bluuebunny/crossref_metadata_2025 huggingface dataset:
Far Infrared Spectra of Potassium Oxalate Monohydrate and Its Deutero Analog
Authors: Fukushima Kunio
Published: July 2006

The far infrared spectra of potassium oxalate monohydrate and its deutero analog in their crystalline state were measured. Assignment of the infrared absorption bands was made on the basis of frequency shift associated with deuterium substitution of hydrogen atoms in water of crystallization and also on the basis of comparison of neutron scattering spectra of the compounds with the infrared spectra.
νO–H Absorptions and Conformations of Epimeric 1-Tetralols and Chroman-4-ols
Authors: Iwamura Hiizu , Hanaya Kaoru
Published: July 2006

The O–H stretching IR absorptions of epimeric 1-tetralols and chroman-4-ols were examined in dilute carbon tetrachloride solutions. The absorption pattern was found to be related to the conformation of the hydroxyl group; the epimers with the quasi-axial OH group showed a singlet νO–H at 3618 cm−1, while those with the quasi-equatorial hydroxyl had doublet absorption at 3622 and 3600 cm−1. Based on these findings 1-tetralol itself was shown to exist preferentially in the OH axial conformation. The bands at 3618 and 3600 cm−1 were assigned severally to the hydroxyl groups bonding to the π-electrons on the benzene ring. When an additional aryl group is present β to the hydroxyl, another O–H···π bonding to the aryl group becomes possible in addition to that between the OH group and the benzene ring of the tetralin and the chroman skeletons. The conformation of the aryl substituents was deduced by applying the empirical correlation relating the geometry of the molecule to the bonded νO–H frequency in a wide variety of aromatic alcohols which incorporate β-arylethanol moiety.
Separation Factors for Several Lanthanon Pairs Obtained at 60°C in the Ion-Exchange System Involving EDTA
Authors: Hagiwara Zenzi , Noguchi Masaru
Published: July 2006

With a view to the accurate determination of the separation factors of adjacent rare-earth pairs between the aqueous and resin phases, measurements have been carried out at 60°C in the exchange system involving EDTA and Dowex 50W, X-8, 50–100 mesh. Under the same experimental conditions as were used for the isolation of the rare earths by ion exchange, the separation factors at 60°C were found to be 3.43 for Nd-Sm, 1.37 for Eu-Gd, 1.84 for Tb-Y, 1.54 for Y-Dy, 2.83 for Tb-Dy, 1.84 for Dy-Ho, and 2.02 for the Ho-Er and Er-Tm pairs. Further, the observed values were discussed from the viewpoints of both thermodynamics and the real elution of the rare earths by an ion-exchange column.
Cobalt(III) Complexes with Schiff Bases Obtained from Salicylaldehyde Derivatives and Alkanol Amines
Authors: Yamada Shoichiro , Kuge Yoshio , Yamanouchi Kuniko
Published: July 2006

Cobalt(III) complexes with Schiff bases (X-SAL.Y-OH) obtained from salicylaldehyde derivatives and alkanol amines (H2N.Y-OH) were synthesized as crystals. Two types of diamagnetic cobalt(III) complexes were obtained, one being green (type A) and the other red (type B). In the complexes of type A with the general formula [Co(H-SAL.R)3], where R=CH2CH2CH2OH and CH2CH2CH2OCH3, the ligands are considered to function as bidentate ligands, the terminal hydroxyl or methoxy groups not being bound with the cobalt(III) ion. In the complexes of type B with the general formula Co(X-SAL.Y-OH)(X-SAL.Y-O), where X=H and 3-CH3O, and Y=CH2CH2, CH2CH(CH3) and C(CH3)2CH2, the ligands function as terdentate ligands.
The Mechanism of Photochromism, Thermochromism and Piezochromism of Dimers of Triarylimidazolyl
Authors: Maeda Koko , Hayashi Taro
Published: July 2006

A stable free radical, 2,4,5-triphenylimidazolyl, which was produced by oxidation of 2,4,5-triphenylimidazole, dimerizes to yield two dimers, a photochromic dimer and a piezochromic dimer. The photochromic dimer shows thermochromism and photochromism at temperatures between −196°C and about 200°C both in solution and in solid state. The piezochromic dimer shows piezochromism in solid state and thermochromism both in solution and in solid state. Spectro-scopic and kinetic studies showed that photochromism, thermochromism and piezochromism are caused by radical dissociation of the dimers of triphenylimidazolyl on irradiation, heating and grinding. Dimers of substituted triphenylimidazolyl also showed these phenomena which are due to the same mechanism as that of the dimers of triphenylimidazolyl.
Reaction of Alkylidenephosphoranes with Nitrosyl Chloride and Decomposition of α-Hydroxyiminophosphonium Chlorides Formed
Authors: Eguchi Chikahiko , Akiba Kin-ya , Inamoto Naoki
Published: July 2006

The reaction of stable alkylidenephosphoranes with nitrosyl chloride in THF gave α-substituted α-hydroxyiminomethyltriphenylphosphonium chloride (A) in high yields. In the case of active alkylidenephosphoranes, “transylidation” took place simultaneously and a mixture of A and α-substituted methyltriphenylphosphonium chloride was obtained along with corresponding amounts of nitrile and triphenylphosphine oxide. By thermal decomposition, all α-hydroxyiminomethyltriphenylphosphonium chlorides (A) afforded nitriles and triphenylphosphine oxide.
Study of the Sapogenins from Albizzia lebbek Benth. Seeds
Authors: Varshney I P , Badhwar Geeta
Published: July 2006

The seeds of Albizzia lebbek Benth. from Madhya Pradesh have been found to contain a mixture of saponins which on hydrolysis gives echinocystic acid (I), oleanolic acid (II) as major sapogenins and an unidentified sapogenin (not albigenin) in traces. The albigenic acid (III) earlier reported to be present has been shown to be an alcoholic hydrochloric acid isomerisation product of echinocystic acid.
Reactions of Thioamides with Haloacids
Authors: Shaikh Ahmedhusen , Chinone Akiko , Ohta Masaki
Published: July 2006

