bluuebunny/crossref_metadata_2025 huggingface dataset:
Role of Macromolecules in Emulsion Stability with Special Reference to Pepsin as Emulsifier
Authors: Prakash Chandra , Srivastava S N
Published: July 2006

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

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

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

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

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

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

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

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

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

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>Et>MeO>Cl>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>MeO>Et>PhO>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

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

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

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

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

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

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

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

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

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

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.
Studies of the Solvent Effects on the Chemical Shifts in NMR Spectroscopy. IV. Methoxyl Proton Signals of Methoxybenzenes in the Benzene Solutions
Authors: Matsuo Taku , Yoshida Toshiaki , Higuchi Osamu
Published: July 2006

The chemical shifts of methoxyl protons of a series of methoxybenzenes and the related compounds in cyclohexane, carbon tetrachloride, and benzene solutions have been investigated. The benzene-induced high-field shifts for methoxyl protons are large if the substituent at the benzene ring is a highly electron-withdrawing group. In carbon tetrachloride, the methoxyl proton signals appear at lower field than those in cyclohexane solutions. The low-field shifts also increase with the electronegativities of the substituents. An attempt has been made to interpret the solvent effects by the use of a model where benzene molecules are assumed to cluster around the methoxyl group and the benzene ring of the solute molecule. The attraction between solute and solvent molecules has been suggested to be due to the van der Waals interactions and partly to the charge-transfer interaction.
ESR Study of the Mercury-photosensitized H2+O2 Reaction
Authors: Shimokoshi Kazuo , Mori Yuji , Tanaka Ikuzo
Published: July 2006

The ESR technique has been applied to a study of the mercury-photosensitized reaction of H2+O2 mixtures in the PO2=10–200 μHg and PH2=0.2–4 mmHg regions. For the determination of this reaction, the concentration (ESR signal amplitude) of H atoms was followed with time throughout the reaction. The concentration of H atoms varied with time; its maximum was determined. The time (Tm) at which the H atom concentration reached a maximum depended on oxygen and hydrogen pressures. From the variations in Tm and some kinetic considerations, it was concluded that oxygen played an important role in this reaction in increasing the stationary concentrations of H atoms in the system. In this experiment, I0=2.4×1015 molecules/sec, the rate of the production of H atoms in Reaction (1), was determined from the variations in Tm with the initial oxygen pressure:

(Remark: Graphics omitted.)

The pressure of oxygen at the maximum concentration of H atoms was found to be little dependent on the PH2 used in this experiment; 5 μHg was found to be this pressure.
The Electron Spin Resonance of γ-Irradiated Sodium Polyphosphate. II. Effects of the Degree of Polymerization and the Kind of Cation
Authors: Hasegawa Akinori , Miura Masaji
Published: July 2006

Sodium polyphosphate irradiated with γ-rays was investigated with ESR by varying the degree of polymerization and by replacing sodium ion with other cation. By irradiating at room and liquid nitrogen temperatures and observing ESR at various temperatures, nine kinds of paramagnetic centers were detected. Two of them were attributed to trapped electrons and the others to trapped holes. Four among the latter groups were assigned to radicals on polyphosphate; fragments by bond rupture, –O3PO°· and °·PO3–, radical on end group, –O3PO°·, and radical on chain, –O2P\overset·°OO–.
Active Sites for the Dehydrogenation of Ethyl Alcohol on Lithium Fluoride Single Crystal
Authors: Yamashina Toshiro , Watanabe Kuniaki
Published: July 2006

The dehydrogenation of ethyl alcohol on LiF single crystal surfaces has been investigated to determine the role of surface dislocations and another defects on the catalysis. The catalytic activity of the single crystal of LiF was greatly influenced by the surface treatments such as the manners of cleaving of the crystal and vacuum heating and so on. After radiation quenching subsequent to vacuum anealing at 350°C for 2 hr, the catalytic activity was greatest in the present work, being over seven times greater than that of nontreated crystal. The catalytic activity after the quenching treatment was found to increase in proportion to logarithm of the dislocation density. In observations with the electron microscope, the small spots concentrated in the center of dislocation was found on the highly activated crystal surface. From the results of kinetic and microscopic observations discussion was made on the catalytic sites of the LiF single crystal.
The Reaction of Tris(acetylacetonato)aluminum with Bromine in Dichloromethane
Authors: Nakamura Yukio , Hirata Masaaki , Kawaguchi Shinichi
Published: July 2006

