bluuebunny/crossref_metadata_2025 huggingface dataset:
On the Emission of Excited Complexes Formed between Condensed Aromatic Hydrocarbons and Aliphatic Amines
Authors: Nakajima Akira
Published: July 2006

Anomalous emission observed at long wavelengths in the systems of condensed aromatic hydrocarbons and aliphatic tertiary amines has been studied. The anthracene-tri-n-butylamine system has been dealt with in detail. On the basis of the absorption spectrum, the temperature dependence of the long-wavelength emission and the relation between the quenching of the hydrocarbon fluorescence and the intensity of the long-wavelength emission, it has been concluded that this emission originates from the excited complex formed between an excited hydrocarbon and an amine. The interaction involved in excited-complex formation is of a charge-transfer type. This was confirmed by the correlation of the wavelengths of the excited-complex emission with the ionization potentials of amines and the electron affinities of aromatic hydrocarbons and by the large dipole moment of the excited complex.
Thermodynamic Properties of Carbon Tetrafluoride from 4°K to Its Melting Point
Authors: Enokido Hisae , Shinoda Takako , Mashiko Yo-ichiro
Published: July 2006

Thermodynamic properties of solid and liquid carbon tetrafluoride were measured at temperatures from 4°K to 100°K. The heat of transition was found to be 349.5±0.9 cal/mol, the transition temperature 76.221°K, the heat of fusion 168.6±0.05 cal/mol, the triple point temperature 89.515°K and the triple point pressure 0.80±0.03 Torr. The amount of impurity in the specimen of CF4 was estimated to be 0.0147 mol% from the measurement of the melting point range. The values of molal entropy of CF4 as an ideal gas at 298.2°K, were calculated from the calorimetric and spectroscopic data as 62.63 e.u. and 62.45 e.u., respectively. The Debye characteristic temperature at 0°K was derived from the low temperature heat capacity data, and the θD(T) curve was compared with that for neopentane taking into account the octupole interaction of molecules in the crystal.
Reactions of Metal Chelates. IV. The Reactions of Bis(salicylaldehydato)-copper(II) with Diethylenetriamine and Triethylenetetramine
Authors: Nakao Yasuo , Nakahara Akitsugu
Published: July 2006

The reactions of bis(salicylaldehydato)copper(II) with diethylenetriamine and triethylenetetramine were investigated under several different conditions. In water, in the absence of other reagents, the reactions gave uncharged bis (salicylaldehyde)-diethylenetriamine- and -triethylenetetramine-copper(II), respectively. In the presence of an acid the resulting complexes were the respective cation complexes, in which only one of the two terminal nitrogen atoms was in the form of Schiff base with salicylaldehyde. In the presence of a salt, the resulting complex from diethylenetriamine was a cation complex, and that from triethylenetetramine an uncharged complex. Three new copper(II) chelates were obtained.
Hydrodynamic Voltammetry with the Convection Electrode. III. The Measurements of the Kinetic Parameters of the Electrode Reaction. Part I
Authors: Suzuki Junsuke
Published: July 2006

We have proposed the determination of the kinetic parameters of the electrode reaction by means of convective voltammetry. At the pushed-out mercury-drop convection electrode (PM-DCE), the ratio of the current on a totally-irreversible wave to the limiting current was derived as follows:

(Remark: Graphics omitted.)

This equation was applied to the determination of the kinetic parameters for the electro-reduction of cupric ions in a 0.1 m perchloric acid solution containing 0.05% Triton X-100. It was found that the values of αn and k° the kinetic parameters are 0.59 and 4.2×10−9 cm/sec respectively.
Studies of Phosphorylation. III. Selective Phosphorylation of Unprotected Nucleosides
Authors: Yoshikawa Masaharu , Kato Tetsuya , Takenishi Tadao
Published: July 2006

During an investigation of the factors affecting the reaction of 2′,3′-O-isopropylidene nucleosides with phosphoryl chloride, trialkyl phosphates were found to be powerful accelerators and useful solvents for the phosphorylation. The addition of a trialkyl phosphate to a large excess of phosphoryl chloride was markedly effective in promoting the phosphorylation; further, the lower alkyl phosphates, such as trimethyl and triethyl phosphates, were able to replace the excessive amount of phosphoryl chloride as solvents. When unprotected nucleosides were treated with phosphoryl chloride in trimethyl phosphate, the corresponding 5′-phosphates were mainly produced, together with a small amount of highly-phosphorylated products, in good yields. On the contrary, the treatment of 5′-O-acetyl nucleosides in a similar manner gave the corresponding 2′(or 3′)-nucleotides in low yields. The formation of the 2′(or 3′)-phosphate was strongly inhibited by the addition of a small amount of water to the reaction mixture. Thus, the selective phosphorylation of unprotected nucleosides to the 5′-nucleotides in a one-step procedure was accomplished.
Photochromic Color Change of the Dimer of Triphenylimidazolyl at Low Temperatures
Authors: Maeda Koko , Hayashi Taro
Published: July 2006

The photochromic dimer of triphenylimidazolyl which is one of two dimers obtained by oxidation of triphenylimidazole shows photochromism at temperatures between room temperature and −196°C in solutions and in a solid state. At temperatures higher than about −20°C the photochromic color in solutions is reddish-purple, at temperatures lower than about −150°C the color is bluish-purple and at intermediate low temperatures the photochromic color does not appear. Absorption spectrum and ESR measured with the change of temperature showed variations corresponding to the change of color. The photochromic color in a solid state was light reddish-purple above about −70°C and bluish-purple at −196°C. The mechanism of the color change was discussed in connection with that of the photochromism at room temperature and the results obtained from spectroscopic and ESR studies.
Mechanism of the Solvent Effect in a Binary Solvent System on the Cationic Polymerization of N-Phenylethylenimine
Authors: Kagiya Tsutomu , Kondo Tomizo
Published: July 2006