The reactions of S-carboxymethylisothioamide RC(=NR′)SCHRCOOH with acetic anhydride proceeded through various courses depending on the reaction conditions and the structure of thioamides. When S-carboxymethylisothiobenzanilide (IIa) was treated with a mixture of acetic anhydride and triethylamine in the cold, an intermediate (A), presumably 2-hydroxy-2,3-diphenylthiazolidin-4-one (V), was isolated which was readily converted to benzoylthioacetanilide (IIIa). Attempts to convert A or IIIa to a mesoionic compound failed. Under the same reaction conditions as for IIa, S-carboxymethylisothiobenz-p-chloroanilide (IIb) afforded benz-p-chloroanilide, while corresponding p-anisidide (IIc) gave only tarry product. Attempts to obtain a mesoionic product from pyrrolidine-2-thione or thiocaprolactam and bromoacetic acid were unsuccessful. However, condensation of pyrrolidine-2-thione with α-chlorophenylacetic acid followed by treatment with a mixture of acetic anhydride and triethylamine gave eight-membered rearranged product (XII).
Anionic Telomerizations of Styrene with Some Aromatic Amines
Authors: Asahara Teruzo , Sen\={o} Manabu , Tanaka Sadayoshi
Published: July 2006

The anionic telomerizations of styrene with some aromatic amines catalyzed by sodium metal were investigated. o-Toluidine, m-toluidine, p-toluidine, 2,4-xylidine, 2,5-xylidine and 3,4-xylidine were used as the aromatic amines. Each amine reacted with styrene to give an addition product, which was identified as N-substituted 2-phenylethylamine. Though both α-hydrogen atoms on α-carbon atoms and hydrogen atoms attached to nitrogen atoms of the aromatic amines are weakly acidic, only the latter hydrogen atoms were detached by alkali species under the present experimental conditions. The formations of the products were discussed from the standpoint of anionic telomerization.
Initial Rate and Aging Effect of Ethylene Polymerization with Ziegler-Natta Catalysts. III
Authors: Matsuda Tsuneo , Furukawa Takashi , Togo Shigeyasu , Tanaka Toyosuke
Published: July 2006

The initial rate and the aging effect of ethylene polymerization with TiCl4- and TiCl3-AlEt3 catalyst were investigated. The initial rate, r, was expressed by the equation; r=k1PE+k2PE2, where pE is the ethylene partial pressure and where k1 and k2 are constants. The explanation of the equation is as follows:

&(active site)+M\xrightarrowk_1(polymerization site), rate, k_1P_E

&(polymerization site)+M^*\xrightarrowk_2(propagation), rate, k_2P_E^2

M shows the ethylene monomer which is liberated by the catalyst formation or which is introduced into the system. M* is the monomer which is introduced into the system. The initial rate decreased in the TiCl4-AlEt3 system with the aging-time interval; on the other hand, in the TiCl3-AlEt3 system the rate showed its maximum at about half an hour’s aging. The optimum aging temperature was found to be 20°C. The decrease in the rates between the two systems may be ascribed to the reduction of the Ti atom in the initial valence state of the reaction to the lower valence.
Polymerization of Vinyl Chloride and Copolymerization of Vinyl Chloride with Styrene by Alkylmagnesium Chlorides
Authors: Minato Hiroshi , Oku Masayoshi , Higosaki Nobuyuki
Published: July 2006

t-Butylmagnesium chloride was found to initiate the polymerization of vinyl chloride efficiently at −22–30°C. The best solvent was diethyl ether, but the degree of polymerization was the highest when no solvent was used (\barPn=1940 at 20°C). The apparent activation energy for the rate of polymerization was 13.2 kcal/mol and the frequency factor was 9.06×104. The rate of polymerization, Rp, was equal to const. ×[VC]3.90×[t−BuMgCl]1.98. Isopropylmagnesium bromide initiated the polymerization with less efficiency, and phenylmagnesium bromide was completely ineffective. Vinyl chloride and styrene were copolymerized in ether by t-butylmagnesium chloride at 30°C. The mole % styrene included in the copolymer was considerably different from those obtained by benzoyl peroxide at 48°C or by di-t-butylperoxy oxalate at 30°C.
Asymmetric Reactions. IV. An Attempted Asymmetric Reduction by a Solution of [Co(CN)5]3− and Optically Active α-Amino Acid, and Its Reactive Species
Authors: Ohgo Yoshiaki , Takeuchi Seiji , Yoshimura Juji
Published: July 2006

Reduction of various olefines by a solution of pentacyanocobaltate and glycine or optically active α-amino acid was studied. There is no essential difference between the reactivity of [Co(CN)5H]3− to olefines and that of the solution of pentacyanocobaltate and α-amino acid. Atropic acid was reduced with the solution containing optically active α-amino acid (l-isoleucine) to give slightly optically active hydratropic acid. It was found that the main reactive species in the solution of [Co(CN)5]3− and α-amino acid was [Co(CN)5H]3− (this might be the reason for the asymmetric reduction not taking place effectively), and the reversible change between [Co(CN)5]3− and [Co-(CN)5H]3− was observed depending on the pH of the solution.
Conformations of Sequential Polypeptides Containing l-Alanyl and Glycyl Residues
Authors: Iio Takayoshi , Takahashi Sho
Published: July 2006

The conformations of four polypeptides containing ordered sequences of l-alanyl(A) and glycyl (G) residues, (A)n, (A3G)n, (A2G)n, and (AG2)n, are investigated in solution. The optical rotatory dispersion and infrared spectra showed that all the polymers assume both an α-helical conformation and a β-conformation in solution. The stability of the α-helix decreases in the oder: (A)n, (A2G)n, (A3G)n, and (AG2)n; this may be explained in terms of the interaction between methyl groups of l-alanyl residues regularly arranged on the surface of the α-helix.
Color Reactions of Poly vinyl Acetate and Its Derivatives with Iodine
Authors: Hayashi Sadao , Kawamura Chozo , Takayama Masanari
Published: July 2006