The reaction between tris(acetylacetonato)aluminum and bromine in dichloromethane was studied. The main product of this reaction was tris(γ-bromoacetylacetonato) aluminum which was soluble in dichloromethane. A small amount of slightly yellow precipitate was also produced as a minor product. The same compound was obtained in the reaction of tris(γ-bromoacetylacetonato) aluminum with hydrogen bromide in dichloromethane containing water, and identified as bromoaquobis(γ-bromoacetylacetonato) aluminum on the bases of the elemental and water analyses, the ion exchange study, and the infrared spectroscopy.
Altenin. V. Pathogenic Activity of Reductones to the Pear
Authors: Sugiyama Noboru , Kashima Choji , Yamamoto Makoto , Takano Tadao , Mohri Ryotaro
Published: July 2006

The three reductones, 3-hydroxy-2, 4-dioxopentane, ethyl 2-hydroxy-1, 3-dioxovalerate and ethyl 2-hydroxy-3-oxobutyrate, were synthesized. These compounds were examined for the pathogenic activities to the pear. The pathogenic activities of reductones have some relations with the endiol contents. The center of pathogenic activity in altenin is shown to be the endiol carbonyl grouping.
The Wolff Rearrangement. I. Kinetic Studies of the Decomposition of α-Diazoacetophenone
Authors: Yukawa Yasuhide , Tsuno Yuho , Ibata Toshikazu
Published: July 2006

Kinetic studies of the Wolff rearrangement of α-diazoacetophenone were performed in t-butyl alcohol, by the volumetric measurement of the evolved nitrogen, using a solution of silver benzoate in triethylamine as a catalyst. A pseudo-first-order rate constant was obtained accompanying the induction period. The effects of the concentrations of silver benzoate and triethylamine on the reaction rate were studied. The concentration of silver ions was determined by the gravimetric measurement of silver chloride in the course of the reaction. The silver ions were found to be consumed only in the initial stage of the reaction. On the basis of these results, a novel reaction mechanism, in which the active entity of the catalyst was thought to be a silver ion-triethylamine complex, was proposed.
The Wolff Rearrangement. II. The Substituent Effects on the Rate of the Catalytic Decomposition of Substituted α-Diazoacetophenones
Authors: Yukawa Yasuhide , Tsuno Yuho , Ibata Toshikazu
Published: July 2006

The substituent effect on the reaction rates of the Wolff rearrangement of meta- and parasubstituted α-diazoacetophenones was studied in t-butyl alcohol, isopropyl alcohol, and t-butyl alcohol-toluene mixed solvents, and also on the decomposition rates in toluene, using a solution of silver benzoate in triethylamine as a catalyst. Similar substituent effects were observed regardless of the solvents used. Strong electron-releasing conjugative substituents at the para position, such as methoxy and ethoxy groups, retard the reaction rate greatly. The other substituents accord roughly with the Hammett relationship, having small negative ρ-values. The decomposition rate constants in toluene were apllicable to the Yukawa-Tsuno equation, which has a negative γ-value:

logk⁄k0=−0.45(σ−2.7ΔσR+)−0.05

proving that the resonance stabilization on the reaction origin are caused by the electron-releasing substituent at the para position. The results of the kinetic isotope effects (no apparent kinetic isotope effect was observed within the range of experimental error) of the Wolff rearrangement of carbonyl-14C, and phenyl-1-14C labeled α-diazoacetophenone under the same reaction conditions favor the two-step mechanism to the concerted one for the elimination of nitrogen and the migration of the alkyl group.
The Preparation of 1-Dimethylamino-1-ethylthioethylene (Ketene-N, S-acetal) and Its Reactions with Some Electrophilic Reagents
Authors: Mukaiyama Teruaki , Aizawa Shin-ichi , Yamaguchi Tatsuaki
Published: July 2006

