bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Polarographic Investigation on the Reaction between Chromium(II)-ethylenediaminetetraacetate and Nitrate Ions
Authors: Tanaka Nobuyuki , Ito Tasuku 
Published: July 2006

Abstract
The effect of nitrate ions on the polarographic waves of ethylenediaminetetraacetatoaquochromate(III) ions has been studied in acetate buffer solutions and acid potassium chloride solutions. Nitrate ions are chemically reduced in the vicinity of the mercury drop of the electrode by chromium(II)-EDTA complexes which are formed by the electroreduction of chromium (III)-EDTA complexes. The chromium (III)-EDTA complexes thus formed are reduced again at the DME and the intermediate products of nitrate ions are reduced further chemically with chromium (II)-EDTA complexes or electrochemically, resulting in the enhancement of the current. The nature of the limiting current is investigated and compared with that predicted from the theoretical treatment. The reaction between chromium(II)-EDTA and nitrate ions has also been investigated in acetate buffer solutions and its rate constant, 35 1. mol−1 sec−1 at nearly 0°C, μ=0.1, has been compared with 30 l. mol−1 sec−1, the value obtained from the polarographic catalytic current under almost the same condition.
The Autoxidation of α-Methylstyrene in the Presence of Metal Salt
Authors: Niki Etsuo , Kamiya Yoshio 
Published: July 2006

Abstract
The azobisisobutyronitrile-initiated autoxidation of α-methylstyrene in the presence of metal salt was studied from the viewpoints of rate and products. The over-all activation energy was found to be 19.7 kcal./mol. In most cases, metal salts had a retarding effect on the rate of oxidation. With manganese and copper salts, an increase in the concentration of the metal decreased the rate of oxidation monotonously. However, cobalt naphthenate had an accelerating effect within a limited range of concentration, although it also had an inhibiting effect at higher concentrations. The products were acetophenone, formaldehyde, α-methylstyrene oxide and α-methylstyrene polyperoxide. Metal salt had little effect on the products of oxidation, with the exception of cobalt salt, which gave α-methylstyrene oxide in considerable yield even at 760 mmHg of oxygen pressure, where little α-methylstyrene oxide was formed in the presence of other metal salts or in the absence of catalysts.
Reactions of 2-Chlorocycloalkanone Oximes. II. Syntheses of 3-Aminocycloalka[C]isoxazoles
Authors: Ohno Masaji , Naruse Norio 
Published: July 2006

Abstract
The displacement reactions of α-chlorocycloalkanone oximes with sodium cyanide in dimethyl sulfoxide or ethanol have been studied. It has been shown that 3-aminocycloalka[C]-isoxazoles can be obtained in excellent yields. α-Chlorooximes of cyclohexanone, cyclooctanone, cycloocten-5-one, cyclododecanone, and cyclododecadien-5, 9-one have been subjected to the reaction, affording the corresponding isoxazole derivatives in 48, 96, 89, 95, and 90% yields respectively. The application of the method to 3-chloronorcamphor oxime and α-chlorooximes from acyclic olefins afforded cyanooximes; it failed to give isoxazole derivatives. The hydrogenation of 3-aminocycloocta[C] isoxazole gave 2-amino-1-cyclooctanecarbonamide by the hydrogenolysis of the nitrogen-oxygen bond of the isoxazole ring system. The amino-carbonamide was treated with either the base or acid to give 2-oxycyclooctanecarboxylic acid.
Syntheses of Peptides Related to the N-Terminal Structure of Corticotropin. VI. The Synthesis of Ser1- and Gly1-Decapeptides Corresponding to the First Ten-amino-acid Sequence of Corticotropin
Authors: Otsuka Hideo , Inouye Ken , Shinozaki Fusako , Kanayama Makoto 
Published: July 2006