It has been found that the addition of a methanol solution containing polyvinyl acetate (PVAc) and iodine to an aqueous solution of potassium iodide results in a red-violet color without precipitating any polymer. The absorption maximum was located at 510 mμ. The absorbance of the PVAc-iodine complex decreased only slightly with an increase in the degree of the polymerization of PVAc. A linear relationship was obtained between the abosrbance and the PVAc concentration. It was found from these results that the color reaction of PVAc with iodine can be used in a colorimetric determination of PVAc, which is insoluble in water. Further, an attempt was made to investigate the complex formation of the vinyl acetate-vinyl propionate copolymer (PVAc-PVPr) and the vinyl acetate-vinyl formacetal copolymer (PVAc-PVFA) with iodine. Although the absorption maximum of the color complex of PVAc-PVPr with iodine appeared at 510 mμ, independent of the copolymer composition, the absorbance decreased with an increase in the number of vinyl propionate units in the copolymer. The absorption maximum of the complex of PVAc-PVFA with iodine was observed to lie at 620 mμ for highly-acetalyzed polyvinyl alcohol and at 520 mμ for polyvinyl alcohol of a low degree of acetalyzation, while a new absorption maximum appeared in the range from 520 to 620 mμ in the intermediate case. The absorbances at the absorption maxima of the complexes of PVAc-PVFA with iodine were approximately the same as those of PVAc. The effect of an elevated temperature on the absorbance was smaller for PVAc-PVFA than for PVAc-PVPr. From these experiments, it became clear that the glass-transition temperature and the color intensity of the polymer-iodine complex have a simple relation.
The Effect of Pressure on the Electronic Absorpion Spectra of TCNQ Ion Radical Salts
Authors: Sakai Nobuko , Shirotani Ichimin , Minomura Shigeru
Published: July 2006

The effect of pressure up to 7 kbar on the electronic absorption spectra of the crystalline TCNQ anion radical salts and Li(TCNQ) in PVA has been studied. For simple TCNQ salts such as Li(TCNQ), a blue shift with an increase in the pressure has been observed in the absorption band associated with the intramolecular transition. The magnitude of the blue shift is between 45 and 86 cm−1/kbar. The observed shift has been discussed in terms of the crystal-field effect of the cations. For N-MePhe(TCNQ) and M(TCNQ)2, composed of the formally-neutral TCNQ and its anion radical such as TEA(TCNQ)2, a pressure-induced absorption band has been observed at around 20 kK; it may be assigned to the charge-transfer band between the anion radicals.
A Chemical Study on Some Archaeological Samples from Iran and Afghanistan
Authors: Muroga Teruko
Published: July 2006

From archaeological interest, chemical analyses were performed on samples which had been collected from Iran and Afghanistan by the Kyoto University Scientific Mission to the Iranian Plateau and Hindukush. As samples were used more than one hundred pieces of glass and glazed material, and two slag-like objects. By analyzing the glass and glazes for major components, it was found that all were made of soda-lime glass except for a fragment of a glaze of tri-colored pottery collected at Kerman, Iran. It is noteworthy that this fragment of tri-colored pottery had a lead content similar to that of Chinese glazes, while Western glasses are rarely found to contain so much lead. Among the minor components detected, detailed consideration was given to the color origins. Although iron and copper were commonly found in blue-colored samples, the origin of the color of the tile from a mosque at Tabriz was confirmed to be cobalt. Investigations of slag-like objects collected from Tepe Sialk have revealed the possibility that these objects are slags from copper smelting. Studies of the silvery effect or of the weathering observed on the surface of glass and glazes of archaeological importance were carried out by semi-quantitative spectrochemical analysis.
Studies of Ion Exchange Membranes. XXXI. The Hydrogen Peroxide Treatment of the Cation Exchange Membrane of Ferric Ion Form
Authors: Mizutani Yukio
Published: July 2006

Neosepta CL-2.5T, the cation-exchange membrane prepared by the “Paste Method,” of the ferric-ion form was treated with hydrogen peroxide, and the changes in the membrane properties (the thickness, the water content, and the ion-exchange capacity) were measured. The porous membrane, having no ion-exchange capacity, was obtained by the treatment with hydrogen peroxide and the water permeation through the membrane was measured. Assuming the capillary model, the water-permeability data of this membrane suggested that the apparent pore radius of this membrane was 15–17 mμ and that the apparent pore distance was about 40 mμ. This suggests that Neosepta CL-2.5T contains a minute and continuous heterogeneity; i.e., there is a localized distribution of the ion-exchange resin component within the membrane.
ESR Spectra of γ-irradiated Linear Aliphatic Polyesters
Authors: Nozawa Yasuo
Published: July 2006

The ESR spectra of γ-irradiated linear aliphatic polyesters (2.2, 2.4, 2.6, 2.7, 2.8 and 6.8 polymer) have been measured at various temperatures ranging from 77°K to room temperature. Two types of spectra are obtained in these polyesters except for 2.2 polymer. The first, the six-line spectrum obtained at low temperatures was relatively short-lived and increased in signal intensity with increasing methylene groups of these polyesters. The well-resolved, second, five-line spectrum is stable even at room temperature in comparison with the former. The possible structures of two radicals were discussed.
The Dye-sensitized Photolysis of Hexamethyleneammonium Hexamethylenedithiocarbamate by Thiazine Dyes
Authors: Yamase Toshihiro , Kokado Hiroshi , Inoue Eiichi
Published: July 2006

Hexamethyleneammonium hexamethylenedithiocarbamate (HMTC) was photolyzed by UV light to yield carbon disulfide as the decomposition product. This photolysis could be sensitized by thiazine dyes, such as methylene blue and thionine. New methylene blue was the most effective among the sensitizers of this type examined. Bewteen the reciprocal concentration of HMTC and the reciprocal quantum yield, a linear relation was observed. The presence of oxygen was essential for the sensitization. Systems containing methylene blue appear to be more sensitive to oxygen than those containing thionine or new methylene blue. In the presence of an appropriate reducing agent such as allylthiourea, the quantum yield was decreased. The sensitization mechanism by thiazine dyes was probably different from that by benzophenone previously reported. It seems that the sensitization by thiazine dyes takes place by means of the interaction of the triplet state of the sensitizer with dissolved oxygen.
Biradical Spin-Labeled Micelles
Authors: Ohnishi Shun-ichi , Cyr Theodore J R , Fukushima Hiroko
Published: July 2006