The effect of the binary solvent systems on the polymerization of N-phenylethylenimine with a formic acid catalyst was studied quantitatively. In an acetonitrile-acetone system composed of components with similar nucleophilicities but with very different dielectric constants, the polymerization rate increases with an increase in the dielectric constant of the binary solvent system. In an acetonitrile - N,N-dimethylacetamide system composed of components with very different nucleophilicities but with similar dielectric constants, on the other hand, the rate was markedly depressed by the addition of a small amount of N,N-dimethylacetamide with a large nucleophilicity. On the basis of these results, a mechanism of the solvent effect in a binary solvent system was proposed; the rate equation of the polymerization was expressed empirically as a function of both the dielectric constant of the binary solvent mixture and the nucleophilic equilibrium constant, and the concentration of the component.
Synthesis of Pyrrole Nucleosides by the Photo-dehydrogenation of Δ3-Pyrroline Derivatives
Authors: Kawana Masajiro , Emoto Sakae
Published: July 2006

1-(β-d-Glucopyranosyl)pyrrole (VI) was prepared by the photo-dehydrogenation of 1-(2′,3′,4′,6′-tetra-O-acetyl-β-d-glucopyranosyl)-Δ3-pyrroline (IV) in the presence of oxygen and benzophenone, followed by deacetylation. The nucleoside (VI) was also derived directly from 1-(d-glucosyl)-Δ3-pyrroline (III) by photochemical means. The synthesis of 1-(α-d-ribofuranosyl)-pyrrole (XI), its β-anomer (XII), and 1-(β-d-ribopyranosyl)pyrrole (XIII) was accomplished by photodehydrogenation of 1-(2′,3′-O-isopropylidene-d-ribosyl)-Δ3-pyrroline, followed by the removal of the protecting group. The treatment of 1-(2′,3′-O-isopropylidene-α-d-ribofuranosyl)pyrrole (VIII) with 80% aqueous acetic acid afforded a novel α-cyclonucleoside, 1-(2-C,2′-O-isopropylidene-α-d-ribofuranosyl)pyrrole (XIV), besides XI–XIII. The formation of pyrrole by the photodehydrogenation of Δ3-pyrroline (II) itself was confirmed by gas chromatography.
Resolution of Amino Acids. IX. Studies on the Preparation of β-Hydroxyasparagines and Configuration of Natural Hydroxyasparagine
Authors: Okai Hideo , Izumiya Nobuo
Published: July 2006

Crystalline threo-and erythro-β-hydroxy-l-asparagine were prepared via asymmetric hydrolysis of the corresponding hydroxy-l-aspartic acid diamide by leucine aminopeptidase. The isomers of hydroxy-l-asparagine obtained were compared with the natural hydroxyasparagine isolated from human urine with respect to optical rotation and chromatography. From the results it is concluded that the spacial configuration of the natural product is that of erythro-β-hydroxy-l-asparagine. Additional studies were also carried out to prepare threo- and erythro-β-hydroxy-Dl-asparagine from the corresponding hydroxy-Dl-aspartic acid diamide without the enzyme.
Mechanism of Intramolecular Energy Transfer in Rare Earth Chelates as Revealed by Infrared Absorption Measurements
Authors: Matsuda Yoshihisa , Makishima Shoji , Shionoya Shigeo
Published: July 2006

The purpose of this paper is to clarify the mechanism of intramolecular energy transfer from the triplet state of the ligand to the excited levels of the central ion in rare earth chelates. As to seven kinds of samarium β-diketonates, the frequency of infrared absorption due to the stretching vibration of the chelate bond, \ ildeνMO, and the manner of energy transfer are investigated. The probability of energy transfer is estimated from the ratio of the intensity of the samarium emission to that of the ligand phosphorescence, ISm⁄IPh. The overlap integral, S, between the ligand phosphorescence spectrum and the samarium absorption spectrum is obtained. It was found that a linear relation roughly holds between log{(ISm⁄IPh)⁄S} and \ ildeνMO. On the basis of this fact, one is led, by making some arguments, to the conclusion that intramolecular energy transfer is dominated by the resonance mechanism due to the exchange interaction of the π electron system of the ligand triplet state with the f electron system of the central rare earth ion.
Association Involving Optically Active Ions. II. Association Constants of Tris(ethylenediamine)cobalt(III) and Tris(propylenediamine)-cobalt(III) Ions with Some Anions
Authors: Ogino Kazuko
Published: July 2006

Association constants of [Co en3]3+ (en=ethylenediamine) and d- and l-[Co d-pn3]3+ (pn=propylenediamine; d- and l- refer to the sign of optical rotation at sodium D-line) with some anions have been determined spectrophotometrically. Values are as follows: [Co en3]3+·SO42−49, [Co-en3]3+·glycollate− ∼5, d-[Co d-pn3]3+·SO42− 70, d-[Co d-pn3]3+·d-tart2− (tart2−=bivalent tartrate anion) 30, d-[Co d-pn3]3+·l-tart2− 28, l-[Co d-pn3]3+·SO42− 43, l-[Co d-pn3]3+·d-tart2− ∼7, l-[Co-d-pn3]3+·l-tart2− ∼16. These association constants are discussed in terms of the microscopic interaction between the ions. The effect of outer-sphere association on the circular dichroism and optical rotatory dispersion is also discussed.
Two-dimensional Dual-band Thin-layer Chromatographic Separation of Polynuclear Hydrocarbons
Authors: Matsushita Hidetsuru , Suzuki Yasutomo
Published: July 2006