The preparation of 1-dimethylamino-1-ethylthioethylene (ketene-N, S-acetal) from N, N-dimethylamino-S-ethylthioacetamidium iodide and the reactions of the ketene-N, S-acetal with some electrophilic reagents were investigated. One equivalent of phenyl isocyanate and two equivalents of diphenylketene reacted with the ketene-N, S-acetal to produce substituted acrylanilide and 2, 3-dihydro-α-pyrone derivative, respectively. On the other hand, the reactions of the ketene-N, S-acetal with carbon disulfide in the presence of elemental sulfur and with electrophilic oleflns, such as acrylonitrile and methyl acrylate, gave 5-dimethylaminotrithione and substituted cyclobutenes, respectively, by eliminating ethyl mercaptan. Further, it was found that α, β-unsaturated carbonyl compounds, such as acrolein and methyl vinyl ketone, afforded bicyclic compounds, 2, 10-dioxabicyclo[4. 4. 0]decadiene-3, 8 derivatives.
Anionic Copolymerization of Styrene and 1, 1-Diphenylethylene
Authors: Yuki Heimei , Hotta Junichi , Okamoto Yoshio , Murahashi Shunsuke
Published: July 2006

The anionic copolymerization of styrene (M1) and 1, 1-diphenylethylene (M2) was investigated. 1, 1-Diphenylethylene, which can not homopolymerize by itself, was copolymerized with styrene by means of an anionic initiator. The copolymerization reaction seemed to proceed without termination or chain transfer, and gave a high molecular alternating copolymer under appropriate reaction conditions. The monomer reactivity ratio, r1, was obtained from the copolymer composition at the complete consumption of M1, assuming the rate constant k22=0. The monomer reactivity ratio was affected by the solvent (n-hexane, benzene, toluene, or THF), but not by the catalyst (n-BuLi, Na-dispersion, Na-naphthalene, or K-dispersion) or the reaction temperature. It was 0.4 in toluene at 30°C.
Polymerization Initiated with a Potassium Complex of Aromatic Ketone and Its Use in the Preparation of a Multi-Chain Copolymer
Authors: Nobutoki Koji , Sumitomo Hiroshi
Published: July 2006

Four kinds of complexes were prepared by the reactions of benzil with a potassium or potassium-sodium alloy in tetrahydrofuran. The polymerizations of styrene (St), isoprene (Ip), methyl methacrylate (MMA), and ε-caprolactone (CL) initiated with these complexes were attempted. St and Ip were found to be polymerized by the dipotassium or tetrapotassium adducts of benzil, but not by the monopotassium ketyl. All these complexes were effective in polymerizing MMA and CL. A new class of multi-chain copolymers with different kinds of branches was also prepared by the polymerizations of MMA and CL with the potassium adducts of polystyrene ketones synthesized by the coupling reactions of one-ended living polystyrene with 2, 4′-dichlorobenzophenone or terephthaloyl chloride.
Solution Properties of the Methyl Methacrylate-Acrylonitrile Copolymer
Authors: Shimura Yuko
Published: July 2006

Short-range interactions between chain units of random copolymers in solution may be influenced by the characters of the pendant side groupes or, more precisely, by the dipole moment of the substituent. In those experiments the steric factor was derived for a random copolymer composed of methyl methacrylate and acrylonitrile from the relation between the limiting viscosity number and the molecular weight. Mark-Houwink relations were obtained in N,N′-dimethylformamide (DMF) and in methyl ethyl ketone (MEK) at 30°C for the copolymer containing 0.48 mol fraction of acrylonitrile, and for polymethyl methacrylate (PMMA) for the sake of comparison:

[η]=4.61×10−4M0.65 for the copolymer in DMF

[η]=1.70×10−4M0.65 for PMMA in DMF

[η]=1.26×10−3M0.52 for the copolymer in MEK

With the Stockmayer-Fixman expression, these correlations become, respectively:

