bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemical Syntheses. IV. The Homolytic Methoxylation and Ethoxylation of Olefins by the Anodic Oxidation of Methanol and Ethanol
Authors: Inoue Tadao , Koyama Kikuhiko , Matsuoka Toru , Tsutsumi Shigeru 
Published: July 2006

Abstract
The electrochemical oxidation of methanol and ethanol in the presence of trans-stilbene, cis-stilbene, norbornene, and styrene has been studied. The major gaseous and nongaseous products have been identified and determined, and the corresponding dimethoxylated derivatives and diethoxylated derivatives have been obtained in fairly high yields. The main path by which these products may have arisen has been discussed, and the stereochemistry of the addition of methoxy radicals to stilbene has been discussed. Particular attention has been given to the possibility that the main product arises from the anodic oxidation of an intermediate radical to a carbonium ion.
The Chemiluminescent Polymer
Authors: Omote Yoshimori , Ohmori Seiya , Sugiyama Noboru 
Published: July 2006

Abstract
The synthesis and the chemiluminescence of poly(acrylylluminol-ir-acrylic acid) (II) are described. It was found that the reaction product of the chemiluminescence of II is roughly identical with the corresponding poly(acrylylaminophthalic acid-ir-acrylic acid). Also, it was found that II shows a stronger chemiluminescence than the monomeric N-propionylluminol (III) based on the same N-acylluminol unit in DMF-water (3:1 in vol), while II shows a weaker chemilluminescence in water.
The Reaction of Cyclooctatetraene Oxide with Grignard Reagents
Authors: Matsuda Tsutomu , Sugishita Masahiko 
Published: July 2006

Abstract
The reaction of cyclooctatetraene oxide with ethylmagnesium bromide, phenylmagnesium bromide and t-butylmagnesium bromide was found to yield 2, 4, 6-cycloheptatrienyl-1-ethyl-, phenyl- and t-butylcarbinol respectively. The treatment of cyclooctatetraene oxide with a catalytic amount of magnesium bromide in ether afforded phenyl acetaldehyde in a 76% yield. The dehydration of the carbinols with a catalytic amount of p-toluenesulfonic acid resulted in their further rearrangement to trans-β-substituted styrenes.
Preparation of Block Copolymer of ε-Caprolactone with Living Polystyrene
Authors: Nobutoki Koji , Sumitomo Hiroshi 
Published: July 2006

Abstract
ε-Caprolactone was polymerized by using living polystyrene prepared by means of an anionic polymerization technique. A gross polymer was elution-fractionated into four fractions which were methanol-soluble low-molecular-weight polyester, high-molecular-weight polyester, a small amount of polystyrene and polystyrene-polyester block copolymer. Both yields and molecular weights of block copolymers were observed to be higher in benzene than in tetrahydrofuran. Formation of block copolymers was concluded from the results of an elementary- and infrared analyses and turbidometry. Polymerization mechanism of ε-caprolactone is discussed.
Role of Macromolecules in Emulsion Stability with Special Reference to Pepsin as Emulsifier
Authors: Prakash Chandra , Srivastava S N 
Published: July 2006

Abstract
Role of pepsin as emulsifier in the stability of Nujol-in-water system has been studied. The flocculation studies were carried out haemocytometrically at different pH values, different amounts of electrolytes and different amounts of emulsifier itself. The zeta potential measurements were carried out at different pH values and varying amounts of electrolytes. In the light of the D. V. O. theory the interaction energy profiles have been drawn by summing up the repulsion and attraction energies. The high energy barriers obtained obviate the possibility of the occurrence of the flocculation in the primary minima. It appears, therefore, that the reversible flocculation occurs in the secondary minima which are about 2 to 4 kT deep. Therefore, assuming a singlet-doublet equilibrium degrees of aggregations have been calculated. In order to explain the observed values of degrees of aggregations, A (van der Waals constant) should be ≈5.97×10−13 erg. This value has been obtained by an indirect approach to fit the aggregation data. In case of Al(III) and Th(IV), however, charge reversal takes place which has been explained by a model picture. Charge densities and binding parameters have also been calculated.
Racemization Catalyst for Amino Acids. I. Racemization with Derivatives of o-Nitrosophenol
Authors: Hirota Kazuhiro , Izumi Yoshiharu 
Published: July 2006

