturated Aldehyde over Raney Cobalt Catalyst Modified with Co-, Mn-, Ni-, and PdCl2
Authors: Hotta Kazuhiko , Kubomatsu Teruo
Published: July 2006

Kinetic studies were carried out on the hydrogenation of the α,β-unsaturated aldehyde, 2-methyl-2-pentenal (UD), over the Raney cobalt catalyst modified with various amounts of Co-, Mn-, Ni- and PdCl2 in n-hexane under atmospheric pressure at 40 and 20°C. Initial rates of formation of the saturated aldehyde (rSD), saturated alcohol(rSA) and unsaturated alcohol(rUA) were determined in the concentration range of UD((CUD) 0.018–0.263 mol/l. It was found that (rSD+rSA) obeyed a Langmuir-type rate equation and rUA a different one. The rate equations are as follows.

r SD+rSA=\frack1·b1·CUD(1+b1·CUD)2, rUA=\frack2·b2·CUD(1+b2·CUD)2

where k and b denote the rate constant of the surface reaction and parameter for the adsorption of UD and hydrogen, respectively, the subscripts 1 and 2 representing the formation of SA and SD and that of UA, respectively. Kinetic parameters k1, k2, b1 and b2 were found to vary with the amount and kind of modifier. The variation of b1 and b2 was irregular. The rate constant k1 decreased with increasing amount of Co-, Mn- and NiCl2 added; it increased remarkably with the addition of PdCl2. The variation of k2 was more complicated. Addition of a small amount of the modifiers did not decrease k2. Further addition of Co- and MnCl2 made k2 decrease, while that of NiCl2 made it increase. Mechanism of the modification with these metal chlorides is discussed on the basis of the active site hypothesis.
The Kinetic Study on the Reaction of Oxaziridine with Tri-n-Butylphosphine
Authors: Tamagaki Seizo , Sakaki Keishi , Oae Shigeru
Published: July 2006

The mechanism of deoxygenation reaction of oxaziridine with trivalent phosphine was kinetically examined by changing substituents, solvents, and temperatures. The reaction proceeds through an attack of phosphine on oxgen in a concerted manner rather than on nitrogen or carbon, eventually producing the corresponding imine and phosphine oxide. The mechanism of the title reaction was compared with those of similar deoxygenations of epoxide and thioepoxide.
Ultrasonic Study on Dilute Aqueous Solutions of Diamines
Authors: Sasaki Katsutaka , Arakawa Kiyoshi
Published: July 2006

Ultrasonic experiments were carried out on aqueous solutions of diamines (ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, and 1,6-hexanediamine) by means of pulse technique in order to study solute-solvent interactions. Sound velocity and absorption coefficient were determined in the frequency range 15–45 MHz. The magnitude of absorption coefficient for each solution increased rapidly with concentration up to about 0.4 mol%. It is concluded that the initial rapid increase is attributed to the proton transfer in base equilibria. The absorption coefficient at the same molar concentration of each solution increases appreciably with the size of hydrocarbon chain from –(CH2)2– to –(CH2)3–. This is ascribed to the formation of icebergs around hydrocarbon groups.
The Effect of Pressure on the Sol-Gel Transformations of Macromolecules
Authors: Suzuki Keizo , Taniguchi Yoshihiro , Enomoto Toshishige
Published: July 2006

The effect of pressure on the gelation of macromolecules, such as gelatin, polyvinyl alcohol, and methyl cellulose, was investigated in order to clarify which binding forces contribute to their gel formations. The values for ΔH and ΔV accompanying the gel formation were calculated from the Eldrige-Ferry’s plot and the Clausius-Clapeyron equation respectively. The values for ΔH and ΔV in the gel fromations of gelatin and polyvinyl alcohol are both negative, while those in methyl cellulose are both positive. From the thermodynamical considerations, it has been found that the formation of hydrogen bonds results in negative values of ΔV Fand ΔH, while that of hydrophobic bonds results in positive values of ΔV and ΔH. Therefore, it may be assumed that the main binding forces in the gelations of gelatin and polyvinyl alcohol may be attributed to hydrogen bonds, and that those in methyl cellulose may be attributed to hydrophobic bonds, at least up to 6000 atm.
Electron Spin Resonance Studies of the Carbon Dioxide Anion Radical Adsorbed on X-Type Zeolites
Authors: Sogabe Kunihisa , Hasegawa Akinori , Yamada Yoshio , Miura Masaji
Published: July 2006

