bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Behavior of Polonium Evaporated from Fused Salt
Authors: Kamemoto Yuichiro , Yamagishi Shigeru 
Published: July 2006

Abstract
Studies were made of the evaporation of polonium from a fused potassium chloride - lithium chloride mixture and of the deposition of the evaporated polonium on several metal plates under different temperatures. Approximately 100% of the polonium evaporates, probably as polonium tetrachloride, from the fused salt at the fused salt temperature higher than 500°C when heated for 3 hr. in an argon atmosphere. The evaporated polonium deposited on copper, platinum, palladium and silver plates which were held over the fused salts. The relationship between the percentage of polonium evaporated from these metal plates and the temperature shows that the polonium deposits on these metal plates as elementary polonium or polonide.
Stuides on the Chemical Decomposition of Simple Sugars. XVII. Pyruvic Acid Formation from d-Glucose-6-14C
Authors: Otani Sinichi 
Published: July 2006

Abstract
The formation of pyruvic acid d-glucose-6-14C in a converted potassium acid phosphate buffer solution (40%, pH 6.6), was studied. It was found that the C-6 of the glucose was converted into the methyl carbon of pyruvic acid. In view of the formation of pyruvic acid from d-glucose-1-14C, the C-1 and C-6 of the glucose were converted into the methyl carbon of pyruvic acid. This reaction mechanism was similar to that of the formation of acetol (J. Hayami, This Bulletin, 34, 927 (1961)). The mechanism presented may be summarized as follows: 1) The formation of α-diketose by β-hydroxy-carbonyl elimination after isomerization to 3-ketose or 4-ketose. 2) The formation of acetylfornoil by a second β-hydroxy-carbonil elimination after isomerization to the β-deketose. 3) The hydrolytic cleavage of the acetylformoin.
The Polymerization of Acetonitrile in the Presence of Acidic and Basic Substances
Authors: Oikawa Eizo , Mori Kyoichi , Saito Goro 
Published: July 2006

Abstract
Complexes of saturated nitriles with metal chlorides polymerize readily. In this paper, the polymerization of acetonitrile was carried out with more nitrile, than was needed to form the complex with metal chlorides. The conversion of the polymer increased in comparison with the case of the polymerization of the complex, indicating that the complex would partly dissociated in the reaction. The trimer of acetonitrile, 4-amino-2, 6-dimethylpyrimidine, was isolated, and ammonia was detected in addition to the brown polymer. The mechanism of the trimer formation in the presence of metal chlorides was illustrated through the removal of a proton from acetonitrile with the help of the chlorides, and through dimer formation. Hydrochloric acid and metaphosphoric acid were less active than metal chlorides. Ammonia itself was found to be inactive for the trimerization, bringing only acetamide. Water was also inactive in response to acetonitrile in the absence of acidic or basic substances. The derivation of ammonia was attributed to the decomposition of the pyrimidine compound and/or to the degradation of the polymer, but not to the hydrolysis of acetamide. The reaction of the polymer with propionaldehyde, the hydrolysis of the product, the carbylamine test, and a treatment of the trimer similar to that used for the complex suggested that the pyrimidine rings are involved in the polymer structure.
The Vicinal Orientation. I. The Pivaloylation of Polymethylbenzenes
Authors: Suzuki Hitomi , Wada Hisayuki , Maruyama Kazuhiro , Goto Ryozo 
Published: July 2006

Abstract
The direct introduction of a pivaloyl group by Friedel-Crafts acylation has been carried out with the following polymethylbenzenes: o-xylene, m-xylene, hemimellitene, pseudocumene, mesitylene, prehnitene and durene. The decarbonylation was not very significant, and seven new polymethylpivalophenones were prepared in fairly high yields. The hydrocarbon mixtures obtained simultaneously in these reactions usually consisted of at least four or five substances. In the pivaloylation of durene, the Jacobsen-type migration (vicinal orientation) of a methyl group was observed.
The Alkaline Sulfide Reduction of Aromatic Nitro Compounds. VIII. The Correlation between Sodium Monosulfide and Hydrosulfide in the Reduction of Sodium m-Nitrobenzene Sulfonate
Authors: Hashimoto Shizunobu , Sunamoto Junzo 
Published: July 2006