A biradical spin-label, N,N′-di-[4-(1-oxyl-2,2,6,6-tetramethylpiperidyl)] urea, has been used for studying the dynamic structure of a micelle, sodium dodecyl sulfate (SDS). Analysis of the ESR spectra of the label has shown that the biradical was incorporated in the micelle. The tumbling motion of the label in the micelle was not strongly inhibited, suggesting a dynamic character of the micelle structure. The exchange rate of the biradical between the micelle and the water phases was slower than 107sec−1. The partition coefficient expressed as the ratio of the concentration of the biradical in the micelle to that of the biradical in the water phase was approximately 6×105 in the SDS concentration lower than 2×10−2m. The biradicals form aggregate in the micelle, when they are present in excess in the solution.
Studies of the Structure of Polyurethane Elastomers. I. The Number-average MW Determination of the Hard-segment in the Poly(Ether)Urethane Elastomer by Means of Perchloric Acid Depolymerization
Authors: Suzuki Hajime , Ono Hiroshi
Published: July 2006

Urea segment which is called a hard-segment in the poly(ether)urethane elastomer (PEUE) consisting of a polyether segment,urethane segment,and urea segment was isolated by means of perchloric acid depolymerization. The number-average molecular weight (MW) of the urea segment obtained by the above method was determined by elemental analysis and by volumetric analysis. By comparing the analytical results with the results calculated for a random polymerization, the number-average MW of the hard-segment was found to deviate from that expected from the equal reactivity of the two isocyanate groups in 4,4′-diphenyl methane diisocyanate (MDI). Therefore, an apparent reactivity ratio of two isocyanate groups in MDI (A) can be calculated from the number-average MW of the hard-segment isolated by means of perchloric acid depolymerization.
Studies of the Structure of Polyurethane Elastomers. II. The Determination of the Blockiness of Poly(Ether)Urethane Elastomes
Authors: Suzuki Hajime , Ono Hiroshi
Published: July 2006

Two types of poly(ether)urethane elastomers (PEUE), which had the same composition ratio but different degrees of blockiness, were synthesized by the reaction of 4,4′-diphenyl methane diisocyanate (MDI), polyoxytetramethylene glycol (PTG), and hydrazine (HD) or ethylenediamine (EDA) by means of the prepolymer method. The degree of blockiness of the PEUE thus synthesized by the reaction of MDI, PTG, and HD was determined by measuring the molecular weight of a hard segment (urea segment), itself obtained by perchloric acid depolymerization. The values of the blockiness of PEUE which had been synthesized by the prepolymer method without any solvent or in a solvent by means of a prepolymer reaction were about 0.4 and 0.7 respectively. The degree of the blockiness of the PEUE prepared from MDI, PTG, and HD, as measured by the above method, corresponded to the infrared absorbance ratio of the PEUE synthesized by the reaction of MDI, PTG, and EDA at 1740 cm−1 and 1720 cm1. From these results two infrared absorbances, at 1740 cm−1 and 1720 cm−1, were assigned to the urethane linkage in a soft segment and at the end of an urea segment respectively.
Diffuse Reflection Spectra of Acid Clays Colored with Benzidine and Some Other Diamines
Authors: Hakusui Akihiko , Matsunaga Yoshio , Umehara Kenji
Published: July 2006

In order to identify the species responsible for the coloration of acid clay upon the addition of benzidine and related aromatic diamines, the diffuse reflection spectra of colored clays in the presence of water, methanol, and benzene were examined in the range from 4 to 29 kK. The coloration appeared to be due to the oxidation of the diamines held between the silicate sheets to the mono-and di-valent cations. The former cations were found to be in various modes of intermolecular interaction, depending on the kind and amount of the liquid. The lightening of the color upon drying was attributed to the disproportionation of the monovalent cations to the divalent cation and the protonated molecule.
Calculation of the Hyperfine Coupling Constants of Some σ Electron Radicals
Authors: Yonezawa Teijiro , Kawamura Takashi , Kato Hiroshi
Published: July 2006

The isotropic hyperfine coupling constants of cyclopropyl, vinyl, formaldiminoxy, formyl, and hydrogen cyanide anion radicals are calculated by a method which corresponds to the extension of the McLachlan procedure. These hyperfine coupling constants are then studied, and the contributions from the spin delocalization and spin polarization mechanisms are estimated. The role of one-center exchange integrals in the estimation of these hyperfine coupling constants is also studied; it is shown to be important in the claculation of the hyperfine coupling constants of the nuclei of the radical-center atom and of the atoms bonded to it.
On the Ligand Exchange Equilibrium in the Propylene-Mercury(II) Complex
Authors: Kawai Itsuro , Nakajima Riichiro , Hara Tadashi
Published: July 2006

The equilibrium between the propylene-mercuric complex and either Cl−, Br−, I−, or EDTA, and their dependences on the pH were investigated manometrically. The propylene-mercuric complexes present in the above equilibrium were found to be (HO−)n-Hg2+-Propylene (n=0, 1 and 2) and (HO−)n-Hg2+(X−)-Propylene (n=0 and 1), and their equilibrium equations were:

& (HO^-)_n-Hg^2++Propylene\oversetK_p1\ightleftharpoons(HO^-)-Hg^2+-Propylene

& X^--Hg^2+-(HO^-)_n+Propylene\oversetK_p2\ightleftharpoons(HO^-)_n-Hg^2+(X^-)-Propylene.