Abstract
The racemization of amino acid catalyzed by several derivatives of o-nitrosophenol in the presence of metal ion was studied in a non-enzymatic system. The racemizations of l-alanine with 1-nitroso-2-naphthol, 2-nitroso-l-naphthol, 2, 4-dinitrosoresorcinol and disodium 1-nitroso-2-naphthol-3, 6-disulfate as catalysts were measured in the presence of metal ion and their activities were compared using various metal ions in these racemizations. Furthermore, racemizations with 1-nitroso-2-naphthol were carried out at various pH values in the presence of cupric or zinc ion and the optima pH values were measured. The racemization activities of 1-nitroso-2-naphthol and 4-nitroso-1-naphthol were compared to elucidate the relationship between the structural features and the activities of these catalysts. A possible mechanism for the catalytic racemization of amino acids is discussed briefly.
The Effect of Added Salts on the Solubilities and Krafft Points of Sodium Dodecyl Sulfate and Potassium Perfluoro-octanoate
Authors: Nakayama Haruo , Shinoda K\={o}z\={o} 
Published: July 2006

Abstract
The solubilities of sodium dodecyl sulfate and potassium perfluoro-octanoate in the presence of added salts have been measured as a function of the temperature. The solubility decrease caused by the added salt was remarkable at temperatures a few degrees higher than the Krafft point of a system which contained no salt. The solubility of the solid agent below the Krafft point decreases, approximately inversely proportionally to the concentration of the gegenion as was expected from the solubility product principle, whereas in these experiments the critical micelle concentration (the single-dispersion solubility of a liquid agent), the CMC, decreases inversely proportionally to about the 0.6th power of the gegenion concentration. Hence, the point of the intersection of the solute-solid and solute-liquid equilibrium curves, i. e., the melting point of a hydrated solid agent, shifts to a higher temperature upon the addition of salt. The Krafft-point elevation caused by added salt is explained by the model; the Krafft point is the melting point of a hydrated solid agent, and the formation of the micelle is regarded as a pseudo-phase separation. It is easy to evaluate graphically the Krafft-point elevation in the presence of a 1-1 type salt by applying the above experimental relations.
Solvent Effects in NMR Spectroscopy. I. Chemical Shifts Induced by the Addition of Protic Substances to Benzene Solutions of Several Polar Compounds
Authors: Yonezawa Teijiro , Morishima Isao , Takeuchi Katsuhiko 
Published: July 2006

Abstract
The variations in the chemical shifts of proton resonances in some polar compounds in benzene solution, when a portion of protic substances, methanol or trifluoroacetic acid, is added, are determined. It is found that protons of a solute molecule undergo an upfield shift which is enhanced by an increase in the concentration of added protic substances. The protons lynig in proximity to the proton-accepting center of the molecule are more sensitive to this upfield shift than are those far remote from it. The shifts induced by the addition of protic substances to a benzene solution are shown to be applicable to the structural determination; this proves to be useful in obtaining informations about the hydrogen bonding.
Nuclear Spin Coupling and Conformation of the P–O–C–H Group
Authors: Tsuboi Masamichi , Kuriyagawa Fukuko , Matsuo Kimiko , Kyogoku Yoshimasa 
Published: July 2006