The hindered motion and the structure of the CO2− radical adsorbed on various zeolites were investigated by means of ESR spectroscopy. The adsorbed CO2− radical was obtained by the γ-irradiation of zeolites with carbon dioxide labeled with 13C. The results show that the interaction of the CO2− radical with the zeolite surface changes with the electrostatic field on the surface. The motion and the structure of the adsorbed CO2− radical are affected by the properties of the zeolite surfaces; the former is also influenced by the extent of exchange of the cation on zeolite, regardless of the time of irradiation, before or after the introduction of carbon dioxide. The formation of the CO2− radical on zeolites was interpreted on the basis of such a mechanism that electrons are initially trapped by the surface of zeolite upon the irradiation and then transferred to carbon dioxide molecules. The results also show that the process of the electron transfer depends on the kind of cation.
The Stereochemistry and the Circular Dichroism of Several Pinane Derivatives
Authors: Hirata Toshifumi
Published: July 2006

The optical rotatory dispersion and the circular dichroism curves were measured for some bicyclo[3.1.1]heptane derivatives. The applicability of the octant rule to a bicyclo[3.1.1]heptane system was discussed in connection with its preferred conformation; the conformation was determined on the basis of nuclear magnetic resonance spectrum measurements.
A Deuteron Magnetic Resonance Study of the Motion of Ligands in [Co(ND3)5(D2O)](ClO4)3
Authors: Ito Takeshi
Published: July 2006

The deuteron magnetic resonance of single crystals of aquopentamminecobalt(III) perchlorate was measured at various temperatures. The observed quadrupole coupling shows that [Co(ND3)5(D2O)]3+ ions execute a rapid isotropic reorientation at high temperatures (above 320°K), while only a C3 axis reorientation of the ligand ND3groups is present at low temperatures (below 290°K). No anisotropic uniaxial reorientation was observed about the C4 axis parallel to the Co–(D2O) direction. At temperatures between 310°K and 320°K, the spectrum of a fast exchange limit was observed, together with the spectrum of a slow exchange limit. This anomaly may be explained by the classical rotation of the D2O ligand.
Characterization of the Geometrical Isomers of the Carbonato(or oxalato)-aminoacidatodiammine Complexes of Cobalt(III)
Authors: Nakai Kiyoshi , Kanazawa Shuji , Shibata Muraji
Published: July 2006

Three geometrical isomers of the [CoCO3(aa)(NH3)2]-type complex (aa stands for the α-alaninate, β-alaninate or valinate ion)—the mer(cis-diammine)-, mer(trans-diammine)- and fac-isomers—have been prepared. Three similar isomers of the [Co ox(gly)(NH3)2] and [Go ox(β-ala)(NH3)2] complexes have been obtained by reactions of the corresponding carbonato complexes with an oxalate. In addition, the corresponding three isomers of a related [Co(gly)(NH3)2(OH2)2]2+ complex have been prepared. The isomers thus obtained have been characterized by their absorption, PMR, and IR spectra. Of the mer(trans) isomers of the present complexes, those of the carbonato-α-alaninato and carbonatovalinato complexes revealed clear shoulders in their second absorption bands. Through the present study, some relationships between the appearance of such a shoulder in the mer(trans-diammine) isomer and the ring size of chelates have been deduced.
Determination of the Stability Constants of the Bis(selenocyanato)mercury(II) and Tris(selenocyanato)mercurate(II) Complexes by a Polarographic Method
Authors: Murayama Teisuke , Takayanagi Akio
Published: July 2006

Selenocyanate ions give an anodic polarographic wave with a half-wave potential of 0.033 V (vs. SCE) at 25°C and 0.044 V at 35°C for a 1 mM solution. The electrode process is: Hg\ightleftharpoonsHg2++2e, Hg2++2SeCN-\ightleftharpoonsHg(SeCN)2, Hg2++3SeCN−\ightleftharpoonsHg(SeCN)3−. By means of an equation which gives the relation between the anodic current and electrode potential, stability constants of the bis(selenocyanato)mercury(II) and tris(selenocyanato)-mercurate(II) complexes (β2 and β3, respectively) were calculated from the polarograms. Values of logβ2 and logβ3 at ionic strength 0.3 are, respectively, 21.43 and 25.66 at 25°C, and 20.44 and 24.48 at 35°C.
The Thermal Reaction of 3-Benzoylguaiazulene and Methyl Guaiazulene-3-carboxylate
Authors: Kurokawa Shinji , Hashimoto Mamoru , Hayashi Shûichi
Published: July 2006