Abstract
In order to examine the correlation between sodium hydrosulfide and sodium monosulfide, the reduction of sodium m-nitrobenzene sulfonate by these aqueous sulfides has been studied kinetically. The rates of the hydrosulfide reduction and the main reaction of the monosulfide reduction were found to be proportional to the concentration of the nitro compound and the square of the concentration of the reducing agent. In the hydrosulfide reduction, the hydroxide ion concentration has a negative effect on the initial state and a positive effect on the final state. The polarographic study on the hydrosulfide reduction confirmed the presence of disulfide ions. From the available data, the correlation among the alkaline sulfides in the reduction was discussed.
The Mechanism of the Alkaline Fusion of Benzenesulfonic Acid.
Authors: Oae Shigeru , Furukawa Naomichi , Kise Masahiro , Kawanishi Mitsuyoshi 
Published: July 2006

Abstract
Benzenesulfonic acid-1-14C was fused with potassium hydroxide at 320—350°C for five minutes. The phenol obtained was then degraded as usual, and the distribution of carbon-14 in the phenol was determined. Practically all the 14C activity was found at the 1 position of the phenol, which means that there is no migration of the 14C originally labeled at the position 1 or the benzenesulfonic acid. Benzenesulfonic acid was also treated with potassium hydroxide enriched with 18O. The resulting phenol was found to be incorporated, with the same concentration of 18O as that of the 18O enriched water used. The results show that the mechanism of the reaction is of a simple SN2 type and not of the elimination-addition type involving the benzyne intermediate, while there was no oxygen migration in the reaction.
Studies of Aminosugars. XII. The Absolute Structure of Kanamycin as Determined by a Copper Complex Method
Authors: Umezawa Sumio , Tatsuta Kuniaki , Tsuchiya Tsutomu 
Published: July 2006

Abstract
N,N′-Dimethyl-di-O-methyldeoxystreptamine has been prepared from kanamycin through the hydrolysis of the totally-methylated product of O-(3-acetamido-3-deoxy-α-d-glucopyranosyl)-N,N′-diacetyldeoxystreptamine. On the other hand, N,N′-dimethyl-4,5,6-tri-O-methyldeoxy-streptamine has been prepared by hydrolysis of the totally-methylated product of N,N′-diacetyl-deoxystreptamine. The shifts in molecular rotations of the both products have then been determined, with solutions of tetramminecopper(II) sulfate, ammoniacal cuprous chloride and Cupra B being substituted for water as the solvent. By the application of the generalizations described in the foregoing paper, it has been found that the former product includes a pair of adjacent methylamino and hydroxyl groups and that the projected angle between them is about +60°. These findings led to the conclusion that the free hydroxyl group in the former product is attached to the C-6 of deoxystreptamine, indicating that, in kanamycin, 6-amino-6-deoxy-α-d-glucosyl and 3-amino-3-deoxy-α-d-glucosyl moieties are attached to the C-4 and C-6 of deoxystreptamine respectively.
Studies of the Mixed Amino-acid Complexes of Cobalt(III). I. The Geometrical Isomers of the [Co en gly (chelate)] Series
Authors: Matsuoka Nobuko , Hidaka Jinsai , Shimura Yoichi 
Published: July 2006