By introducing Kp1=K′p1 and Kp2=K′p2 when n=0, the dependences on the pH were shown by:

logK_p1=logK’_p1+2·pH, logK_p2=logK’_p2+pH

where K′p1=2.2×105, K′p2(cl)=4.1×105, and K′p2(Br)=2.7×106 at 25°C and μ=0.8. As was to be expected from the above equilibrium, K′p1 was idependent of the presence of Cl−, Br−, I−, and EDTA, while K′p1 varied in the presence of Cl−, Br−, and I−. The above relationships were also derived theoretically.
The Reaction between Mercury(II) and Organic Compounds. VIII. Titrimetric Determination of Mercury(II) with o-(2-Thiazolylazo)-2,4-dichlorophenol as a Metallochromic Indicator
Authors: Kai Fumiaki
Published: July 2006

The reaction between mercury(II) and o-(2-thiazolylazo)-2,4-dichlorophenol (TADC) was investigated spectrophotometrically. A mixture containing TADC and a large excess of mercury-(II) showed the absorption maxima in the range of pH 2.3–5.0 at 570 mμ. The composition of the chelate was considered to be as Hg(II) : TADC=1:2. No homologous color was obtained by the reaction between TADC and the other metal ions in the above pH range. Therefore, TADC was suggested as a suitable metallochromic indicator for the direct titrimetric determination of mercury(II) ions with EDTA at pH 3.8–5 (citric acid plus disodium hydrogenphosphate buffer). Sharp color changes were observed from deep violet to orange or to reddish orange at an equivalence point. The titrimetry could be carried out satisfactorily within a range of error of ±0.5% at mercury(II) concentrations of more than 2×10−4m by the present method.
Cobalt(III) and Chromium(III) Complexes with Ethylenediaminemonoacetic Acid
Authors: FuJii Yuki , Kyuno Eishin , Tsuchiya Ryokichi
Published: July 2006

Cobalt(III) and chromium(III) complexes with ethylenediaminemonoacetic acid (EDMA), [Co(edma)2]Cl·2H2O and [Cr(edma)2Cl·3H2]O, (edma: H2NCH2CH2NHCH2COO−), were prepared. The former complex was isolated as two geometrical isomers. From the electronic absorption spectra, the two isomers were assigned to trans and cis forms with respect to the carboxylate oxygen atoms coordinated. Chromium(III) complex was concluded to have the trans form by comparing the IR spectrum with those of the above two isomers of cobalt (III) complexes.
The Thermal Decomposition of Potassium Trioxalatoferrate(III) Trihydrate
Authors: Tanaka Nobuyuki , Sato Katsuya
Published: July 2006

The thermal decomposition of K3[Fe(C2O4)3]·3H2O in solid state was studied by the thermogravimetric, the infrared spectroscopic and the manometric methods. It was found that, with elevating temperatures, three moles of water were evolved as the first step to form an anhydrous complex K3[Fe(C2O4)3], which was then decomposed as the second step by an electron transfer from a ligand to the central iron(III) with the formation of an iron(II) complex. K2[Fe(C2O4)2], K2C2O4 and CO2 were found as products in the second step. The total pressure of CO2 gas evolved was measured at suitable time intervals. The shape of a curve of α (the fraction isothermally decomposed) vs.  t (time) was sigmoidal. The initial part of the decomposition reaction was kinetically of a first-order and the activation energy was obtained to be 43.6 kcal/mol. A main part of it (0.2<α<0.8) was of a second-order and obeyed the Prout-Tompkins’ law. The activation energy was calculated to be 35.3 kcal/mol.
Synergistic Effect in Solvent Extraction—Effect of Oxygen and Nitrogen Containing Organic Bases on the Stability of Zinc(II) and Cobalt(II) β-Diketonate Adducts—
Authors: Shigematsu Tsunenobu , Honjyo Takaharu , Tabushi Masayuki , Matsui Masakazu
Published: July 2006

The effect of the organic Lewis bases acting as a synergist on the extraction of zinc(II) and cobalt(II) with benzoyltrifluoroacetone was studied. n-Hexyl alcohol, TBP TBPO and TOPO were used as oxygen-containing bases, and quinoline, isoquinoline, lepidine, acridine and quinaldine as nitrogen-containing bases. The stability constants between metal chelates and the adduct forming materials in the organic phase were obtained by curve fitting method. The results are summarized as follows: (1) Zinc(II) and cobalt(II) chelates formed adducts including one or two molecules of the bases per metal ion. Adduct formation was carried out successively. (2) The stability of adducts with oxygen-containing organic bases increased in the order, n-hexyl alcohol<TBP<TBPO≈TOPO. This is the same order with that of the basicity of donor oxygen in the compounds. The stability of adducts with nitrogen-containing bases increased in the order, quinaldine<acridine<quinoline<lepidine<isoquinoline. In this case, however, the steric effect of the bases preferably contributed to the adduct formation. (3) The overall stability constants of the adducts are affected by the coordination number of the metal ions. Cobalt(II) adducts are more stable than zinc(II) adducts.
Studies on the Substrate Specificity of Taka-amylase A. III. Syntheses of Some New Derivatives of Phenyl α-Maltoside
Authors: Arita Hitoshi , Isemura Mamoru , Ikenaka Tokuji , Matsushima Yoshio
Published: July 2006

In order to obtain information of the interaction between various portions of the substrate molecule and the enzyme protein, mono-O-methyl derivatives of phenyl α-maltoside and its analogues were synthesized and the enzymatic action was investigated. The purity and chemical structure of the compounds were confirmed by chromatographic method, phenol determination, and elemen talanalyses. The anomeric configuration of the glycosidic linkage to phenol was presumed to be of an alpha type on the basis of the high positive value of specific rotation. Some regularities in the enzymatic action on these synthetic substrates were observed.
Thermal Decomposition of Uranyl Dihydrogen Orthophosphate Trihydrate
Authors: Kamo Mutsukazu , Ohashi Shigeru
Published: July 2006