A two-dimensional dual-band thin-layer chromatographic procedure for the separation of a mixture containing many polynuclear hydrocarbons is described. A chromatoplate composed of two adsorbent layers, aluminum oxide G and acetylated cellulose, is used in this chromatography. A sample containing various polynuclear hydrocarbons is first developed on an aluminum oxide G layer with n-hexane - ether (19:1, v/v) and then on an acetylated cellulose layer with methanolether-water (4:4:1, v/v). A mixture of 15 polynuclear hydrocarbons was completely separated into its components by this treatment. This method was then applied to the separation of a vacuum-sublimation extract of particulates obtained from Tokyo air. The extract was separated into 69 spots, and it was proved that several hydrocarbons, including benzo(a)pyrene, has been isolated in a pure state.
The Configuration of 6,8(9)-p-Menthadien-2,4-diols and p-Menthane-2,4-diols
Authors: Sakuda Yoshitsugu
Published: July 2006

The 6,8(9)-p-Menthadien-trans-2,4-diol (I) and 6,8(9)-p-menthadien-cis-2,4-diol (II) were obtained by the oxidation of l-cis-carvyl acetate with selenium dioxide. The hydrogenation of each 6,8(9)-p-menthadien-2,4-diol gave a different pair of p-menthane-2,4-diols, one pair being p-menthane-2,4-diols (III and IV) from trans-2,4-diol (I) and the other pair being p-menthane-2,4-diols (V and VI) from cis-2,4-diol (II). The absolute configurations of the p-menthane-2,4-diols (III, IV, V and VI) were assigned as follows on the basis of the chemical evidence, the IR and NMR data, and the Cotton-effect sign of the oxidation products of these isomers: III, (1S : 2R : 4S); IV, (IR : 2R : 4S); V, (1R : 2R : 4R) and VI, (1S : 2R : 4R)-p-menthane-2,4-diol. The identification of these diastereoisomeric diols III–VI made possible the assignment of a configuration to diols I and II.
Organic Syntheses by Means of Metal Complexes. II. Oxo Reaction Catalyzed by Cyclopentadienyliron Dicarbonyl Dimer
Authors: Tsuji Jiro , Mori Yoichi
Published: July 2006

It was found that cyclopentadienyliron dicarbonyl dimer is an active catalyst for oxo reaction and the characteristic features of the catalysis have been studied.
Study of Wall Effect on the Flow of Polyvinylpyrrolidoe Solutions in Capillary
Authors: Watanabe Takehiko , Mineshita Takeshi , Ono Sôzaburo
Published: July 2006

Dependence of the viscosity of the polyvinylpyrrolidone (\barMv=4.0×104 and 9.0×105) solutions on the bore-size of capillary viscometer has been studied at 35°C, in pure water, in dimethyl sulfoxide (DMSO), in water-DMSO, and in aqueous solution with various cosolutes, at various concentrations (0.5–5.0 g/100 ml). Viscosity measurements were carried out with a Maron-Belner type low shear capillary viscometer with various capillary radii (0.0190–0.0761 cm) within the shear stress range of 0.2–20 dyn/cm2 at the capillary wall. The solutions showed a behavior of non-Newtonian flow and dependence on the size of the capillary. The viscosity of the polymer solutions in DMSO, and in water-DMSO decreased with the decrease in the capillary bore-size within the range of shear stress studied, and that in pure water, although similar phenomena as above were observed in higher shear stress, increased with the decrease in the capillary bore-size at the range of the lower shear stress, and this capillary bore-size dependence could not be observed with the aqueous solutions with cosolutes. The difference in the characteristics of the capillary bore-size dependence of the viscosity may be attributed to the difference in the behavior of the polymer molecules existing near the wall at which the thermal motion of the polymer molecules will be hindered by the existence of the capillary wall. The results were represented by the modified Ree-Eyring generalized flow formula for a flow system containing one Newtonian flow unit and one non-Newtonian one which included the additional terms dependent on the capillary bore-size. The viscosity equation suitable for analysing the dependence of the viscosity on the capillary bore-size at entire ranges of the rate of shear, was derived by assuming the wall layer composed of the double layers (of thickness do and di–do) in the flowing liquid in the capillary tube, and by combining this equation with the modified Ree-Eyring equation, the values of do and di were calculated.
Electronic Spectra of Crystalline TCNQ Anion Radical Salts. II. Complex Salts
Authors: Iida Yôichi
Published: July 2006

The present paper deals with crystalline TCNQ anion radical “complex” salts of (M+)2-(TCNQ)3\ewdot\ewdot and M+(TCNQ)2\ewdot composed of the formally-neutral TCNQ and its anion radical TCNQ\ewdot Their crystalline electronic spectra were measured in the range between 4.0 and 30.8 kK by diffuse reflectance and in the 0.65–4.0 kK range by transmittance. None of their spectra except those of the (2 : 3) compounds were found to bear any resemblance to those in the simple salts. Although the spectra of the (2 : 3) compounds are similar to those of the simple salts with low conductivities, the former exhibit an additional weak absorption in the range lower than 6 kK. The (1 : 2) compounds with intermediate conductivities show a strong band around 3 kK, and those with high conductivities, around 2.0–2.5 kK. Their spectra are discussed on the basis of the interaction among unpaired electrons in connection with their electrical and magnetic properties. The difference in the interaction modes of the ion radicals between “simple” and “complex” salts is also speculated upon.
The Etherification Reactions of Allyl Alcohol Catalyzed by the Copper(I) Chloride Complex
Authors: Ogura Tetsuya , Furuno Nobuo , Kawaguchi Shinichi
Published: July 2006

Diallyl ether was produced exclusively when an allyl alcohol solution containing copper(I) chloride and ammonium chloride was heated in the absence of air. A mixture of allyl and ethyl alcohols gave diallyl and ethyl allyl ethers, but no trace of diethyl ether. The tracer experiment employing 18O-enriched allyl alcohol showed that the C–O bond in allyl alcohol was ruptured in the ethyl allyl ether formation. The kinetic study of these etherification reactions showed that the rate determining step would include the nucleophilic attack of an allyl or ethyl alcohol molecule on the catalyst-substrate complex. A novel allyl alcohol complex, (NH4)2Cu2Cl4(C3H6O)2, was isolated and characterized, but the active catalyst species was assumed to be (NH4)2Cu4Cl6. Methyl derivatives of allyl alcohol were also allowed to react in the presence of the same catalyst and the possible mechanism of etherification was discussed.
The Microwave Spectrum, Structure, and Dipole Moment of Ethylene Episulfoxide
Authors: Saito Shuji
Published: July 2006