Abstract
Proton magnetic resonance spectra have been observed of eight phosphoric acid esters in heavy water solutions. Among these esters, 1-phenyltrimethylene phosphate (1-phenyl-1, 3-propanediol cyclic phosphate) is a new compound. It was shown that the six-membered ring in this compound is fixed in a conformation at room temperature. On assuming that it is a chair form, 1-proton should be on the axial bond and this should be in a gauche relation with respect to the O–P bond around the C1–O1 bond. The proton-phosphorus coupling constant, JHp, in this H-C1–O1–P system was found to be 1.5 cps. The JHp in the CH3OP system was found to be 10.3–10.5 cps, and, therefore, JHp in the trans form is considered to be much greater (∼28.2cps) than that in the gauche form. The JHp the RCH2OP systems were found to be 6.3–7.0 cps, and, therefore, C–R bond in these systems are considered to have a greater chance of taking trans position with respect to the O–P bond around the C–O bond than the chance of taking gauche position.
Electron Spin Resonance of Anion Radicals of Aromatic Esters. I. The Anion Radicals of Methyl, Ethyl and Isopropyl Benzoates, and of Methyl and Ethyl Isonicotinates
Authors: Hirayama Masatoshi 
Published: July 2006

Abstract
The ESR spectra of the anion radicals of methyl, ethyl and isopropyl benzoates, and of methyl and ethyl isonicotinates were observed. When the spin densities of these anions were calculated by using McLachlan’s method, the results were in good agreement with the experimental data. It has been found that the electron-withdrawing effect of the ester group is situated between those of the cyano and acetyl groups, and that the ester group may be locked into the benzene plane. Comparatively large splittings due to the α-protons in the ester group were observed. The proton position is defined by the notation:
(Remark: Graphics omitted.)
An equation, aCH3H=QOCH3Hρoπ, was assumed, and for these anion radicals values of |QOCH3H| much larger than 27.2 gauss for the C–CH3 hyperconjugation were evaluated.
Preparation of the Schiff Base Complexes of Lanthanide(III) Ions
Authors: Isobe Toshiyuki , Kida Sigeo , Misumi Seizo 
Published: July 2006

Abstract
The 1 : 1 complexes of lanthanide(III) ions such as La(III), Pr(III), Nd(III), Gd(III) and Er(III) with tris-(salicylidene amino)-triethylenetetramine have been prepared. Among these complexes, the lanthanum(III) complex is unique in infrared spectra and solubility to the solvents; it is soluble in chloroform and nitrobenzene and found to be dimeric in chloroform solution. The other lanthanide(III) complexes are practically insoluble in any available solvents, and are assumed to be polymeric.
Reactions of 1,3-Dienes with Acrylates by Means of Transition Metal Complex Catalysts
Authors: Misono Akira , Uchida Yasuzo , Saito Taro , Uchida Keiichi 
Published: July 2006

Abstract
The reactions of 1,3-dienes with acrylates by the use of catalyst systems composed of transition-metal acetylacetonates and triethylaluminum were studied. Butadiene and isoprene react with acrylates to give hepta-2, 5-dienoates and 5- or 6-methylhepta-2, 5-dienoates respectively, by means of the binary catalyst system consisting of cobalt (III) or iron (III) acetylacetonate and triethylaluminum. The effects on this reaction of changing the catalyst concentration, the molar ratio of triethylaluminum to the transition-metal acetylacetonates, and the mixing order of the reagents were examined, as was the difference in catalytic activities between cobalt and iron catalyst systems.
Kinetic Studies of Bimolecular Nucleophilic Substitution. II. Structural Effects of Alkyl Halides on the Rate of SN2 Reactions —A Reinvestigation of the Linear Free-Energy Relationships for the Structural Variation of the Alkyl Groups
Authors: Okamoto Kunio , Nitta Issei , Imoto Tetsuo , Shingu Haruo 
Published: July 2006