The thermal decomposition of uranyl dihydrogen orthophosphate trihydrate was studied by means of paper chromatography, X-ray diffractometry, differential thermal analysis, thermogravi-metric analysis, infrared spectroscopy and chemical analysis. From these studies, it was revealed that in the thermal decomposition of the uranyl salt the following reactions take place. 1) The formation of condensed phosphates with relatively small polymerization degrees such as di- and triphosphates takes place below 300°C, accompanied by the elimination of water. 2) A uranyl salt of long-chain metaphosphate, [UO2(PO3)2]n is produced bewteen 300 and 840°C. 3) The metaphosphate is melted at about 900°C, while uranium(VI) is reduced to uranium(IV) at the same time. 4) As a result of the reduction, the formation of uranium(IV) diphosphate, UP2O7, starts. 5) Finally, almost pure uranium(IV) diphosphate is produced at 1200°C.
The Formation of Pyrazolo[1,5-a]pyrimidine Derivatives
Authors: Hori Isaburo , Saito Koji , Midorikawa Hiroshi
Published: July 2006

The combination reactions of 3-alkyl-2-cyano-3-methoxyacrylic esters (I) and their 3-hydrazino derivatives (II) in the presence of pyridine in alcohol at room temperature mostly gave chain intermediates, whose cyclizations led to the formation of only 2,7-dialkyl-5-hydroxypyrazolo-[1,5-a]pyrimidine derivatives. On the other hand, the reaction of Ia (3-Me) with the 5-aminopyrazole derivative (IIIa) obtained by the cyclization of IIa (3-Me) gave 7-hydroxy- and 7-aminopyrazolopyrimidine derivatives in alcohol under reflux via an intermediate. The reactions of 2-cyano-3-ethoxycrotononitrile with IIa or IIIa both afforded 7-aminopyrazolopyrimidine derivatives directly.
Reactions of Nitrones with Free Radicals. I. Radical 1,3-Addition to Nitrones
Authors: Iwamura Michiko , Inamoto Naoki
Published: July 2006

Reactions of the aldonitrones with α,α′-azobisisobutyronitrile or dimethyl α,α′-azobisisobutyrate gave trisubstituted hydroxylamines as addition products, whose structures were determined to be radical 1,3-addition products to the nitrones. Reactions of N-benzyl-α-phenylnitrone with di-t-butyl peroxide and aralkyl hydrocarbons possessing at least one α-hydrogen atom gave similar 1,3-adducts and substituted N-benzylaldonitrones. Reaction of α,N-diphenylnitrone with phenylazotriphenylmethane gave similarly α,α,N-triphenylnitrone. Mechanisms for the formation of these products were discussed.
The Structure of Salts of β-Dione Dioximes
Authors: Iwakura Yoshio , Uno Keikichi , Haga Kazuo
Published: July 2006

Cyclohexane-1,3-dione dioxime hydrochloride was prepared and investigated with reference to its structure. Analysis and a study of its NMR and IR spectra suggested that the salt is the enamine form of the oxime. Further, the salts of 5-methylcyclohexane-1,3-dione dioxime, 5,5-dimethylcyclohexane-1,3-dione dioxime and acetylacetone dioxime were prepared and found to have the same structure.
Effect of Pressure on Graphitization of Carbon. VII. Effect of Pre-Heat-Treatment on Graphitization of Carbon under High Pressure
Authors: Kamiya Kan-ichi , Inagaki Michio , Saito Hajime , Noda Tokiti
Published: July 2006

The soft carbon samples PV-15, -17 and -20, and the hard carbon samples PH-15 and -20, which were prepared by pre-heat-treatment of a polyvinylchloride coke PV-7 at 1500, 1700 and 2000°C and a phenolformaldehyde resine char PH-7, at 1500 and 2000°C, respectively, under reduced pressure, were re-heat-treated under quasi-hydrostatic pressure of 5 kbar. The strctural changes in these carbons by the re-heat-treatment under pressure were studied by X-ray diffraction analysis. On the soft carbons, the rate of development of graphitic compenent was found to become small with the increase in temperature pre-heat-treatment. On these samples, especially on PV-20, the normal homogeneous graphitization of turbostratic component was observed above about 1700°C besides the heterogeneous graphitization. However, the hard carbon samples PH-15 and PH-20 showed the same abrupt heterogeneous graphitization at around 1500°C as the original PH-7. These results suggest that the structure of carbon sample is related to the heterogeneous graphitization under high pressure. One can deduce a conclusion from results of this series of experiments that the heterogeneous graphitization is more dominant in a carbon sample having a lower degree of graphitization, for example, a larger c0-spacing and a smaller crystallite size.
Cobalt(II, III), Nickel(II) and Copper(II) Complexes with Tetra-and Hexamethylenediaminetetraacetate
Authors: Ogino Hiroshi , Kobayashi Shigeru , Tanaka Nobuyuki
Published: July 2006

Synthesis of new complexes of cobalt(II), cobalt(III), nickel(II) and copper(II), [Co2hdta]·6.5H2O, K[Co tdta]·3H2O, [Ni2 hdta]·6.5H2O, Na2[Cu tdta]·6H2O, [Cu2 tdta]·1.5H2O and [Cu2 hdta]·6.5H2O, has been carried out, where tdta and hdta represent (OOCCH2)2N(CH2)4N(CH2-COO)24− and (OOCCH2)2N(CH2)6N(CH2COO)24−, respectively. The infrared, nuclear magnetic resonance and visible and ultraviolet absorption spectra were measured. The infrared and the NMR spectra of the Co(III) complex with tdta indicate that a quadrivalent tdta anion behaves as a hexadentate in this complex.
Non-Equilibrium Thermodynamics: Steady State Thermodynamic Relations in the Non-Linear Current-Affinity Region
Authors: Tykodi R J
Published: July 2006

A simple heat conduction example is used to show that the choice of boundary conditions for describing a steady process, although of no consequence in the linear current-affinity region, governs the applicability (or the lack thereof) of various thermodynamic assertions to the non-linear current-affinity region. The need for a whole family of classificatory principles to aid us in organizing our knowledge about steady processes is pointed out.
Alkoxysilanes. VII. The Preparation of Alkylalkoxysiloxanes
Authors: Kijima Ichiro , Okuda Keisuke , Abe Yoshimoto
Published: July 2006