[η]=213×10−5M1⁄2+12.4×10−7M

[η]=78.2×10−5M1⁄2+5.05×10−7M

[η]=163×10−5M1⁄2+1.05×10−7M

The unperturbed mean square end-to-end distance, 〈L2〉0, determined from the first term of the latter expressions, together with the 〈L2〉0f value calculated by assuming the completely free rotation, gives the steric factor of σ=(〈L2〉0⁄〈L2〉0f)1⁄2 2.59±0.01 from the DMF solution; this factor is larger than that for polymethyl methacrylate (2.11±0.08),, and that for polyacrylonitrile (2.20+0.05). The steric parameter derived from the MEK solution is 2.37±0.05 for this co-polymer; this value does not agree with the value obtained from the DMF solution. In both cases, it may be concluded that the dimensions of the copolymer between acrylonitrile and methyl methacrylate are influenced by the electrostatic interactions between nitrile groups of acrylonitrile units and methoxy-carbonile and/or methyl groups of methyl methacrylate units. The second virial coefficient in MEK obtained from the light scattering measurements also has a larger value for this copolymer than for polymethyl methacrylate. This tendency of copolymers to show a larger second virial coefficient seems to be an essential characteristic of some copolymers.
Some Applications of the Regular Solution Theory to Solvent Extraction. IV. Oxine-Inert Solvent System
Authors: Wakabayashi Toshiki
Published: July 2006

The distribution coefficients of oxine between aqueous solutions with the ionic strength of 0.1 and 12 inert solvents were determined photometrically at 25°C. By a previously-proposed equation, the distribution coefficients were then correlated quantitatively with the solubility parameters of the solvents. The solubility parameter for oxine was evaluated as 10.9, and that for an aqueous solution, as 16.95, while the molar volume of oxine was estimated to be 124 cc/mol. The distribution of the two methyl derivatives of oxine was also discussed.
Studies of Phosphorylation. I. Phosphorylation of 2′, 3′-O-Isopropylidene Nucleoside by Phosphoryl Chloride
Authors: Yoshikawa Masaharu , Kato Tetsuya
Published: July 2006

5′-Nucleotides could be conveniently prepared in high yields by the phosphorylation of 2′, 3′-O-isopropylidene nucleosides with phosphoryl chloride in the absence of any organic solvent. The rate of phosphorylation in a large excess of phosphoryl chloride was markedly promoted by the partial hydrolysis of phosphoryl chloride with a small amount of water. The undesirable cleavage of the glycosidic linkage in nucleoside, which was observed particularly in a strongly acidic medium caused by the addition of excessive water, could be suppressed by the addition of ethers or amines in a phosphoryl chloride solution. 2′, 3′-O-Isopropylidene derivatives of adenosine, inosine, and guanosine gave the corresponding 5′-nucleotides in good yields, whereas that of xanthosine reacted very slowly, unlike the above nucleosides. All attempts at the phosphorylation of 2′, 3′-O-isopropylidene-2-mercaptoinosine were unsuccessful. The influence of substituents at the 2-position in purine bases on phosphorylation was investigated by comparing the reactivity between the above-mentioned nucleosides and their methylated derivatives, such as 2-dimethylaminoinosine, 2-methoxyinosine, and 2-methylthioinosine; it was found that these methylated nucleosides were readily phosphorylated to give the corresponding 5′-nucleotides in nearly quantitative yields.
Effects of Ligands in the Cobalt Salt-catalyzed Decomposition of t-Butyl Hydroperoxide
Authors: Onuma Kazuhiko , Wada Keisuke , Yamashita Junzo , Hashimoto Harukichi
Published: July 2006