The microwave spectra of the normal species as well as the 13C and 34S isotopic molecules of ethylene episulfoxide have been observed. The rotational constants thus obtained lead to the following structural parameters: S–O=1.483±0.003 Å, C–S=1.822±0.003 Å, ∠OSC=111°1′±10′, ∠CSC=48°46′±10′, on the assumption that the C–H distance and the ∠HCH and ∠H2CC angles are the same as those of ethylene sulfide. From the Stark shifts, the dipole moment has been determined to be μa=3.61±0.04 D, μc=0.89±0.01 D and μtotal=3.72±0.04 D. The bond nature of S–O and C–S has then been discussed on the basis of these data.
Chemical Effects Associated with β-Decay Process. IV. Kinetic Studies of the Chemical Behavior of 144Pr Decayed from the 144Ce(III)-Diethylenetriaminepentaacetate Complex
Authors: Shiokawa Takanobu , Omori Takashi
Published: July 2006

The chemical behavior of 144Pr as a result of the β−-decay of the 144Ce(III)-diethylenetriaminepentaacetate (144Ce(III)-DTPA) complex was investigated in detail on the basis of the substitution reaction mechanism. The experimental results, represented in terms of the yield of the 144Pr(III)-DTPA complex, were explained quantitatively by the application of Bateman’s equation. An increase in the nuclear charge in the β-decay of the 144Ce(III)-DTPA complex may result in the formation of 144Pr(IV)-DTPA, which would then be reduced to an intermediate complex of 144Pr(III) by an intramolecular electron-transfer. The mechanisms and the rate constants are established for the decomposition of the intermediate leading to the formation of the uncomplexed ion. It was also suggested that the uncomplexed 144Pr(III) ion is produced directly by an exhaustive bond-rupture of the daughter complex ion, without any formation of the intermediate. The ratio of bond-rupture was determined to be 0.25; this value is in accordance with the theoretical value for the formation of the multiply-charged 144Pr ion due to electron shake-off and the internal conversion of γ-rays, followed by the Auger process.
Electronic Spectra of Crystalline TCNQ Anion Radical Salts. I. Simple Salts
Authors: Iida Yôichi
Published: July 2006

The present paper deals with crystalline TCNQ, anion radical “simple” salts of M+ TCNQ\divdot, where M+ represents a diamagnetic counter cation. Their crystalline electronic spectra were measured in the range between 4.0 and 30.8 kK by means of diffuse reflectance. The crystalline spectra thus obtained were quite different from that of the TCNQ, radical anion monomer and exhibited a broad and intense low-energy band around 9 kK in the low-conductivity compounds and at 4.3 kK in the high-conductivity compound. These bands were ascribed to inter-radical charge-transfer in the solid state. The crystalline spectra were found to be closely correlated to their unusual electrical and magnetic properties. It was concluded that these physical properties were based on a unique TCNQ molecular arrangement in groups of several or an infinite number of face-to-face molecular systems.
Reactive Fiber. VII. Preparation and Polymerization of Vinyl Sulfonyl (β-Chloroethyl)amide
Authors: Iwakura Yoshio , Uno Keikichi , Nakabayashi Nobuo , Chiang Wen-Yen
Published: July 2006

Vinyl sulfonyl (β-chloroethyl)amide (III) was prepared from vinyl sulfonyl chloride and aziridine. The monomer reactivity ratios of III (M2) (r1=3.0, r2=0.075) were determined from the result of copolymerization with styrene (M1), and Q2 and e2 values calculated were 0.13 and 0.42 respectively. Radical polymerization of III gave a polymer with low viscosity and the polymer had good reactivity with nucleophilic reagents. To compare the functional group in polymer chain with that of monomeric compound, methane sulfonyl (β-chloroethyl)amide (IV) was prepared and the reaction between the function and several nucleophiles was studied. Reactive fibers were obtained from copolymers of acrylonitrile and III. Reaction of the fibers with Congo Red was carried out in the presence of pyridine.
Studies of Peptide Antibiotics. XIV. Analogs of Gramicidin S Containing d-Valine or d-Leucine in Place of d-Phenylalanine
Authors: Aoyagi Haruhiko , Kato Tetsuo , Waki Michinori , Abe Okitoshi , Okawa Reiko , Makisumi Satoru , Izumiya Nobuo
Published: July 2006

Two analogs of gramicidin S, 4,4′-d-valine- and 4,4′-d-leucine-gramicidin S (XVI-A and XVI-B), have been synthesized and tested for the antibacterial properties. The crude product obtained after the cyclization of a linear pentapeptide active ester was composed of the protected monomer and dimer. The pure protected dimer was obtained by a column chromatography of Sephadex LH-20, and the hydrogenolysis of this product in the presence of hydrogen chloride afforded the crystalline hydrochloride of XVI-A or XVI-B. These analogs were as active as natural gramicidin S; the results indicated that the aromatic side chains of the d-phenylalanines in the molecule of gramicidin S can be replaced by the aliphatic side chains without an influence for the activity.
The Decomposition of Cyclohexyl Hydroperoxide in the Presence of Cyclohexanone and a Novel Rearrangement Product
Authors: Chubachi Sumio , Matsui Hideo , Yamamoto Kiyoshi , Ishimoto Sachio
Published: July 2006