Trimethylsiloxytri-t-butoxysilane (I), bis(trimethylsiloxy)di-t-butoxysilane (II), and bis(trimethylsiloxy)bis(tri-t-butoxysiloxy)silane (III) were prepared by the reaction of trimethylchlorosilane with tri-t-butoxysilanol, di-t-butoxysilanediol, and bis(tri-t-butoxysiloxy)silanediol respectively. Bis(tri-t-butoxysiloxy)dimethylsilane (IV) was also obtained by the reaction of dimethyldichlorosilane with tri-t-butoxysilanol. The reaction of dimethyldichlorosilane with di-t-butoxysilanediol or bis(tri-t-butoxysiloxy)silanediol gave tetramethyltetra-t-butoxy (V) or tetramethyltetra(tri-t-butoxysiloxy)cyclooctasiloxane (VI). These compounds were identified by means of elemental analysis, molecular-weight determination, and a study of the IR and NMR spectra.
Stereoselectivity of Phenylcarbenoid of Zinc in Cycloaddition with Olefin
Authors: Nishimura Jun , Furukawa Junji , Kawabata Nariyoshi , Koyama Hiroaki
Published: July 2006

The stereoselectivity of phenylcarbenoid of zinc generated from diethylzinc and benzal iodide was investigated in the cycloaddition reaction with olefin. The carbenoid showed larger syn-selectivity than phenylcarbenoid of lithium. Electron-donating substituent attached to the phenyl group of the phenylcarbenoid enhanced the syn-selectivity of the carbenoid. The syn-selectivity of the phenylcarbenoid was larger in ether than in n-pentane, contrary to the case of phenylcarbenoid of lithium.
Electronic Structures of the Oxocarbon Anions. III. Application of the Extended Hückel and Variable Electronegativity Extended Hückel Methods
Authors: Sakamoto Kazuyoshi , I’Haya Yasumasa J
Published: July 2006

The extended Hückel (EH) method with different basis functions and the variable electronegativity extended Hückel (VEEH) method are applied first to the calculation of the electronic structure of CO and then to that of three oxocarbon anions, (C4O4)2−, (C5O5)2−, and (C6O6)2−. MO energies of CO calculated by both methods are closer to those computed by a non-empirical SCF method and also to observed values, compared with those obtained by the CNDO/1 method. It is also found for CO and the three anions that in the EH method the charge distributions are not dependent on the basis functions chosen and are much more localized on the oxygen atoms than in the VEEH method. The latter method yields a π-electron distribution which is close to that predicted by the variable electronegativity π-electron SCF method. The EH and VEEH methods predict reasonable values for the lower excitation energies of these oxocarbon anions; specifically the calculated σ→π* excitation energy of (C4O4)2− agrees well with an observed value.
The Emission Spectra of Pyrazine and Deuterated Pyrazines in the Vapor and in Rigid Matrices at 90°K
Authors: Ishii Hajime , Koyanagi Motohiko , Kanda Yoshiya
Published: July 2006

Emission spectra of pyrazine and its deuterated derivatives have been observed in the vapor and the vibronic structure has been analyzed in detail. The vibronic structures of the phosphorescence spectra of these compounds have been explained all in terms of totally symmetrical vibrations, while the first main bands of the fluorescence spectra were anomalous as well as their progression bands in respect to the band position and intensity distribution. For comparison, the fluorescence spectra have also been studied in rigid matrices at 90°K.
Spectroscopic Determination of Quenching Cross-Sections of Excited Mercury Atoms (63P1, 63P0) in Molecular Collisions
Authors: Horiguchi Hiroyuki , Tsuchiya Soji
Published: July 2006

The concentrations of Hg(63P1) and (63P0) atoms, [Hg1*] and [Hg0*], were determined from the absorptions of 4358 and 4047 Å lines in the Ar-diluted mercury vapor in the presence of several quenching molecules, under the radiation of 2537 Å emission. An apparent absorption intensity was not proportional to [Hg1*] or [Hg0*], and was sensitive to the ratio of the spectral half-width of the light source to that of the absorption line. Therefore, a method to correct an absorption intensity was proposed. The relation of [Hg1*] to [Q], a concentration of quenching molecules, is explained well by the Stern-Volmer equation. The value of [Hg0*] increases with [Q] until it reaches a maximum at a certain value of [Q], and a further increase of [Q] results in a decrease of [Hg0*]. These findings are explained well by the following mechanism: (1) Hg+hν→Hg1*, (2) Hg1*→Hg+hν, (3) Hg1*+Q→Hg+Q, (4) Hg1*+Q→Hg0*+Q, (5) Hg0*+Q→Hg+Q, (6) Hg0*→Hg (by collisions with a wall). The respective values of cross-sections (σ2) of N2, CO, and NO for process (3) are ≤0.03, 0.60, and 20 Å2, and those for process (4) are 0.36, 2.1 and 5 Å2, and those for process (5) are ≤3.6×10−4, 0.15 and 8.0 Å2.
Conformation of Adsorbed Polymeric Chain. IV
Authors: Motomura Kinsi , Moroi Yoshikiyo , Matuura Ryohei
Published: July 2006

In order to develop further the theoretical treatment of a polymeric chain adsorbed at an interface, a random walk model, in which each step has the same probability except that no step can retrace the preceding one on a simple cubic lattice, has been used. The average number of adsorbed segments \barν, the average number of trains \barm, and the mean square end-to-end distance \barr2 are calculated as functions of the adsorption energy of segment ε and the number of segments n when n is infinitely large. The average numbers of segments in a train and a loop, \bark′ and \bark′, are also calculated. Through the increment in the value of critical adsorption energy εc, prohibition of immediate reversal for the random walk fairly influences the average properties of adsorbed polymeric ,chain. The decrease in \barm and the increase in \bark′ with ε⁄kT at its large values are remarkable in comparison with those of the symmetric random walk, which may be accounted for by the diminution of the chance of making loops. It is shown that \barr2 is equivalent to the mean square two-dimensional end-to-end distance of a restricted random walk without immediate reversals on a simple cubic lattice at εc⁄kT and approaches that on a simple square lattice in the limit ε⁄kT→∞.
The Reactions of Aroyl Peroxides with Grignard Reagents. II. Relative Reactivities of Substituted Benzoyl Peroxides
Authors: Okubo Masao , Maruyama Kazuhiro , Osugi Jir\={o}
Published: July 2006