Abstract
t-Butyloxycarbonyl-seryl-(and-glycyl-)tyrosyl-seryl-methionyl-glutamyl-histidyl-phenylalanyl-arginyl-tryptophyl-glycine have been synthesized as the first step of the synthesis of adrenocortico-tropically active peptides. The trifluoroacetic acid treatment of these two compounds afforded the free decapeptides, seryl-tyrosyl-seryl-methionyl-glutamyl-histidyl-phenylalanyl-arginyl-tryptophyl-glycine, which corresponded to the amino-acid sequence of positions 1 to 10 in the corticotropin molecule, and its glycine1-analog. Concerning the synthesis of serine peptides, a tetrapeptide derivative, corresponding to the first four amino acid residues of corticotropin, was obtained by using O-benzyl-serine.
Amino Acid-Carbohydrate Coordinated Compounds. II. The Synthesis and the Stability of 3-O-Aminoacyl-d-glucoses
Authors: Muramatsu Nobutoshi 
Published: July 2006

Abstract
3-O-Aminoacyl-d-glucoses (amino acids; Gly, l-Ala, l-Lys, l-Asp (α and β) and l-Glu (α and γ)) have been prepared by the condensation of 1,2; 5,6-di-O-isopropylidene-d-glucose with suitably protected amino acid derivatives in the presence of N,N′-dicyclohexylcarbodiimide, followed by the removal of the protected groups. The effect of free amino and carboxyl groups on the stability of these compounds has been clarified.
The Sensitive Gas Chromatography of Para-, Orthohydrogen, Hydrogen Deuteride and Deuterium
Authors: Yasumori Iwao , Ohno Seigo 
Published: July 2006

Abstract
A sensitive gas chromatograph of the reduced-pressure type was devised to analyze hydrogen nuclear spin isomers and isotopes, and its characteristics were studied in order to obtain the optimum conditions for analysis. It was shown that the para and ortho composition of 0.01 ml. S. T. P. of normal hydrogen could be determined within an accuracy of 1% by employing an alumina column cooled at −196°C, while the composition of 0.02 ml. S. T. P. of the equilibrated mixture of hydrogen, hydrogen deuteride and deuterium at 25°C could be determined within the same accuracy by employing an alumina column coated with manganese chloride. The alumina column was no longer capable of separating the spin isomers when it was treated above 350°C. Kinetic studies of the hydrogen-deuterium equilibration (21°C) and of the orthohydrogen conversion (−196°C), using the alumina as a catalyst, revealed that this strong activation creates active sites for the equilibration and the magnetic conversion which makes the peak separation obscure. The nature of these active centers was briefly discussed.
The Crystal and Molecular Structure of the Dehydrated Tetramer of 1,2-Dimethyldisilanetetraol, (CH3)8Si8O8
Authors: Higuchi Taiichi , Shimada Akira 
Published: July 2006

Abstract
The crystal and molecular structure of (CH3)8Si8O8 has been determined by means of the Patterson projections and refined by the two-dimensional Fourier technique and the least-squares method. The space group is P4/nnc, with four molecules per unit cell. The unit cell constants are a=11.73±0.02 Å, and c=17.17±0.02 Å. The skeleton of a molecule consists of two “crown-shaped” (–Si–O–)4 rings which are crystallographically independent of each other and are connected by four Si–Si bonds along the c axis. The four six-membered (–Si–Si–O–)2 rings thus formed have boat forms. Hence, a molecule forms a cage-like conformation with an approximate symmetry of 4/mmm. Each molecule in the unit cell is surrounded by four adjacent molecules related with centers of symmetry; these molecules form, in a sense, a layer perpendicular to the c axis.
The Adsorption Equilibria of Dl-Mandelic Acid on Starch in an Aqueous Phase
Authors: Ohara Masaaki , Chen Chau-Yang , Kwan Takao 
Published: July 2006

Abstract
The selective adsorption of d- or l-mandelic acid on starch from an aqueous solution of racemate has been quantitatively investigated. l-Mandelic acid has been judged from the distinct negative value of the optical rotation in the solution to be adsorbed preferentially over the d-isomer. The separation factor for the adsorption of the two enantiomers was 1.06±0.02 at 0°C. From the saturation value estimated by the Langmuir equation for adsorption, the ratio of the glucose residue to the Dl-mandelic acid adsorbed has been calculated as 5, indicating that not all the glucose residues in the starch constitute adsorption sites for mandelic acid.
The Basicities of Tropone and Tropolone
Authors: Hosoya Haruo , Nagakura Saburo 
Published: July 2006