Abstract
Five new complexes of the [Co en gly (chelate)] type, i. e., mer(N)- and fac(N)-[Co en gly CO3], mer(N)- and fac(N)-[Co en gly ox] and mer(N)-[Co en gly malo], have been derived from a new dinitro complex, cis-[Co en gly (NO2)2], through an intermediate complex, [Co en gly Cl (OH2)]Cl. The geometrical structures of these complexes have been determined on the basis of the processes of their derivation and their absorption spectra. Two new bisglycinato complexes, trans(O)- and cis(O)-[Co en gly2]I·H2O, have been prepared from mer(N)- and fac(N)-[Co en gly CO3] respectively.
Organic Sulfur Compounds. V. Reactions of Arylsulfonic Acids with Alkyl and Aryl Chlorosulfites
Authors: Yamamoto Asami , Kobayashi Michio 
Published: July 2006

Abstract
Silver p-toluenesulfonate has been found to react with alkyl and aryl chlorosulfite to give p-toluenesulfonic esters. Mixed anhydrides of the sulfonic acid and monoalkyl or monoaryl sulfite were postulated as the intermediates. No rearrangement of the alkyl group was observed during the reaction. The reaction mechanism was studied by means of the 18O tracer technique.
The Preparation of 2-Alkoxy-1,3,2-oxazaphospholidines and Some Reactions
Authors: Mukaiyama Teruaki , Kodaira Yasuto 
Published: July 2006

Abstract
The preparation of 2-alkoxy-1,3,2-oxazaphospholidines and some reactions will be described. 2-Alkoxy-1,3,2-oxazaphospholidines were prepared either from ethyl phosphorodichloridite and aminoethanols or, more conveniently, from tris[diethylamino]phosphite, aminoethanols and alcohols. 2-Alkoxy-1,3,2-oxazaphospholidines reacted easily with alcohols or p-toluenesulfonic acid monohydrate to give dialkyl aminoethyl phosphites or alkyl aminoethyl phosphite by the ring-opening at the P–N linkage of the phospholidines. It was oxidized by means of sulfur or nitrogen tetroxide to give 2-thione or 2-one in high yields. Further, it was found that it reacted with ethyl isocyanate to form 1 : 1 adducts. The structure of the adducts was confirmed, by a study of its chemical transformations, to be a seven-membered cyclic compound. It also reacted with carbon dioxide at about 120°C to yield the phosphorous-containing polyamide.
The Synthesis and Reactions of 2-Chloro-5-hydroxytropone
Authors: Nozoe Tetsuo , Asao Toyonobu , Takahashi Eijiro , Takahashi Kazuko 
Published: July 2006

Abstract
The acid hydrolysis of some polyhalotropones and some reactions of the products were investigated. The treatment of 2,5-dichlorotropone with hydrochloric or sulfuric acid afforded 2-chloro-5-hydroxytropone (I) and a small amount of 5-chlorotropolone. The compound I gives only one kind of the methyl ether and one kind of the acetyl or benzoyl derivative. From the methyl ether, 5-amino- and 5-methylamino-2-chlorotropone were derived. The methoxyl and the amino groups of these compounds are reactive to alkaline hydrolysis, giving I without any of the skeletal rearrangement usually observed in the alkaline treatment of similar 2-halotropones. The hydrolysis of 2,4,7-tribromotropone with hydrochloric acid gave 3,6-dichlorotropolone and 7-chloro-4-hydroxytropolone.
A Comparison of Equations for Powder Compression
Authors: Kawakita Kimio , Tsutsumi Yuhbun 
Published: July 2006

Abstract
Several equations representing the relation between the pressure and the apparent volume of a powdered mass under compression, as proposed by various authors, sometimes have essentially the same form as one other, and sometimes have contradictory characters. Various equations can be modified so as to be a function of the porosity and thus compared with each other. As a result, they can be classified into two types by means of the gradient of the porosity with the pressure (−dn⁄dP, n=porosity). One is −dn⁄dP=knx (Athy: x=1, Kawakita: x=2), and the other is −dn⁄dP=k(1−n)y⁄Pz (Smith: y=0, z=2⁄3, Nutting: y=1, z\doteqdot1, Balshin: y=2, z∼1, Terzaghi: y=2, z∼1, Jones: y=3, z=1), where k is a constant and x,y and z are parameters. In Kawakita’s equation the rate of the decrease of the porosity is considerably larger in an early period of compaction than in Athy’s equation. The second type of equation indicates that a major part of the porosity disappears at lower pressures.
Photoemission from Polycyclic Aromatic Crystals in the Vacuum Ultraviolet Region
Authors: Harada Yoshiya , Inokuchi Hiroo 
Published: July 2006