Benzoyl peroxide was found to react with Grignard reagents (RMgBr) in tetrahydrofuran at 0°C to form PhCOOR and PhCOOMgBr. The latter which was isolated as a complex containing two molecules of the solvent, can be coordinated by benzoyl peroxide to form an orange-colored complex. Similar complexes were found to be formed in the cases of some substituted benzoyl peroxides. The initial stage of the reaction was studied with the technique of competitive reaction. The results can be explained by assuming the coordination of the carbonyl oxygen atom of benzoyl peroxide to the Grignard magnesium atom. The effect of the substituent of the peroxide on the reaction was discussed.
The Thermodynamic Properties of the Nonstoichiometric Ceric Oxide at Temperatures from 900 to 1300°C
Authors: Iwasaki Bunji , Katsura Takashi
Published: July 2006

Oxygen partial pressure in equilibrium with nonstoichiometric ceric oxide of a definite composition were determined by equilibration with pure oxygen, air, CO2, and CO2-H2 mixtures at 900, 1000, 1100, 1227, and 1300°C, using a thermobalance. The values for the activities and the relative partial enthalpies and entropies of both Ce2O3 and CeO2 were calculated on the basis of the relation between the Po2 and its composition.
The Zinc Bromide-catalyzed Rearrangement of Pulegone Oxide and Piperitone Oxide
Authors: Watanabe Hajime , Katsuhara Jun , Yamamoto Noriyuki
Published: July 2006

The rearrangement of (+)-cis- (I) and (−)-trans-pulegone oxide (II) was effected by the catalysis of zinc bromide in boiling benzene to give the same (−)-2,2,5-trimethylcyclohepta-1,3-dione (III), with a retention of the optical activity. The structure of (−)-III with the expanded 7-membered ring was confirmed by the chemical transformation into 1,1,4-trimethyl-cycloheptane(IV), which was identical with that derived from eucarvone(V). Piperitone oxide(VIII) was also converted into diosphenol(X) in the same manner as in pulegone oxides.
Reactions of Allenes. IV. New Palladium Complexes Having a Bridged Allene Trimer Ligand
Authors: Okamoto Tadashi
Published: July 2006

Di-μ-acetato-[2,2′-(1-methyleneethylene)bis-π-allyl]dipalladium (I) was obtained (18%) by the reaction of allene and palladium acetate. Its structure was estimated from the data of elemental analysis, molecular weight, hydrogenolysis reaction, IR, and NMR. Complex I was synthesized otherwise by the reaction of allene with di-μ-acetato-2,2′-bi-π-allyldipalladium. The insertion mechanism for the latter reaction was confirmed by the product of the reaction using allene-d4, Pd2(C9H8D4)(CH3COO)2. It was found that this insertion reaction was by far faster than analogous reactions with bis(acetylacetonato)-2,2′-bi-π-allyldipalladium or di-μ-acetato-bis-(π-allyl palladium). The observed acceleration was assumed to be due to strain in the substrate. From NMR data of I and other π-allylpalladium complexes already published, it was shown that the difference in chemical shifts between syn and anti protons of π-allyl complexes is dependent on the substituents on the central carbon; the nonconjugated substituents give smaller values (0,9–1.01 ppm for μ-chloro complexes), and α,β-unsaturated substituents give larger values (1.27–1.28 ppm for μ-chloro complexes). Chloro and acetylacetonato derivatives of I, and the activation energy for spin exchange of saturated methylene protons in I are also described.
Peptide Synthesis by Oxidation-Reduction Condensation. II. The Use of Disulfide as an Oxidant
Authors: Matsueda Rei , Maruyama Hiroshi , Ueki Masaaki , Mukaiyama Teruaki
Published: July 2006

A peptide synthesis starting from free N-protected amino acid and free amino acid ester by the use of triphenylphosphine, an oxygen acceptor, and disulfide, a hydrogen acceptor, was studied. The oxidation-reduction condensation reaction affords peptides with high optical purity in excellent yields by simple procedure.
The Water Structure Model of Narten et al. and the Pressure Effect on Sound Absorption in Water
Authors: Nomoto Otohiko , Endo Harumi
Published: July 2006

The mechanism of the temperature dependence of ultrasonic absorption in water under atmospheric pressure has hitherto been studied by means of the two-state-model theory of water. For an explanation of the pressure dependence of ultrasonic absorption by the two-state model, however, we are obliged to adopt the contradictory assumption that the open-packed structure of water has a higher energy than the more close-packed one. In order to avoid this contradictory assumption inherent in the two state-model theory, we have here employed the water model recently proposed by Narten et al. on the basis of X-ray scattering analysis. Although the calculation based on the Narten-model succeeds in explaining the pressure dependence of the ultrasonic absorption without the above-mentioned contradictory assumption, the structual compressibility (βst) thus obtained is about two times larger than the most reasonable value. The origin of this discrepancy seems to be that the Narten model of water considers the framework of the ice-1 lattice to be of infinite extent, without any boundary. By assuming the cluster-structure to be of a finite size, we can reduce βst to a reasonable value in agreement with the experimental results. The water cluster is found to be about eight molecules in diameter at 4°C.
The Activity of Dilute Sodium in Liquid Au-Na Alloy
Authors: Hirota Kazushi , Katsura Takashi
Published: July 2006

The electromotive force of the cell;

Au–Na alloy |Na2CO3| CO2+O2, Pt-Rh,

was determined as a function of the temperature and the concentration of sodium in the alloy. The results were consistent with the activity values determined previously by the equilibrium method. The overpotential due to the current passing through the Au–Na alloy surface is less than 1 mV per mA/cm2 of the current density at 1400°K. The activity of sodium, referred to the pure liquid standard state, was calculated from the electromotive force of this cell. The activity coefficient of sodium in Au–Na alloy is:

logγNa=−2.55⁄T·10−3+0.39±0.05

in the temperature range from 1250°K to 1500°K and in the concentration range of less than 10 atom%Na.