Abstract
The ultraviolet absorption spectra of tropone (I) and tropolone (II) were measured with sulfuric acid solutions of various acidities. The accurate pKa values, as determined by the proposed method, were −1.02 and −0.86 for I and II respectively. The Raman spectra of II were measured with sulfuric acid solutions of various acid concentrations. The bands in the 6 and 15 μ regions change sharply when the solvent acidity changes from 5 to 25%, corresponding well to the ultraviolet absorption change. The infrared absorption spectra of II were measured with the concentrated deuterosulfuric acid solution in the 6 μ region. The vibrationals mode of the protonated tropolone were discussed.
Nuclear Magnetic Resonance Spectra of Polyethylene
Authors: Kato Yoshinori , Nishioka Atsuo 
Published: July 2006

Abstract
A quantitative study of some structural irregularities of polyethylenes by an improved proton magnetic resonance method is reported. The background noise of a nuclear magnetic resonance spectrometer can be remarkably eliminated with the aid of the Mnemotron Computer of Average Transients. The total numbers of methyl groups in polyethylenes were estimated by this method using 5% solutions of the polymer in tetrachloroethylene. Spectra were obtained at about 110°C in order to suppress the thermal degradation of the polymer. The results agree well with those estimated by an infrared compensating method. Information about the species of branches and, in some cases, the number-average molecular weight of the polymer can be obtained by examining the resonance shape of methyl groups. The chemical shift difference between the triplet due to ethyl branches and that due to the other longer branches was found to be less than 0.05 p.p.m. This method can also be applied to the detection of unsaturations in polyethylene. In this case, however, the signal-to-noise ratio has to be increased to a factor of at least 20. Thus, the purification of the solvent is very important in the experiment.
Specific Effects in Acid Catalysis by Polymeric Sulfonic Acids in the Hydrolysis of Some Carboxylic Esters
Authors: Yoshikawa Sadao , Kim Oh-Kil 
Published: July 2006

Abstract
The catalytic effects of polymeric sulfonic acids in ester hydrolysis in aqueous acetone were inferior to that of hydrochloric acid. However, the hydrolysis rate was accelerated by increasing the water content of acetone-water mixtures, and, in a water solution, polymeric sulfonic acids were much more effective catalysts. Furthermore, the catalytic efficiency of polymeric sulfonic acid in ester hydrolysis in water increased with the length of the ester molecule. The polymeric sulfonic acid with a strong hydrophobic character was more effective; 69% sulfonated polystyrene-sulfonic acid, for example, hydrolyzed methyl hydrogen azelate in water over five times more rapidly than hydrochloric acid. The specificity thus obtained suggests that, in the hydrolysis of electrically-neutral esters in water, ester molecules are concentrated in the neighborhood of the polymer by the hydrophobic interaction between catalyst and substrate. Besides, in the hydrolysis of aliphatic esters catalyzed by polyvinylsulfonic acid in 50% aqueous acetone, there was a linear relationship between the reciprocal of the rate constant and the intrinsic viscosity of the polymer, while in the case of polystyrenesulfonic acid hardly such any relationship was found. These remarkably different behaviors of the two kinds of polymer catalysts should be attributed to the difference in the expansion of the polymer chain in solutions.
Organoboron Compounds. X. On the Reaction of o-Hydroxybenzeneboronic Acid Anhydride with Some Sulfonamides
Authors: Kato Seiji , Kimura Keiko , Nagata Katsuhisa , Tsuzuki Yojiro 
Published: July 2006