Abstract
The external photoelectric effect of thin films of tetracene, pentacene, violanthrene, quater-rylene and tetrathiotetracene was studied in the vacuum ultraviolet region. The contact potential differences between the emitters, organic crystals, and the collector (Aquadaq) were determined from the saturation points of the current-voltage characteristics. It was observed that the quantum yields of photoemission increase markedly with an increase in the photon energy, reaching the order of 10−2 electrons/quantum at hv=10 eV. The threshold energies were lower by 1–2 eV. than the molecular ionization potentials. An energy diagram for the external photoelectric process of organic molecular crystals was introduced on the basis of the intrinsic band model. With the aid of this diagram, the band gap energies, Δε, were obtained from the observed values of photoemission. The values of Δε thus obtained were in fairly good agreement with those based on the results of the temperature dependence of semiconduction.
The Photochemical Reactions of Ethylene Glycol and Its Ethers in the Presence of Ferric Chloride
Authors: Inoue Hiroo , Tamaki Kentaro , Komakine Nobuyuki , Imoto Eiji 
Published: July 2006

Abstract
The photochemical reactions of ethylene glycol, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether with ferric chloride have been carried out under a nitrogen atmosphere and with irradiation by ultraviolet light. These reactions have involved the cleavage of the carbon-carbon bond to give formaldehyde and chloromethyl methyl ether; of the carbon (–CH2–)-oxygen bond to give acetaldehyde, methanol and water, or of the carbon (CH3–) -oxygen and hydrogen-oxygen bonds to give methane, ethane, hydrogen chloride and methyl chloride. Furthermore, they have been accompanied by the photo-reduction of ferric chloride to ferrous chloride. From these results, it has been assumed that ferric chloride acts as an oxidizing reagent and Lewis acid in the photochemical reactions.
The Solvent Extraction of Europium Ions with Benzoyltrifluoroacetone. The Synergistic Effect of Oxygen- and Nitrogen-containing Solvents
Authors: Shigematsu Tsunenobu , Tabushi Masayuki , Matsui Masakazu , Honjyo Takaharu 
Published: July 2006

Abstract
The Synergistic effect of many kinds of oxygen- and nitrogen-containing solvents on the extraction of europium ions with benzoyltrifluoroacetone in n hexane has been studied. The addition of alcohols, esters, ketones amines and heterocyclic compounds enhances the extraction, and in general, the solvents with longer carbon chain, especially alcohols and amines, have the larger synergistic effects. At a constant benzoyltrifluoroacetone concentration, the logarithm of the distribution coefficients is linear with pH. The slope of the log D vs. pH plot is about 1.5 in the extraction with 0.05 m benzoyltrifluoroacetone in n hexane, but it is 2 in the presence of 0.04m oxygencontaining compound and 3 in the presence of 0.04 m nitrogen-containing compound. It may be considered that europium benzoyltrifluoroacetonate forms some adducts with these oxygen-or nitrogen-containing lewis bases, and that the coordination of nitrogen-containing lewis bases to the chelates is stronger than that of oxygen containing ones.Since the solvent extraction of neodymium and lutetium ions with β-diketones is performed as well as that of europium ions, it seems to be a favorable procedure for the extraction of rare earth ions with β-diketones to utilize the adduct formation between β-diketonates and active oxygen- or nitrogen -containing Lewis bases.
The Catalytic Hydrogen Exchange of Aniline on Supported Metal Catalysts
Authors: Hagiwara Hiroshi , Echigoya Etsuro 
Published: July 2006