Abstract
The linear free-energy relationships have been examined for 35 SN2 reaction series, including 4 series of the SN2 reactions of alkyl bromides which rates were measured in these laboratories. These results have then been treated using the equation, log(k⁄k0)=rα, where α is a structural constant for methyl, ethyl, n-propyl, n-butyl, i-propyl, i-butyl, and neopentyl groups and where r is a reaction constant. The α values have been estimated as the arithmetic means of the logkSN2 values of the reaction series examined for each alkyl. The correlation coefficients for r’s are greater than 0.960 for all of the reaction series except two. The inapplicability of Taft’s polar and steric substituent constants (σ* and Es) to the SN2 reactivity of these alkyl groups has been discussed.
Kinetic Studies of Bimolecular Nucleophilic Substitution. IV. Rates of the SN2 and E2 Reactions of β-Substituted Ethyl Chlorides with Sodium Acetate in Aqueous Solutions
Authors: Okamoto Kunio , Kita Teruo , Araki Kiyoshi , Shingu Haruo 
Published: July 2006

Abstract
Rates in the SN2 and E2 reactions of a series of β-substituted ethyl chloride (RCH2CH2Cl, R=Et, MeO, PhO, Gl, and H) in aqueous solutions have been measured at temperatures ranging from 90 to 150°C, using sodium acetate as a nucleophile. The mild rate-retarding effect of β-subtituents in the SN2 reactions, observed in the rate order, H&gt;Et&gt;MeO&gt;Cl&gt;PhO, may be attributed to the steric effects. In a similar fashion, the retardation of E2 reaction rates by the β-substituents, which is in the rate sequence H&gt;MeO&gt;Et&gt;PhO&gt;Cl, may be ascribed to the steric effects, which outweigh the electronic effects. The β-substituent effects of several other substituents, which are known in the literature, have also been discussed.
Studies on Amino-hexoses. XI A Synthetic Substrate of Egg White Lysozyme: Phenyl 6-O-(2-Acetamido-2-deoxy-β-d-glucopyranosyl)-2-acetamido-3-O-(d-1′-carboxyethyl)-2-deoxy-β-d-glucopyranoside
Authors: Yamamoto Kazuhiko , Matsushima Yoshio 
Published: July 2006

Abstract
In the course of the study of the substrate specificity of egg white lysozyme, a phenyl glycoside of a disaccharide, N-acetyl-β-d-glucosaminyl(1→6)N-acetyl-muramic acid, was synthesized as a model substrate of the enzyme. Evidence for the 1→6 linkage between two component sugars was obtained by chemical and NMR studies. As a reference standard for a chromatographic investigation, 4-O-methyl muramic acid was prepared. The lysozyme action on the model substrate, if any, was found to be extremely weak.
Synthesis of cyclo-Diglycyl-l-lysyl-diglycyl-l-lysyl and Hydrolysis by Trypsin
Authors: Abe Okitoshi , Takiguchi Hideo , Ohno Motonori , Makisumi Satoru , Izumiya Nobuo 
Published: July 2006

Abstract
A protected cyclic hexapeptide (XVI), cyclo-(diglycyl-ε-benzyloxycarbonyl-l-lysyl)2, was synthesized in three different ways; the cyclization reactions of a protected tripeptide azide, a protected tripeptide active ester, and a protected hexapeptide active ester produced the protected cyclic hexapeptide (XVI) in fairly good yields. The product (XVI) was then converted by hydrogenolysis to the cyclic hexapeptide (XVII), cyclo-(digrycyl-l-lysyl)2. It was found that the cyclic hexapeptide was hydrolyzed slowly by trypsin to a tripeptide diglycyl-lysine, whereas a synthetic hexapeptide, diglycyl-lysyl-diglycyl-lysine, was hydrolyzed very rapidly to the tripeptide.
The Zinc Oxide-Copper Catalyst for Carbon Monoxide-Shift Conversion. I. The Dependency of the Catalytic Activity on the Chemical Composition of the Catalyst
Authors: Uchida Hiroshi , Isogai Norio , Oba Masaaki , Hasegawa Toji 
Published: July 2006