One of the major reaction products besides cyclohexanol from the reaction of cyclohexyl hydro-peroxide with cyclohexanone was isolated and confirmed as ε-cyclohexyloxycaproic acid. The rate of formation of ε-cyclohexyloxycaproic acid was measured in excess cyclohexanone and found to follow a first order law for cyclohexyl hydroperoxide. The activation energy of 10.1 kcal/mol was found for the formation of the acid. The rate of decomposition of cyclohexyl hydroperoxide in cyclohexane was measured in the presence of various concentrations of cyclohexanone and the rates of formation of cyclohexanol and the free carboxylic acids were also measured. An adduct formation between cyclohexyl hydroperoxide and cyclohexanone followed by homolytic decomposition of the adduct was suggested to explain the experimental results.
Photochemical Ethoxycarbonylmethylation of Benzene with Ethyl Haloacetates
Authors: Ogata Yoshiro , Itoh Teruo , Izawa Yasuji
Published: July 2006

The ultraviolet light-induced reaction of ethyl haloacetate with an excess benzene gives ethyl phenylacetate (1.7%) and diethyl succinate (1.6%) as main products, while the same reaction of excess chloroacetate with benzene gives ethyl phenylacetate higher yield (optimum 78.4%). Addition of aluminum chloride to the reaction mixture using an excess benzene gives ethyl phenylacetate as a sole product (11.5%). The effect of reaction conditions on the yield is examined.
t-Amyloxycarbonyl as a New Protecting Group in Peptide Synthesis. V. Direct Synthesis of t-Amyloxycarbonyl- and t-Butyloxycarbonyl-amino Acids Using the Respective t-Alkyl Chloroformates
Authors: Sakakibara Shumpei , Honda Ichiro , Takada Katsumi , Miyoshi Muneji , Ohnishi Takanobu , Okumura Kentaro
Published: July 2006

t-Amyloxycarbonylamino acids (Aoc-amino acids) were found to be synthesizable under the conditions of the Schotten-Baumann reaction with t-amyl chloroformate in the presence of a water-soluble inert solvent. The procedure was applied to almost all amino acids or their derivatives; the yields of the products and their purities were satisfactory except in the cases of asparagine, glutamine, and nitroarginine. Many t-butyloxycarbonylamino acids (Boc-amino acids) were also synthesized successfully using the same procedure. Similarly, t-amyl and t-butyl carbazates were synthesized in satisfactory yields with these chloroformates and hydrazine hydrate. Thus, the procedure was demonstrated to be the simplest for the preparation of Aoc-or Boc-amino acids and hydrazide.
A Study on Electron Spin Resonance of the Complex between Metal Ions of Group II and o-Quinone Anion
Authors: Kuwata Keiji , Shimizu Yasuhiro
Published: July 2006

An electron spin resonance study on the complex formation between o-quinone anion and metal ions of group II was undertaken, and the change in g-factor and proton hyperfine splittings of o-quinone anion by the complex formation were examined in detail. The change in g-factor was closely related to both the change in the unpaired electron distribution and the change in energy difference between lone pair orbital of oxygen and unpaired electron orbital. The stabilization of the quinone anion against its coupling reaction was seemed to be related to the shift in g-factor by complex formation. The interaction between quinone anion and metal ions was deduced to be partly ionic. An open shell SCF calculation with CI for the free quinone anion was carried out in order to discuss the electronic spectra of the complex.
K-Band Electron Paramagnetic Resonance of Sulfur Monoxide in the Gaseous Phase
Authors: Uehara Hiromichi
Published: July 2006

Four K-band electron paramagnetic resonance transitions of 3Σ−  32S16O in the gas phase have been observed. One of these occurs between the Zeeman levels of the K=1, J=0→K=0, J=l states and three between the Zeeman levels of the K=2, J=2→K=3, J=2 states. The analysis of the spectra has led to the g values of gse, gle, and gr (in accordance with the notation by Tinkham and Strandberg). Knowledge of the rotational magnetic moment gave the equilibrium internuclear distance of Re=1.48101±0.00006 Å.
Fragmentation of the Excited Isobutane Ion Produced by Charge Transfer from the Nitrogen Molecule Ion
Authors: Miyazaki Tetsuo , Kohama Tadahiko , Fueki Kenji , Kuri Zen-ichiro
Published: July 2006

The radiolysis of the N2-isoC4H10 (0.0153 mol/mol of N2) mixture has been studied by using such ion scavengers as ammonia and sulfur hexafluoride. It was found that the C3H7+ ion is formed by the fragmentation of the excited isobutane ion produced by the charge transfer from the nitrogen ion. Although nitrogen is an effective quencher of the excited ion, the yield of the C3H7+ ion is constant over the pressure range from 0.66 to 130 atm. It has been concluded that the excited isobutane ion produced by the charge transfer with 5 eV excess energy decomposes very fast and that it can not be deactivated by nitrogen of 130 atm, while it has been reported by other authors that the excited isobutane ion with 1.2 eV excess energy can be deactivated below 1 atm. This difference in the characters of the excited isobutane ions can be explained by the previously-proposed mechanism of the fragmentation.
Photochemistry of Acetanilide. IV. The Photochemical Reactions in the Vapor Phase and Rigid Matrixes
Authors: Shizuka Haruo , Tanaka Ikuzo
Published: July 2006

The photolysis of acetanilide in the vapor phase at 2537 Å and 120°C has been studied by means of mass spectrometry, gas chromatography, and spectrophotometry. In the vapor phase, no such rearrangements of acetanilide as in the liquid phase occurred, only the decomposition of acetanilide. Carbon monoxide and ethane were formed as the main products, and the ratio of carbon monoxide to ethane was about 2. The quantum yield of the predissociation for the N–C bond of acetanilide in the vapor phase was estimated to be 0.28 from the data of the quantum yields for the formations of carbon monoxide and ethane. A small amount of methane and traces of hydrogen and benzene were also detected. The reaction scheme of acetanilide in the vapor phase at 2537 Å and 120°C has been proposed. On the other hand, the photochemical reactions of acetanilide in the rigid matrixes (MP, ME, and EPA) at −196°C and in the PVA sheet at room temperature have also been carried out by the use of a spectrophotometer and an ESR spectrometer. In the rigid matrixes at −196°C, the photochemical rearrangements did not occur, only the back reaction resulting in the distortional structure of acetanilide; this mechanism can be explained by the stiffness of the solvent cage. The cage effect on the photochemical reaction of acetanilide is also discussed.
Solubility of Chlorine in Mixed Solutions of HCl and CuCl2
Authors: Hine Fumio , Inuta Shusei
Published: July 2006