A kinetic study has been made of the cobalt acetate-catalyzed decomposition of t-butyl hydroperoxide in acetic acid at 40.4°C, and the effects of added lithium salts on the decomposition rate have been studied. The observed rate law for the cobalt acetate-catalyzed decomposition is: v=k2[Co(II)][t-C4H9OOH]+k3[Co(II)]2[t-C4H9OOH]. When lithium halides (chloride and bromide) are added to this system, the cobalt acetate is changed to cobaltous halide and the rate of decomposition is markedly decreased. In the case of lithium bromide the hydroperoxide decomposition is accompanied by the generation of molecular bromine. The mechanisms for the bromine formation will be discussed. The role of these cobalt salts in the course of autoxidation in relation to the hydroperoxide decomposition will also be discussed.
Studies of Peptide Antibiotics. XII. Syntheses of [2,2′-α,γ-Diaminobutyric acid]- and [2,2′-Lysine]-gramicidin S
Authors: Waki Michinori , Abe Okitoshi , Okawa Reiko , Kato Tetsuo , Makisumi Satoru , Izumiya Nobuo
Published: July 2006

To investigate the contribution for the antibacterial activity of the ornithine residues in gramicidin S, two analogs of gramicidin S, [2, 2′-l-α,γ-diaminobutyric acid]- and [2, 2′-lysine]-gramicidin S, were synthesized by the cyclization reaction of linear pentapeptide active esters with pyridine. It was indicated that the crude product of the cyclization of each of the linear active esters was composed of two components. The protected cyclic decapeptide, a less soluble material, was easily isolated by fractional crystallization, and the hydrogenolysis of this product in the presence of hydrogen chloride afforded the crystalline hydrochloride of [2, 2′-diaminobutyric acid]-or [2, 2′-lysine]-gramicidin S. These cyclic decapeptides were as active as natural gramicidin S; the results indicated that the side chains of the ornithines in gramicidin S could be replaced by other chains without a loss of activity.
Über die Reduktion von 5-Oxo-2-methyl-4, 4-dibenzyl-3-äthoxycarbonyl-4, 5-dihydroindol und die Umsetzungen des Reduktionsproduktes mit Säuren
Authors: Suehiro Tadashi , Nakagawa Akihiro
Published: July 2006

5-Oxo-2-methyl-4, 4-dibenzyl-3-äthoxycarbonyl-4, 5-dihydroindol (I) ist ziemlich beständig gegen allgemeine Reduktionsmittel, wird aber reduziert mit Aluminium-Amalgam oder mit Natriumborhydrid. Bei der ersten Reduktion entsteht ein dimerer Alkohol. Bei der letzteren wird 5-Hydroxy-2-methyl-4, 4-dibenzyl-3-äthoxycarbonyl-4, 5, 6, 7-tetrahydroindol (III) gebildet. Die Hydroxy-Gruppe von III wird leicht bei der Behandlung mit Eisessig-Salzsäure oder -Schwefelsäure mit der Chlor- oder Acetyloxy-Gruppe unter Deäthoxycarbonylierung ausgetauscht. Dehydratisierung von III gelingt bei der Einwirkung von syrup. Phosphorsäure unter gleichzeitiger Deäthoxycarbonylierung and Umlagerung einer Benzyl-Gruppe in 2-Methyl-4, 5-dibenzyl-6, 7-dihydroindol (VII). VII lässt sich über Palladium-Kohle in 2-Methyl 4, 5-dibenzylindol (IX) dehydrieren, dessen Struktur synthetisch festgestellt wurde.
An X-Ray Emission Spectroscopic Investigation of the Chemical Bond of Sulfur. I. The Peak Shift of Kα and the Number of Valence Electrons of the Sulfur Atom in Compounds
Authors: Sato Toshio , Takahashi Yoshihito , Yabe Katsumasa
Published: July 2006