3-Benzoylguaiazulene (I) and methyl guaiazulene-3-carboxylate (XI) were heated at 250–260°C. From 3-benzoylguaiazulene we obtained, besides S-guaiazulene (II), three new azulenoids, which were established to be 2-benzoylguaiazulene (III), 1-benzoyl-7-isopropyl-3,4-dimethylazulene (IVa) and 2-benzylguaiazulene (V). On the other hand, the products yielded from methyl guaiazulene-3-carboxylate, together with S-guaiazulene, were elucidated to be methyl 7-isopropyl-3,4-dimethylazulene-1-carboxylate (XII) and methyl guaiazulene-2-carboxylate (XIII). In addition to the loss and the migration of the acyl group, the exchange of acyl and methyl groups in the five-membered ring took place in both acylguaiazulenes, as well as in the case of 3-acetylguaiazulene reported earlier. Moreover, the reduction of the acyl group was also observed in 3-benzoylguaiazulene.
The Synthesis of 3′-Phosphate and 2′,3′-Cyclic Phosphate of 2-Amino-4-hydroxy-6-(1′,2′,3′-trihydroxypropyl)pteridine
Authors: Sugiura Katsura , Yamashita Haruhiro , Goto Miki
Published: July 2006

2-Amino-4-hydroxy-6-(d-erythro-1′,2′,3′-trihydroxypropyl)pteridine 3′-phosphate and 2′,3′-cyclic phosphate, important intermediates of pteridine biosynthesis, were prepared by simple methods. d-erythro-, l-erythro-, d-threo-, and l-threo-isomers of 2-amino-4-hydroxy-6-(1,′,2,′3′-trihydroxypropyl)pteridine, prepared by the method of Viscontini, were phosphorylated with a mixture of phosphorus pentoxide and phosphoric acid. The products were separated by chromatography on a DEAE-cellulose column. The main phosphorylated compounds were 3′-phosphates; small amounts of 2′,3′-diphosphates were also produced. On treatment with DCC, the 3′-phosphate gave 2′,3′-cyclic phosphate.
Crystal and Molecular Structure of ω-Amino Acids, ω-Aminosulfonic Acids and Their Derivatives. I. The Crystal and Molecular Structure of γ-Guanidinobutyric Acid Hydrochloride and Hydrobromide
Authors: Maeda Tomie , Fujiwara Takaji , Tomita Ken-ichi
Published: July 2006

The crystals of γ-guanidinobutyric acid (GGBA) hydrochloride and hydrobromide, C5H12O2N3Cl and C5H12O2N3Br, are both triclinic, space group P\bar1, with two molecules in a unit cell with the following dimensions; hydrochloride: a=7.41, b=9.12, c=7.25 Å, α=101.5°, β=112.4°, γ=65.2°; hydrobromide: a=7.94, b=9.36, c=7.78 Å, α=103.2°, β=115.5°, γ=61.5°. The X-ray structure analysis was carried out by the application of heavy atom method and refined by three dimensional least-squares method. Since GGBA hydrochloride and hydrobromide are isomorphous, the structure analysis was started by using of X-ray data of the hydrobromide to determine the rough atomic coordinates of its molecule, and the data of hydrochloride were used for the further refinement. The positions of the involved twelve hydrogen atoms were located by a three dimensional difference Fourier analysis. GGBA cation, +NH2(NH2)CNH(CH2)3COOH, and Cl− ion were almost perfectly on the (20\bar1) plane and formed a pararell sheet structure with six hydrogen bonds. The possible resonance structures were also discussed.
Reaction of Organoaluminum Coordination Compound with Carbon Dioxide
Authors: Inoue Shohei , Yokoo Yoshiharu
Published: July 2006

The reaction of trialkylaluminum with carbon dioxide was suppressed by the presence of N,N,N′,N′-tetramethylethylenediamine, 2,2′-dipyridyl, N-methylimidazole (MIm), and diethyl ether. On the other hand, the insertion reaction of carbon dioxide into the Al–N bond of diethylaluminum diethylamide was accelerated by the presence of MIm, N-methylbenzimidazole, and pyridine. The complexing agents are considered to play two different roles, i. e., affecting the nucleophilicity of Al–C or Al–N bond and the ability of aluminum atom to accomodate carbon dioxide.
Studies of Organosulfur Compounds. VI. The Preparation of Carbamoyl Esters of Aromatic Dithio Acids and Their Spectral Properties
Authors: Kato Shinzi , Mitani Tsuyoshi , Mizuta Masateru
Published: July 2006