The solubility of chlorine in a mixed solution of HCl and CuCl2 under various conditions of concentration, temperature, and partial pressure was determined. The concentration of chlorine in a solution as the sum of Cl2 and Cl3− was found to be proportional to the partial pressure of chlorine in the gas phase; its slope decreased with an increase in the concentration of cupric ions due to the salting-out effect.
Fluorescence Lifetime of Acridine in Water-Organic Solvent Mixtures
Authors: Kokubun Hiroshi
Published: July 2006

Fluorescence lifetime of acridine has been measured in water-ethanol and water-glycerol mixtures of different composition at 25°C. Remarkable decrease in lifetime value was found as the amount of organic component increases. The lifetime of 10.3 ns was obtained for the aqueous solution. The lifetimes in glycerol and in ethanol were determined as 3.2 and 0.72 ns, respectively. The observed ratio of the lifetime in the mixture to the lifetime in water, τ⁄τ0, has the same functional dependence on solvent composition as the ratio of fluorescence yield, Φ⁄Φ0. These quenching phenomena by organic molecules have been interpreted as due to the solvent effects upon the radiationless transition rate. Both static and dynamic mechanisms of quenching are not applicable in the present cases of solvent quenching.
Determination of a Small Amount of Iodide by Atomic Absorption Spectrophotometry Using a Cadmium Hollow Cathode Lamp
Authors: Kumamaru Takahiro
Published: July 2006

A new application of atomic absorption spectrophotometry to the determination of iodide has been proposed. The method is based on solvent extraction into nitrobenzene of the colorless ion-pair formed between tris(l,10-phenanthroline)cadmium(II) and the iodide anion, and the subsequent determination of the cadmium concentration in the extract by atomic absorption in an air-acetylene flame at the 2288 Å cadmium line. The absorbance due to cadmium in the extract shows a linear relationship to the concentration of iodide over the range from 4×10−6 to 4×10−5  m initially present in the aqueous solution. The optimum conditions for the determination of iodide have been established, and the extraction efficiency and the effect of other anions have also been studied.
Acid Decomposition of Metal Xanthate Complexes and Their Stability Constants
Authors: Nanjo Michio , Yamasaki Taro
Published: July 2006

The formation of 1 : 1 complexes was confirmed by means of the kinetic method. The acid decomposition of xanthate was delayed by the addition of metal ions because of the decrease in the concentration of ethyl xanthic acid in an equilibrium. By using the rate equation, the stability constants were found to be (1.0±0.2)×104, (1.7±0.4)×10 and (2.5±0.4)×104 for Cd(EX)+, Zn(EX)+, and Pb(EX)+ respectively.
Excitation Transfer in the Radiolysis of Solid Hydrocarbons as Studied by ESR Spectroscopy and Product Analysis
Authors: Wakayama Terunobu , Kimura Toyoaki , Miyazaki Tetsuo , Fueki Kenji , Kuri Zen-ichiro
Published: July 2006

The effect of carbon tetrachloride on the radiolysis of isobutane and methylcyclohexane at 77°K is studied by ESR spectroscopy and by product analysis. The yields of solvent radicals from the γ-irradiation of isobutane and methylcyclohexane are not changed by the presence of conventional electron scavengers. This indicates that solvent radicals are not formed by the neutralization of solvent cations with electrons. On the contrary, the yields of solvent radicals decrease remarkably upon the addition of CCl4. Though the yield of propylene from the γ-irradiation of isobutane is not affected by the addition of electron scavengers, it decreases significantly upon the addition of CCl4. Though the decrease in the hydrogen yield in the radiolysis of methylcyclohexane at 77°K upon the addition of electron scavengers is only about 1G-unit, it amounts to more than 3.5G-units upon the addition of CCl4. These characteristic effects of CCl4 can possibly be explained in terms of excitation transfer from the excited solvent molecule to CCl4. A kinetic treatment suggests that its mechanism may be an exciton transfer.
The Zero-point Average Structure of Acetone
Authors: Iijima Takao
Published: July 2006

The zero-point average structure of acetone has been determined from the moments of inertia obtained by means of microwave spectroscopy by Nelson and Pierce, as incorporated with the average distances from gas-electron diffraction by Kato et al. In addition to the normal species (CH3)2CO, three isotopically-substituted species, (13CH3)2CO, (CH3)2C18O, and (CD3)2CO, have been used in the analysis. The following values of the rz-parameters have been determined: C=O, 1.2122±0.0025 Å; C–C, 1.5190±0.0008 Å; C–H, 1.0614±0.0010 Å; ∠HCH, 108°30′±6′; and ∠CCC, 116°9′±10′ (∠CCC for (CD3)2CO, 115°51′±10′). The slightly smaller value of ∠CCC found for the deuterated species has been reasonably attributed to the anharmonicity associated with the symmetric rocking motion of the two methyl tops. The equilibrium values for C-H(D) and ∠CCC have also been estimated to be 1.078 Å and 115°0′ respectively.
Solvent Effect on the Electronic Spectra of Bis(8-quinolinolato)- nickel(II) at 80°C
Authors: Moriguchi Yoshiki , Ueno Keihei
Published: July 2006

The visible absorption spectra were observed on bis(8-quinolinolato)nickel(II) in molten 8-quinolinol as well as in other solvent systems such as molten naphthalene, molten β-methoxynaphthalene or toluene containing various amounts of 8-quinolinol at 80°C. Little interaction was found between the solute and naphthalene or toluene. However, a weak interaction was observed between the solute and β-methoxynaphthalene or 8-quinolinol. The extent of interaction between the solute and 8-quinolinol in toluene was evaluated spectrophotometrically.
Cobalt(II) Complexes with Nitrilotriacetic Acid, Nitrilopropionicdiacetic Acid and Nitriloisopropionicdiacetic Acid
Authors: Tachibana Mitsuo , Uehara Akira , Kyuno Eishin , Tsuchiya Ryokichi
Published: July 2006