Abstract
The hydrogen exchange reaction of aniline with deuterium was investigated on supported nickel, cobalt and platinum. The following results were obtained: 1) At 150°C, the hydrogen of the amino group of aniline exchanges at a higher velocity than the hydrogen attached to the benzene ring. At temperatures as high as 300°C, the hydrogen exchange in the benzene ring increases further. 2) The suggested hydrogenation mechanism obtained from the results of the exchange reaction can not be correlated with that obtained from the kinetic study. 3) The catalytic activity for the exchange reaction in the benzene ring is in the order Pt&gt;Co&gt;Ni. 4) The basic oxide support seems to suppress the adsorption of the amino group. 5) The relationship between the adsorption state of the aniline on the catalyst surface and the various reaction products, such as cyclohexylamine, benzene and dicyclohexylamine, has been well established.
Rearrangement. IV. Pyrolysis and Acetolysis of Some Sulfonic Esters
Authors: Kotani Ryotaro 
Published: July 2006

Abstract
The pyrolysis of cyclohexanemethyl methanesulfonate and 1-methylcyclohexanemethyl p-toluenesulfonate has been investigated, yielding predominantly rearranged cycloalkenes, with lesser amounts of cycloalkanes. The experiments support the suggestion that the pyrolysis may proceed, at least in part, through a free radical process. The methanesulfonic ester, on acetolysis in a 50% aqueous acetic acid solution, gave rearranged-unrearranged cycloalkenes and alcohols, and an unrearranged acetate, whereas the p-toluenesulfonic ester gave exclusively rearranged cycloalkenes, alcohols and acetates.
The Interaction between a Polysoap and a Monosoap
Authors: Tokiwa Fumikatsu 
Published: July 2006

Abstract
The way in which a cationic polysoap, prepared by quaternizing the nitrogen of poly-2-vinylpyridine with n-dodecyl bromide, interacts with additives, such as a cationic monosoap (n-dodecyl-α-picolinium bromide), a non-ionic surfactant (polyoxyethylene dodecyl ether) and potassium bromide, has been studied in aqueous solutions in terms of the viscosity and solubilizing power for oil-soluble dyes of the mixed solutions of the polysoap and the additives. An experiment on the effects of these additives on the behavior of a polyelectrolyte (poly-2-vinyl-N-ethylpyridinium bromide), prepared from the same parent polymer as the polysoap, has also been included for the purpose of comparison. The hydrophobic hydrocarbon chains in the polysoap and additive molecules play an important role in the interaction of the polysoap with the additives. Co-micellization or mixed micellization occurs between the polysoap and the monosoap or the non-ionic surfactant in aqueous solutions.
The Reaction Rate of the Alkaline Hydrolysis of Ethyl Acetate
Authors: Tsujikawa Hiroo , Inoue Hakuai 
Published: July 2006

Abstract
The reaction rate of the alkaline hydrolysis of ethyl acetate was studied by means of a continuous measurement of the electric conductivity change. The second-order rate constant decreased as the reaction proceeded. The decrease was evident when the initial concentrations of the ester and the base were close together. The initial rate constant at 25°C was measured as 0.1120 1./mol./sec. and the activation energy was 11.56 kcal./mol., values agreed well with those of previous studies. From the standpoint of the electronic theory of organic chemistry, Day and Ingold proposed a sequential reaction mechanism passing through an addition complex. The results of the approximate calculations to the pseudo-first-order reaction and the analog-computation of the exact models coincided with the experimental results. The difference in the activation energies of the forward and reverse reaction rates was calculated from the experimental data. At lower temperatures this reverse reaction rate was small, and the overall reaction rate was approximated as a pure second-order reaction. Other probable reasons for the rate constant decrease were also discussed.
The Variation in Carbon-Halogen Bond Length with the Environment
Authors: Rajput Arjun Singh , Chandra Suresh 
Published: July 2006