Abstract
Several new azo compounds containing boron atoms have been synthesized by the use of sulfonamides; these compounds have an excellent effect on bacilli. It was expected that the antibiotic effect would be very remarkable, since it had been reported that boron-containing azo dyes are useful for therapy on brain tumors. A mixed solvent of ethanol-water (1:1) and acetone was found useful for recrystallizing this class of compounds. The infrared spectra of these compounds show absorption bands at the 1090—1100cm−1, 1375—1380 cm−1 and 1600—1610 cm−1 regions these bands may be assigned to the carbon-boron, boron-oxygen and nitrogen-nitrogen bonds respectively.
Perchloro-(dimethylene-1,2-cyclobutanedione) and Its Solvolytic Degradation
Authors: Fujino Akira , Kusuda Kousuke , Sakan Takeo 
Published: July 2006

Abstract
Perchloro-(3,4-dimethylenecyclobutene) has been converted to 1, 3′, 3′, 4′, 4′-pentachloro-2-methoxy-3,4-dimethylenecyclobutene; in some solutions exposed to the air, this then gradually decomposed to perchloro-(dimethylene-1, 2-cyclobutanedione). The further spontaneous degradation of the last compound in an aqueous ethanol solution has also been investigated in order to elucidate the structures of an unstable intermediate (an adduct of ethanol to the carbonyl) and the end product (the hemi-ketal lactone ester). The physical and chemical properties of these compounds have been given and discussed. A possible bicyclic intermediate caused by the interaction between the hydroxyl group and the diagonally-positioned dichloromethylene group in above unstable ethanol adduct has been suggested in the process from the latter compound to the end product.
The Chemistry of Protactinium. II. The Behavior of Pentavalent Protactinium in a Perchloric Acid Solution
Authors: Suzuki Shin , Inoue Yasushi 
Published: July 2006

Abstract
Studies of the chemical behavior of protactinium(V) were carried out with the TTA-benzene extraction method, the ion exchange method and the filtration method. When the protactinium concentration is less than 10−6 m and the perchloric acid concentration is 0.3—2.0 n, the reaction of TTA extraction may proceed as:
PaOm(OH)n5−2m−n+4HT\ightleftarrowsPa(OH)T4+(m+n−1)H2O+(5−2m−n)H+
where 2m+n is 3 and 4, or as:
PaOm(OH)nT4−2m−n+4HT\ightleftarrowsPaT5+(m+n)H2O+(4−2m−n)H+
where 2m+n is 2 and 3.
The cation exchange experiment gives results consistent with this conclusion. On the other hand, when the concentration of protactinium is higher than 10−6 m, the above relation does not hold, even in the 5 n perchloric acid solution, because protactinium forms the aggregates to a great extent. This has been confirmed by the filtration experiment.
Compounds Related to Imido-Substituted Ethylenes. I. The Preparation of Diimido-Substituted Ethylenes
Authors: Tsuge Otohiko , Yanagi Kiyoshi , Fukuhara Sh\={o}ji 
Published: July 2006

Abstract
Methods for the preparation of cis-, trans-1, 2-diphthalimidoethylene, its nitro derivative, 1,1-diphthalimido- and 1, 2-bis(o-sulfobenzimido)ethylene are described. In this connection, the thermal, irradiated and iodine-catalyzed isomerization of cis- and trans-1, 2-diphthalimidoethylene have also been studied in detail.
Specific Effects in Acid Catalysis by Polymeric Sulfonic Acids in the Hydrolysis of the Amino Ester and Related Compounds
Authors: Yoshikawa Sadao , Kim Oh-Kil 
Published: July 2006