The following cobalt (III) complexes containing nitrilotriacetic acid (NTA), nitrolopropionicdiacetic acid (NPDA) and nitriloisopropionicdiacetic acid (NIPDA) were prepared: (NH4)3[Co-(nta)2]·2H2O (pink) (I), NH4[Co(Hnta)2]·2H2O (pale pink) (II), K3[Co(npda)2]·2H2O (pink) (III), K[Co(Hnpda)2]·3H2O (pale pink) (IV), [Co(npda)(o-phen)]·H2O (reddish violet) (V), [Co-(npda)(bipy)] (reddish violet) (VI), K[Co(OH)(nipda) (H2O)]·H2O (bluish violet) (VII) and [Co-(nipda) (o-phen)] (reddish violet) (VIII); where nta, npda, nipda, o-phen and bipy are the abbreviations of nitrilotriacetate-, nitrilopropionicdiacetate-, nitriloisopropionicdiacetate-ion, o-phenanthroline and 2,2′-bipyridyl, respectively. On the basis of electronic spectra, it was found that complexes I to IV have the trans form, while complexes V, VI and VIII have the mer form structure with respect to the nitrogen atoms in the coordinating ligands. Complex VII showed a dehydrationdimerization reaction on heating by “Derivatograph”. Comparison of chemical and physical properties of the complexes with those of the corresponding chromium (III) complexes was made.
Spectral and Magnetic Studies on Bi- and Tri-Nuclear Complexes Derived from Copper(II) Complexes with Tetradentate Schiff Base and One of the Chlorides, Nitrates and Perchlorates of Copper(II), Nickel(II), Cobalt(II) and Zinc(II)
Authors: Kato Michinobu , Muto Yoneichiro , Jonassen Hans B , Imai Kyoko , Tokii Tadashi
Published: July 2006

We have prepared a variety of binuclear and trinuclear complexes of the composition Cu-(TDSB)·MX2 and 2Cu(TDSB)·M(ClO4)2, where Cu(TDSB)=N,N′-ethylenebis(salicylideneiminato)copper(II) or N,N′-1,2-propylenebis(salicylideneiminato)copper(II), and M=Co, Ni, Cu and Zn. A few higher polynuclear species were also prepared. The previously reported empirical rule found in binuclear copper(II) complexes, where the two copper ions are in the same environment, that the “higher energies of d-d bands - lower magnetic moments,” was proved to hold in the binuclear copper complexes of the present study, even though the two copper ions are in different environments. For a series of complexes with M = Cu or other metals, and with X = NO3 or ClO4, it was observed that “d-d bands of Cu(TDSB) apperas at the shortest wavelengths when M = Cu.” For perchlorate complexes, the energy of the d-d band is in the order, Co<NiZn, the same as the Irving and Williams’ order of complex stability. It can then be generalized that in a hetero-polynuclear complex molecule, the strengthening of the coordinate bonds around one metal ion strengthens the coordinate bonds around the other metal ion or ions.
ESR Studies of Some Copper(II) β-Diketone Chelate Complexes in Heterocyclic Basic Solvents
Authors: Yokoi Hiroshi , Sai Mitsuru , Isobe Taro
Published: July 2006

Three representative copper(II) β-diketone chelate complexes, bis-(ethylacetoacetato)copper-(II), bis-(salicylaldehydato)copper(II), and bis-(acetylacetonato)copper(II), have been investigated by the ESR method in order to estimate their structures in various solvents. The super-hyperfine structures due to the equal coupling of the unpaired electron with two nitrogen atoms were clearly observed for the first two complexes dissolved in pyridine or γ-picoline. The structures of these two complexes in pyridine or γ-picoline could be estimated to be as follows; a new square-planar coordination occurs through two nitrogen atoms of these basic solvent molecules and two oxygen atoms of the four originally-coordinating ligand oxygen atoms, and the other oxygen atoms are coordinated as apical ligand atoms with less strength. On the other hand, the ESR spectra of the latter complex dissolved in pyridine or γ-picoline show a significantly strong ligand field only in the axis normal to the molecular plane; this indicates that the coordination of the basic solvent molecules along the axis normal to the molecular plane occurs.
The Hydrolysis of the Beryllium Ion in Heavy Water
Authors: Kakihana Hidetake , Maeda Masunobu
Published: July 2006

The hydrolysis of Be2+ ion in heavy water containing 3m NaClO4 as an ionic medium was investigated at 25°C by potentiometric titrations, employing a technique of constant-current coulometry. The deuterium-ion concentrations was measured by the use of a commercial glass electrode. The emf data in the range of the total beryllium concentration from 2.5 to 10 mm can be explained on the basis of the following complex formation: Be2(OD)3+, −logβ1,2=3.28±0.04; Be3(OD)33+, −logβ3,3=9.399±0.007; Be(OD)2, −logβ2,1=11.89±0.07. The composition of the species formed in heavy water is the same as that in light water, but the values of the stability constants are smaller in heavy water than in light water.
The Optical Rotatory Dispersion and Circular Dichroism of Aromatic Amino Acids
Authors: Sakota Naokazu , Okita Kozo , Matsui Yasuhiko
Published: July 2006