The energy shifts of the SKα doublet have been measured in fifty sulfur compounds in solid or liquid states, using rhombic sulfur as a standard. The values were the same as those obtained by Faessler and Goehring, although a slight discrepancy was observed on sulfites and sulfates. The mean number of the valence electrons, N, associated with the sulfur atom in compounds has then been calculated from the shifts according to a theoretical correlation presented by Coulson and Zauli. The values of N have been found to be 6.7, 6.3, 5.2, 4.7, 4.7, and 4.3 for inorganic sulfides, organic sulfides, sulfoxides, sulfites, sulfones and sulfates respectively, assuming that N=6.0 for rhombic sulfur. The dipole moments evaluated from the values of N and structural data were 4.9, 4.8 and 5.2D, for dimethyl sulfoxide, dimethyl sulfone and diphenyl sulfone, respectively; these values were almost compatible with the experimental values of 3.9, 4.41 and 5.14D. respectively.
A Molecular Orbital Investigation of the Electronic Structures of Alkyl Peroxides. II Peracids and Peresters
Authors: Yonezawa Teijiro , Kato Hiroshi , Yamamoto Osamu
Published: July 2006

The electronic structures of several alkyl peroxides including the carbonyl group, i. e., performic acid, peracetic acid and their methyl esters, are investigated by the extended Hiickel method proposed by Hoffmann. The structure of the bond between peroxy oxygens, the intramolecular hydrogen bonding in peracid, the pyrolysis of peracid which is caused by the fact that the bond strength between peroxy oxygen atoms is weakened by an intramolecular hydrogen bonding, and the reaction mechanism of both the epoxidation of olefin by peracid and the ionic decomposition of peresters by basic catalysts can be successfully explained on the basis of the calculated results.
The Extraction of Gallium and the Direct Spectrophotometric Determination in the Organic Phase with 4-(2-Pyridylazo)-resorcinol
Authors: Bansho Kenji , Umezaki Yoshimi
Published: July 2006

A rapid method for the spectrophotometric determination of microgram amount of gallium with 4-(2-pyridylazo)-resorcinol (PAR) in the organic phase after the extraction of gallium from a hydrochloric acid solution with isopropyl ether and butyl acetate will be described. A red color is formed in an aliquot of the organic extract by the addition of PAR, pyridine, and sodium acetate in methanol. The complex formed in the organic phase has a maximum absorbance at 510 mμ. The color reaction conforms to Beer’s law, and the molar absorptivity of the complex is estimated to be approximately 100000. The coefficient of the variation of the absorbance measurements on a standard gallium solution at 510 mμ was about 0.8%. A study of the effect of diverse ions showed the method to be highly selective.
The Synthesis and the Electronic Spectra of 1, 1′-Dianthrylpoly-ynes
Authors: Akiyama Shuzo , Nakagawa Masazumi
Published: July 2006

The synthesis of 1, 1′-dianthryldi- and tetra-acetylenes has been reported previously by the present authors. Now, 1, 1′-dianthryltri-, penta- and hexa-acetylenes have been synthesized in order to complete the series of 1, 1′-dianthrylpoly-ynes. It is well known that the square of the wavelength of the longest absorption maxima, λmax in the electronic spectra of some series of poly-enes and poly-ynes varies linearly with the number of the multiple bonds, n(λmax2∞n). It was anticipated that the dianthrylpoly-ynes would exhibit analogous spectral behavior. Unexpectedly, however, it was observed that the λmax of the dianthrylpolyacetylenes varied linearly with the square of the number of the triple bonds, n(λmax∞n2).
The Synthesis of the Cyclohexenone Palladium Complex and Related Compounds
Authors: Kasahara Akira , Tanaka Keiko , Asamiya Kazunori
Published: July 2006

The chloro-bridged π-allylic palladium complex has been prepared from cyclohexenone and sodium chloropalladite. 6-Oxo-4, 4-dimethylcyclohex-2-enyl, 1,2-(4-oxo-2, 2-dimethylbutano)-π-allyl and 1, 2-(1-oxo-butano)-3-phenyl-π-allyl palladium complexes have also been prepared from the corresponding cyclic α, β-unsaturated ketones. The structures of all these compounds have been confirmed by a study of their absorption spectra and of the NMR spectra.
The Synthesis of Friedelan-3-on-24-al
Authors: Hoshino Tokiko , Tsuyuki Takahiko , Takahashi Takeyoshi
Published: July 2006