Abstract
The amino ester hydrolysis by polymeric sulfonic acids increased as the concentration ratio, Cester/Cacid, was lowered, and a maximum in the plot of the rate constant, k, against the Cester/Cacid ratio was attained near the ratio=0.4 in the case of the β-alanine methyl ester as well as in the case of γ-methyl l-glutamate. At this optimum concentration, the catalytic effect of polyvinylsulfonic acid (A), for example, in the hydrolysis of the β-alanine methyl ester was 16 times greater than that of hydrochloric acid, while the effect of polystyrenesulfonic acid was about 7 times greater. The catalytic effects of hydrochloric acid and ethanesulfonic acid were the same in all cases, and there was no such specific behavior as in the former. Furthermore, the catalytic efficiency of polyvinylsulfonic acid in amino ester hydrolysis increased with an increase in the polymer molecular weight, in contrast with the case of the carboxylic ester, while no such correlation was found in the polystyrenesulfonic acid. Besides, the catalytic effect of partially-neutralized polymeric sulfonic acid, polyvinylsulfonic acid especially, decreased remarkably with the degree of neutralization. These different kinds of behavior can be interpreted as being due to the difference in the expansion in solutions and in the geometrical distances between nearest-neighboring sulfonic acid groups on the polymer chain.
Multiple Charge-transfer Bands of the Pyrene-Tetracyanoethylene Complex
Authors: Kuroda Haruo , Ikemoto Isao , Akamatu Hideo 
Published: July 2006

Abstract
The polarized absorption spectra of the single crystal of the pyrene-tetracyanoethylene complex have been observed by means of a microspectrophotometer. It is shown that two absorption bands, at 12700 cm−1 and 20000 cm−1 respectively, are polarized along the c-axis, the direction connecting the molecular center of the donor and that of the acceptor; hence, both have been assigned to the charge-transfer bands. The interactions of 32 possible charge-transfer states with the no-bond state are discussed in terms of the simple molecular orbital theory, and their contributions to the energy of the complex formation are compared with each other. It is revealed that the interactions of higher charge-transfer states are relatively important and can not be neglected compared with that of the lowest charge-transfer state, and that the appearance of the multiple charge-transfer bands is a natural consequence of such a configurational interaction. It is also suggested that the ratio of the intensities of the first and the second charge-transfer bands may be a parameter that offers information on the orientation of the donor molecule to the acceptor molecule. A probable model is proposed for the structure of the pyrene-tetracyanoethylene complex formed in the solution.
Aminocyclitols. X. A Synthesis of Deoxyinosamine and Deoxyinosadiamine and Their Nuclear Magnetic Resonance Spectra
Authors: Suami Tetsuo , Yabe Kenji 
Published: July 2006

Abstract
(±)-1-Deoxy-muco-inosamine-4, (±)-1-scyllo-inosamine-2 and (±)-2-deoxy-allo-inosadiamine-3, 5 pentaacetates have been synthesized from 1-deoxy-myo-inositol (I). The hydroxyl groups of I are mesylated, and the mesyloxy groups are replaced by azido groups. The reduction of the azido compounds, followed by acetylation, gives the pentaacetyl-deoxyinosamines and deoxyinosadiamine. Their structures have been established by means of a study of the proton magnetic resonance spectra.
The Anionoid Substitution Reaction of Diethyl 2-Acetamido-6-bromoazulene-1, 3-dicarboxylate
Authors: Tada Masao 
Published: July 2006

Abstract
The bromine atom in diethyl 2-acetamido-6-bromoazulene-1, 3-dicarboxylate (I) is as reactive toward the anionoid reagents as in diethyl 6-bromoazulene-1, 3-dicarboxylate. Twentyseven 6-substituted azulene derivatives have been synthesized from I by the nucleophilic substitution reaction. On one of them, diethyl 2-acetamido-6-diethylaminoazulene-1, 3-dicarboxylate, the removal of the 2-acetamido group has been carried out, giving diethyl 6-diethylaminoazulene-1, 3-dicarboxylate.
Benzo-1, 4-thiazino[3,2-b]tropone 5-Oxides and 5, 5-Dioxides
Authors: Nozoe Tetsuo , Asao Toyonobu , Takahashi Kazuko 
Published: July 2006

Abstract
The oxidation of benzo-1, 4-thiazino[3,2-b]tropone and its 8-isopropyl derivative with hydrogen peroxide afforded the corresponding 5-oxides or 5, 5-dioxides. The stability of these oxides to heating, acid and alkali was examined. The bromination or nitration of these oxides gave mainly 9-bromo or 9-nitro derivatives. 7- or 9-Aminobenzo-1, 4-thiazino[3,2-b]tropones were obtained by the reduction of the corresponding nitro compounds.
Studies of Aminosugars. XIII. The Synthesis of Paromamine
Authors: Umezawa Sumio , Koto Shinkiti 
Published: July 2006