The CD and ORD of d-phenylglycine and l-phenylalanine were measured at various pH’s. The superficial small pH dependence of the CD maximum around 220 mμ and the anomalous large [θ] value at the CD maximum in both aromatic amino acids suggest an interaction between the 1La transition of the benzene ring and the n→π* transition of the carboxyl group. The ORD and CD of l-α-amino-β-benzalpropionic acid, l-α-amino-β-benzylpropionic acid, and l-2-amino-4-phenyl-butanol-1 were also measured, and the screening effect of the methylene groups which exist between a benzene ring and an asymmetric carbon atom was discussed.
Selectivity in the Metal-Complex-Catalyzed Decarboxylation of Oxaloacetic Acid and a Role of Metal Ion in an Enzyme System
Authors: Munakata Megumu , Matsui Masakazu , Tabushi Masayuki , Shigematsu Tsunenobu
Published: July 2006

The catalytic action of metal ions in the presence of various coordinating agents and a role of metal ions for the activations of an enzyme in a decarboxylation reaction were investigated. Many of the ligands studied decreased the catalytic activity of metal ions. However, α,α′-dipyridyl selectively enhanced the catalytic activities of divalent metal ions, except Cu2+. The activity of Cu2+ was specifically enhanced only with histidine and its derivatives. Histidine destroyed Ni2+ and Co2+ catalysis. The specific enhancement may be due to the increase in the electronegativities of the metal ions with dπ (metal)-pπ(ligand) back donation and to the stereo-configuration of the metal complexes. The catalytic behavior in these metal ion coordinating agent systems was different from that in the metal-enzyme systems. It was assumed that the activation of enzyme resulted from the change in the configuration of enzyme by the coordination of metal ions, and not from the catalytic action of metal ions enhanced by the coordination of enzyme. This was supported by the fact that the catalysis of compounds containing amino groups, active sites of enzyme, remarkably depended on the stereo-configuration. In the enzyme-model system, Mn2+ was generally preferable to Cu2+ and Ni2+. The catalytic actions of Cu2+ and Ni2+ were lowered by the complex formation with the active sites. This may solve the question why, in enzymatic reactions, Mn2+ having small complex-forming ability is more selective and effective than Cu2+ and Ni2+ with large complex-forming abilities.
A Novel Reduction in the Presence of Precipitated Metals. II. The Behavior of Precipitated Metals and Water in Catalytic Reduction
Authors: Sakai Koji , Ishige Masayoshi , Watanabe Ken-ichi , Hata Kazuo
Published: July 2006

The ppt-metal-catalyzed reduction, which is performed by refluxing the substrates with water in the presence of ppt-metals, was investigated in detail. The participation of water as a hydrogen donor was demonstrated by the fact that benzaldehyde was reduced to the corresponding deuterated alcohols when heated with D2O in the presence of ppt-Ni. The scope of the reduction was established by the reaction of cyclohexanone with ppt-metals and water. The most preferable H2O/cyclohexanone molar ratio was found to be about 15 : 1. The reaction was accelerated when a 0.25n aqueous solution of sodium chloride was used instead of water. It was found that the order of the abilities of various ppt-metals to decompose water is different from that of the abilities to catalyze the reduction of cyclohexanone. The values of the activation energies for the reduction catalyzed by ppt-Ni and ppt-Ni,Co were found to be 4.0 kcal/mol and 7.5 kcal/mol respectively. From these facts, it was concluded that the ppt-metal-catalyzed reduction consists of two steps: the reaction of water with zinc or zinc compounds to supply a hydrogen source necessary for the hydrogenation, followed by ordinary catalytic hydrogenation.
The Photosensitized Reaction of Deoxyguanosine in the Presence of Methylene Blue
Authors: Fujita Hitoshi , Yamazaki Hideo
Published: July 2006

The kinetics of the photosensitized decomposition of deoxyguanosine with methylene blue was studied by means of spectrophotometric measurements. The reaction rate increased with an increase in the concentration of the reactant or of oxygen up to a saturation level for each case at a given concentration of the dye. In a buffer solution of a lower phosphate concentration, a larger rate was observed. On the basis of these dependencies of the rate, the reaction scheme was discussed, and the ratios of some rate constants were estimated based on Schenck’s mechanism. A preliminary NMR measurement of the protons of deoxyguanylic acid in D2O suggested that the basepart of the nucleotide was specifically attacked by this photosensitized reaction.
Rearrangement of Aryl Sulfides in the Presence of Aluminum Chloride
Authors: Fujisawa Tamotsu , Ohtsuka Noriko , Tsuchihashi Gen-ichi
Published: July 2006

Aluminum chloride-catalyzed rearrangement of aryl sulfides leads to thermodynamically controlled equilibrium mixtures at room temperature. On treatment of o-, m- or p-tolyl phenyl sulfide without solvent, the isomer distribution converges to an equilibrium point, 17% ortho, 47% meta and 36% para isomer by intramolecular isomerization. Intermolecular disproportionation by methyl-group exchange to produce diphenyl sulfide and ditolyl sulfide accompanied isomerization. In addition, a new type of aromatic rearrangement, intermolecular disproportionation by exchange of the arylthio group, was found to occur simultaneously giving benzene, toluene and thianthrene derivatives. The rate of this reaction is slower than that of the methyl rearrangement. A similar treatment of α-naphthyl phenyl sulfide gave the β-isomer from intramolecular isomerization and diphenyl sulfide, naphthalene, thianthrene and benzene from intermolecular disproportionation. The mechanisms of the rearrangement of aryl sulfides are discussed.
The Graft Copolymerization of a Vinyl Monomer Containing a Glucose Residue onto Polypropylene Fiber
Authors: Iwakura Yoshio , Uno Keikichi , Kojima Takakazu , Ueno Akihiko
Published: July 2006

The graft copolymerization of 3-O-methacryloyl 1,2; 5,6-diisopropylidene-α-d-glucofuranose (MDG) onto polypropylene fibers was carried out by the γ-ray pre-irradiation technique in the presence of oxygen. The isopropylidene groups of the glucose residue grafted on the copolymer were removed by hydrolysis in aqueous formic acid, and the hydroxyl and hemiacetal groups were regenerated. The deacetonated fibers exhibited a considerable affinity for water vapor and could be dyed with a reactive dye.