Abstract
The zinc oxide-copper catalysts under investigation included a series of catalysts of different copper contents prepared by kneading zinc oxide powder with copper hydroxide cake (the “kneaded series”), and two other catalysts prepared by the impregnation and the coprecipitation methods. Only the catalysts of the kneaded series show a high activity in the carbon monoxide-shift conversion, provided the catalysts contain appropriate amounts of copper. The observed dependency of the catalytic activity on the copper content can be interpreted in view of the catalyst scheme in which the copper forms its own fine particles among the original zinc oxide particles. On the basis of this picture, the study was then extended to other copper-containing catalysts; an active alumina-copper catalyst could be produced by kneading the cake with alumina powder with a high specific surface area.
NMR Study of the Benzoxazole Derivatives
Authors: Okuda Hisashi , Nagai Makoto 
Published: July 2006

Abstract
The PMR spectra of 5 benzoxazole derivatives were measured in CCl4 (or CDCl3) and CF3COOH. It was found that, due to the magnetic anisotropy of heteroatoms and the electricfield effect, ring protons shift to a lower field than had been anticipated from the π-electron densities (in the case of 4-H, ca. 0.4 ppm). In acid media, the π-electron density distribution of benzoxazole is changed because of the protonation of the nitrogen atom, and these two effects vanish. Correcting the measured shifts with Pople’s and Buckingham’s expressions for these effects, the following relation has been found to hold between the corrected shifts and the π-electron densities calculated with the Hückel LCAO MO method:
τ−2.95=3.37 (π−1)
Kinetics of the Catalytic Decomposition of Methanol, Formaldehyde and Methyl Formate over a Copper-wire Surface
Authors: Miyazaki Eizo , Yasumori Iwao 
Published: July 2006

Abstract
In order to reveal the selective action of nickel and copper in the catalytic decomposition of methanol, kinetic studies of the decomposition of methanol, and methanol-d1 (CH3OD), and also of that of formaldehyde and methyl formate, both the assumed intermediates of the methanol decomposition, were undertaken over the temperature range between 100 and 330°C and the pressure range up to 30 mmHg. We also made studies of the exchange reaction of methanol, formaldehyde, or methyl formate with deuterium. The obtained rate equation for the methanol decomposition and the results on the deuterium exchange lead to the following conclusion: the rate is controlled by the unimolecular dehydrogenation of adsorbed methanol, which gives formaldehyde at first and finally hydrogen and carbon monoxide via a more stable intermediate, methyl formate. A comparison of activities between copper and nickel was made on the basis of the different behavior of formaldehyde on these catalyst surfaces. The nature of the catalyst surface and of the sites effective for the reaction were also briefly discussed.
Melting of Complexes of Polyribocytidylic Acid Plus Copolymers of Inosinic and Guanylic Acids in Solution
Authors: Maeda Masako , Matsuo Kimiko , Nakanishi Mamoru , Tsuboi Masamichi 
Published: July 2006

Abstract
Three copolymers of riboinosinic acid and riboguanylic acid (poly IG), with guanylic acid contents of 21.6%, 33%, and 45%, have been prepared, as well as three homopolymers of ribocytidylic acid (poly C), riboinosinic acid (poly I), and riboguanylic acid (poly G). On mixing both the poly IG and the poly G with poly C in various mole ratios in an aqueous solution, a marked hypochromicity was observed in the 250 mμ region, and it was shown that there are double helical complexes similar to the well-known poly(I+C) formed in the solutions. The optical melting profile of each complex into random coils was examined, and it was found that the guanine-cytosine pair is 20% (in enthalpy) more stable than the hypoxanthine-cytosine pair. It was also found that actinomycin D, which has no effect on the melting of poly (I+C), stabilizes the helical structure of poly(IG+C).
Charge-carrier Mobility in Anthracene Single Crystals
Authors: Maruyama Yusei , Inokuchi Hiroo 
Published: July 2006