24-Oximinofriedelan-3β-ol (V) was converted via either lactone (VI) or hemiacetal (VIII) into diol (VII). Monoacetylation of the diol gave 24-acetoxyfriedelan-3β-ol (X), which was oxidized to keto acetate (XI). Hydrolysis of XI afforded the corresponding keto alcohol, followed by Jones’ oxidation giving rise to friedelan-3-on-24-al (I), mp 248—249°C, [α]578 +66°. The physical constants of I are not identical with those of friedelan-3-on-y-al, isolated by Courtney et al. from Siphonodon australe Bent. This furnishes a further evidence that friedelan-3-on-y-al is not friedelan-3-on-24-al (I), but friedelan-3-on-25-al, confirming the recent Courtney’s proposal.
Oxidation of Propylene over Vanadium and Molybdenum Oxide Catalysts
Authors: Wakabayashi Katsuhiko , Kamiya Yoshio
Published: July 2006

The oxidation of propylene with a large amount of propylene has been studied over vanadium and molecule oxide catalysts in a flow system. The relation temperature was 470°C; the partial pressure of oxygen was kept at 0.1 atm, while that of propylene was varied from 0.1 to 0.8 atm. The main oxidation products were carbon monoxide, carbon dioxide, and acrrolein. In the oxidation with a pure vanadium oxide catalyst, the yield of acrolein increased with the proplene partial pressure, and the selectivity to acrolein was about 30% at the propylene partial pressure, and the selectivity values of the selectivity to various reaction products at the contact time of 0 sec did not change even though the propylene partial pressure was changed from 0.1 to 0.8 atm. X-ray patterns of the catlyst used (free of carriers) show the presence (of V2O4 or a mixture) of V2O4and V2O3 according to the partial pressure of propylene. It is concluded that acrolein undergoes a secondary reaction more severly when a vanadium oxide catalyst is in the higher oxidative state, that is, when it is richer in V2O4. In the system of vanadium-molybedenum oxides, the three mixed catalysts, containing 10, 18 and 30 mol% moO3, acted in a similar way and raised the selectivity to acroline to some extent in coparison with a pure vanadium oxide catalyst, whatever was partial pressure of propylene. In the mixtures containing more than 50 mol% MnO3, MoO3 had a dilution effect on the catalytic activity. A pure molybenum oxide catalyst scarcely oxidized propylene at all 470°C. It has thus been found that the catalytic cativity of this system is closely related with the formation of solid solutions MoO3 in V2O5.
The Acid Strength and the Catalytic Activity of Solid Catalysts in the Oligomerization of Propylene
Authors: Misono Makoto , Yoneda Yukio
Published: July 2006

The reaction activities and the reaction products of the oligomerization of propylene on several acidic solid catalysts, e. g., silica-alumina, sodium-exchanged silica-alumina and some other acidic catalysts, have been investigated in a circulation system in the range of 130–300°C and 100–600 mmHg. The acid strength and the acid contents of catalysts were qualitatively measured by amine titration, using several indicators, over the range from 1.5 to −12.8 in H0 function. Correlations between the reaction activity of the oligomerization of propylene and the acid strength as well as the acid content of the catalysts were demonstrated. The activation energies, the pressure dependency of the rate, and the reaction products were correlated with the acid strength as well. The high activity of some catalysts due to very strong acid sites was deactivated by coke formation in the initial stage of the reaction process. On the basis of an analysis of the reaction products, the major reaction at the stationary stage was ascertained to be the trimerization of propylene, which seemed to occur on moderately strong acid sites. The acid types responsible for the activity were discussed by the aid of “added back water.”
Chloranilate Complexes of Iron(III) and Nickel(II)
Authors: Cabbiness Dale K , Amis Edward S
Published: July 2006

Nickel(II) and iron(III) have been found to complex with chloranilic acid in 1 : 1 and 1 : 2 ratios, respectively. The complexes were studied spectrophotometrically by the method of continuous variations in aqueous solutions at an ionic strength of 0.15 and at different values of pH and temperature. Formation constants and other thermodynamic properties have been determined. It is proposed that these complexes are chelates.