It was found that aromatic dithio acids readily reacted with aryl isocyanate at room temperature to give the corresponding mixed thioanhydrides with the general formula of (ArCS·S·CONHAr) in excellent yields as stable crystals. The mixed thioanhydrides reacted with primary amines at room temperature to give the corresponding thioamides and asymmetric ureas, while the reaction with secondary amines gave the corresponging amine salts and asymmetric ureas in good yields. The spectral properties of the mixed thioanhydrides were discussed.
Asymmetric Hydrogenation of the C=N Bond. A Study of the Controlling Factors on the Stereoselectivity
Authors: Yoshida Takao , Harada Kaoru
Published: July 2006

Asymmetric catalytic hydrogenation of Schiff bases, i. e., N-(methylbenzylidene)-α-methylbenzylamine and N-(ethylbenzylidene)-α-ethylbenzylamine, using 10% palladium hydroxide on charcoal was studied to elucidate the steric course of the reaction. Effects of temperature, solvent, pressure, the amount of the catalyst, and ratio of the syn and anti isomers on the asymmetric hydrogenation were investigated. Temperature, solvent, the amount of the catalyst were found to be factors which controlled the stereoselectivity of the reaction. The hydrogenation of N-(methylbenzylidene)-α-methylbenzylamine always gave a higher asymmetric yield than that of N-(ethylbenzylidene)-α-ethylbenzylamine. Lowering the reaction temperature, lowering the polarity of the solvent, and decreasing the amount of the catalyst gave higher stereoselectivities in the hydrogenation reactions.
Abnormal Hyperfine Splitting in the ESR Spectra of α,α,γ,γ-Tetraphenylallyl-type Organic Stable Free Radicals
Authors: Watanabe Kohji , Yamauchi Jun , Ohya-Nishiguchi Hiroaki , Deguchi Yasuo , Takaki Hideo
Published: July 2006

The ESR spectra of α,α,γ,γ-tetraphenylallyl radical have been first observed. An abnormal ESR hyperfine splitting of this radical has been compared with the ESR hyperfine splitting of other tetraphenylallyl-type radicals; it can be explained very well by introducing the idea of a twisted-allyl model of the molecule.
Monolayers of Poly-γ-benzyl-l-glutamate N-Alkylamides
Authors: Suzuki Asahi
Published: July 2006

To elucidate the effect of long alkyl chains on the surface properties of polypeptides, various poly-γ-benzyl-l-glutamate (PBLG) hexylamides or dodecylamides with different degrees of polymerization were synthesized and their monolayers were examined. PBLG-alkylamides with a low degree of polymerization form expanded type monolayers on water and their surface pressure-area (π-A) curves have two plateaus. The lower plateau in the π-A curve is not seen in the curves of PBLG-alkylamides with a degree of polymerization of more than 10. The lower plateau in the π-A curve is due to the behavior of the terminal alkyl groups. The effect of temperature on the properties of monolayers was examined. Structures formed in the monolayers were discussed.
Syntheses of Some Medium Sized Cyclic Triamines and Their Cobalt(III) Complexes
Authors: Koyama Hiroyuki , Yoshino Tamotsu
Published: July 2006

Four cyclic triamines of a medium ring size (9–12-membered ring) which form three mutually-adjacent five- and/or six-membered chelate rings on complexation, such as 1,4,7-triazacyclononane (abbreviated TACN), 1,4,7-triazacyclodecane (TACD), 1,4,8-triazacycloundecane (TACUD), and 1,5,9-triazacyclododecane (TACDD) were synthesized and isolated as their trihydrobromides. The complexation of TACN and TACD with a cobalt-(III) salt yielded metal complexes of a sandwich-type structure, such as [Co(TACN)2]Br3 and [Co(TACD)2]Br3·H2O, which were then isolated. In the case of TACUD, a complex [Co(TACUD)BrCl2] containing only one molecule of the triamine was isolated. However, although the formation of a cobalt (III) complex with TACDD in solution was inferred spectroscopically, no expected complex was isolable. On the basis of the spectrophotometric data, the ligand-field strength was found to increase in the following order:

[Co(NH3)6]3+<[Co(TACD)2]3+<[Co en3]3+<[Co(TACN)2]3+.