Abstract
Paromamine has been synthesized by condensing the N,N′-dinitrophenyl derivative of deoxystreptamine with the N-dinitrophenyl derivative of acetobromoglucosamine in nitromethane in the presence of mercuric salts, and by then removing the protecting groups by treatment with methanolic ammonia and hydrolysis with Dowex 1X2. The synthetic sample was shown to be identical with natural paromamine by a comparison of their infrared spectra and by microbiological assay. The identity was also proved by the determination of the Δ[M]Cu Am values of the tri-N-acetate of the synthetic and natural specimens by the copper-complex methods.
Sigma-Pi Interaction Accompanied by Stereoselection
Authors: Fukui Kenichi , Fujimoto Hiroshi 
Published: July 2006

Abstract
A simple molecular orbital theoretical treatment of the sigma-pi interaction caused by chemical reactions of planar-conjugated systems has been developed. The problem of the streo-selection of the two alternative directions of configuration altering due to the hybridization change at the centers of interaction has been considered by means of a simple perturbation treatment. Two theoretical indices, which represent the conjugation stabilization by way of the sigma-pi and reagent-pi interactions, have been introduced for this purpose. The theoretical results are consistent with the results of experience so far accumulated in various organic reactions, such as additions, eliminations, substitutions, and rearrangements, of conjugated molecules.
Dielectric Relaxation and Molecular Structure. III. Relaxation Times of Aniline Derivatives in Benzene and Dioxane
Authors: Chitoku Kazuo , Higasi Keniti 
Published: July 2006

Abstract
A brief description is made of the experimental methods for measuring microwave dielectric constants and losses of solutions in the frequency range 10–50 Gc./sec. Dielectric data obtained in this experiment were analysed from the viewpoint of molecular interaction between the solute and the solvent molecules. Six benzene derivatives with the amino group, aniline (A), N,N′-di-methylaniline (B), N,N′-diethylaniline (C), 2, 6-dimethylaniline (D), p-nitroaniline (E) and N-methylaniline (F) were chosen as solutes. Benzene and dioxane were used as solvents. The relaxation times of A, D and E obtained in dioxane are about three or five times larger than the corresponding relaxation times in benzene. The relaxation times of B and G in dioxane were about twice or one and half of the corresponding values obtained in benzene. The dielectric behavior of F is intermediate between A and B. These results are attributable to the hydrogen-bond formation between an oxygen atom of the dioxane molecule and an amino-hydrogen atom (F) or atoms (A, D and E).
The Separation of Zirconium and Hafnium by Tributyl Phosphate - Celite Reversed-phase Partition Chromatography
Authors: Ueno Kaoru , Hoshi Michio 
Published: July 2006

Abstract
The distribution ratios, Kd, for zirconium and hafnium were measured in the hydrochloric acid-TBP-celite system, the acid concentration being varied from 5 n to 8 n. The data obtained showed that the separation factor for the above elements, Kdzr⁄KdHf, is fairly high, –4, in the 7–8 n hydrochloric acid range. Thus, the separation of these elements was carried out in 7.1 n hydrochloric acid by the use of a TBP-celite column.
The Mechanism of the Alkaline Fusion of Diphenylsulfone
Authors: Oae Shigeru , Furukawa Naomichi 
Published: July 2006

Abstract
Diphenylsulfone-1-14C was treated with fused potassium hydroxide at 300°C for 7 hr. in a sealed metal tube. The yield of phenol, as determined by the isotope dilution technique, was found to be almost quantitative. The distribution of 14C in the resulting phenol was determined by degradating it by the usual method. Practically all the activity of 14C in the phenol was found at the position 1, which corresponded to the originally-labeled position in the diphenylsulfone-1-14C used. This indicates that the mechanism of the alkaline fusion of diphenylsulfone proceeds thruogh a simple SN2-type mechanism, not the elimination-addition mechanism.