Abstract
In order to examine the effect of space-charge polarization in the course of drift-mobility measurements in anthracene single crystals, we employed a pulse electric field and measured the change in photoresponses according to the light-delay times. No distinct reduction of photoresponses was found, and the value of mobility was nearly the same as the one obtained by measurement with the conventional dc field. To obtain knowledge of the microscopic mobility in anthracene crystals, we also measured the photo-Hall effect of anthracene using the Redfield, Kobayashi and Brown method. The observed Hall mobility was in the range of 25–200 cm2/ V.sec. This large value of Hall mobility will be briefly discussed in terms of the multiple-trapping effect.
Studies of the Grinding of Condensed Phosphates. III. The Effect of the Relative Humidity on Grinding of Sodium Trimetaphosphate
Authors: Motooka Itaru , Hashizume Genzo , Kobayashi Masamitsu 
Published: July 2006

Abstract
The effect of the atmosphere, particularly of the relative humidity, on the process of grinding of sodium trimetaphosphate was examined, and the following results were obtained: 1) In the case of grinding in air, as the relative humidity increased, the grinding effect—for example, the time required to reduce trimetaphosphate molecules to one half—decreased in the humidity range from 20 to 60%. 2) In the case of grinding in nitrogen or carbon dioxide gas, the grinding effect was the same as that in air. In view of these results, it may be said that humidity is one of most important factors in the process of grinding sodium trimetaphosphate.
Electronic Aspect of the Antibacterial Activity of Nitrofuran Derivatives
Authors: Hirano Koichi , Yoshina Shigetaka , Okamura Kimiko , Suzuka Isamu 
Published: July 2006

Abstract
In order to interpret the antibacterial activity of nitrofuran derivatives (N. F.) in connection with their electronic properties, an approximate superdelocalizability, Sr(N)′, the frontier electron density, fr(N), and the energy of the lowest vacant level, klv, were calculated. The simple Hückel MO method was adopted in this calculation. The activity for typical compounds of N. F. correlated closely with the values of klv. On the contrary, no significant correlation was found between the reactivity index, Sr(N)′, and this activity. These suggest that the bactericidal action of N. F. can be interpreted in terms not of the reactivity of N. F., but of the electron transfer from a biomolecule such as NADH to the N. F. molecule. On the other hand, between NADH and N. F. a molecular complex was found. This enables one to conclude that, by the use of their electron affinity, N. F. molecules inhibit the electron transfer coupled with the NADH of the respiratory chain in the body of bacteria.
The Chromium(III) Complexes with Ammoniatriacetic Acid. I. The Complexes with Ammoniatriacetic Acid as a Tridentate or Tetradentate Ligand
Authors: Uehara Akira , Kyuno Eishin , Tsuchiya Ryokichi 
Published: July 2006

Abstract
The following chromium(III) complexes, each containing ammoniatriacetic acid (ATA) as a tridentate or a tetradentate ligand, were newly prepared: (NH4)3[Cr(ata)2]·4H2O (pale red) (I), NH4[Cr(ataH)2]·2H2O (pink) (II), NH4[Cr(OH)(ata)(H2O)]·2H2O (purple) (III) and NH4[Cr(OH)(ata)(H2O)]·3H2O(green)(IV), where ata is an abbreviated form of N(CH2COO−)3. On the basis of the chemical and thermal analyses and the measurement of electronic absorption spectra, it was considered that the I and II complexes belong to the [Cr·N2·O4] type, III belongs to the [Cr·N·O5] type, and IV to the [Cr·O6] type. The further information on the conductivity in an aqueous solution suggested that the II and III complexes are gradually aquated to form the [Cr·N·O5] and [Cr·O6] types respectively. The X-ray powder diffraction patterns show that all these complexes have crystals of the tetragonal system. The values of the effective magnetic moments for these complexes were 3.7–3.9 B. M., nearly equal to the spin-only magnetic moments of tervalent chromium.