Abstract
The data on carbon-halogen bond lengths which have been obtained in recent years are summarized. It has been found that the interatomic distances corresponding to carbon-halogen bonds show a linear dependence on the number of adjacent atoms or bonds. Simple equations for these bond lengths are given to make it possible to estimate different carbon-halogen bond lengths empirically. It has been shown that this variation can be adequately explained on the basis of the hybridization effect. New values for the radii of the hybrid orbitals of carbon have been assigned and used to calculate the bond lengths in a variety of compounds. The agreement between calculated and experimental values is good.
Molecular Vibrations and Structures of Polyalkyl Polysulfides. I. Polymethylene Disulfide
Authors: Hayashi Michiro , Shiro Yuji , Murata Hiromu 
Published: July 2006

Abstract
The polarized infrared spectra of oriented sheets of polymethylene disulfide were measured in the 4000—200 cm−1 region, and the fiber period was found to be 4.18 Å by X-ray diffraction. It was found that this polymer does not have the expected twofold symmetry axes intersecting the helical axis at right angles. The infrared active normal vibrations of two likely structural models were calculated by the use of a modified Urey-Bradley force field. The structure of polymethylene disulfide was concluded to be the GG′G conformation along the sequence of the –S–CH2–S–S– bonds of the 21 helical model.
The π-Electronic Excitation Energies of Anthraquinone
Authors: Kuboyama Akira , Wada K\={o}ichi 
Published: July 2006

Abstract
Following our previous work on o-benzoquinone, the calculation of the π-electronic excitation energies of anthraquinone has been carried out with the Pariser-Parr-Pople method. The calculated excitation energies which correspond to the five distinct π→π* bands have been obtained, though the agreement of the calculated excitation energies and the transition dipole-strengths with the observed energies and strengths are unsatisfactory. The π-electronic charge distribution in carbonyl groups of anthraquinone is almost the same as that of p-benzoquinone.
The Synthesis of 2-Alkyl-8-hydroxyquinolines and Their Chelating Behavior with Metal Ions
Authors: Kaneko Hisamitsu , Ueno Keihei 
Published: July 2006

Abstract
2-Ethyl-, 2-n-propyl- and 2-n-butyl-8-hydroxyquinolines have been synthesized by the reactions of 8-hydroxyquinoline with alkyl-lithium. The dissociation constants and the chelate stability constants of these ligands with copper(II), zinc(II), nickel(II) and cadmium(II) have been measured in 50% v/v aqueous dioxane at 25.0±0.1°C with no additional electrolyte. Factors affecting the acid dissociation constants and the chelate stability constants will be discussed in this paper.
The Reaction of Butadiene with Ethylene. I. A New Synthesis of 3-Methyl-1,4-pentadiene
Authors: Iwamoto Masao , Yuguchi Sadao 
Published: July 2006

Abstract
3-Methyl-1,4-pentadiene, 1,4-hexadiene, and 1,3-hexadiene were obtained, in the weight ratio of 2:1:2, by the use of a ternary catalyst consisting of a combination of ferric chloride and triethylaluminum, with triphenylphosphine as the third component. The products were identified by means of gas chromatography, infrared spectroscopy, mass spectroscopy, NMR, and hydrogenation. The effects of the catalyst compositions and the reaction conditions on the yield and the product composition were also studied. In order to obtain the C6-dienes in the weight ratio described above, the following conditions are desirable; temperature 20—30°C, P/Fe mole ratio 1—2, Al/Fe mole ratio 3—5, and a high ethylene pressure. Although the use of several phosphorus compounds as the third component in the catalyst instead of triphenyl phosphine was investigated, these compounds were ineffective in the selective formation of C6-dienes. It was suggested that the compound which serves as the third component in the catalyst plays an important role.