bluuebunny/crossref_metadata_2025 huggingface dataset:
A Shock-Tube Study of the Acetylene-Oxygen Reaction
Authors: Takeyama Tetsu , Miyama Hajime
Published: July 2006

Acetylene-oxygen reaction in shock waves has been studied over the range of conditions 820°≤T≤1630°K, 1.8≤P≤5.6atm., 8.4×10−4≤[O2]≤4.1×10−3mol./l. and 0.4≤[C2H2]/[O2]≤1.5. Visible emission, OH absorption, and pressure have been measured simultaneously at the same location in the tube. The induction periods obtained from these measurements have been found to be identical with each other and to be dependent upon the oxygen concentration. It has also been found that the activation energy derived from the log(τ[O2]) vs. 1/T plot is equal to 19.0±0.6 kcal./mol. Thus, the reaction H+O2→OH+O is considered to be rate-determining during the induction period, as in the hydrogen-oxygen reaction.

The visible emission has been found to have a sharp peak at about 4320Å and has been attributed to the 2Δ–2π transition of CH radicals.
Polyesters Containing Carbazole Rings in the Main Chain. I. Syntheses of Diacylcarbazoles and Carbazoledicarboxylic Acids
Authors: Nagai Yoshio , Huang Chin-Chuan
Published: July 2006

Acetylation of carbazole with acetyl halide or acetic anhydride gave both monoacetyl and diacetylcarbazoles. Several carbazoledicarboxylic acids were prepared in quantative yields by oxidizing the corresponding diacetylcarbazoles.
The Alkaline Sulfide Reduction of Aromatic Nitro Compounds. VII. The Induction Period of the Sodium Monosulfide Reduction of Sodium m-Nitrobenzene Sulfonate
Authors: Hashimoto Shizunobu , Sunamoto Junzo
Published: July 2006

In the sodium monosulfide reduction of sodium m-nitrobenzene sulfonate, an induction period appears. The present investigation was undertaken in order to determine the causes of this induction period. The induction period is due not to the nitro compound, but to the reducing agent. The induction period is shortened by means of irradiation by ultraviolet light, the addition of potassium persulfate, ferric chloride, and α,α′-azobisisobutyronitrile, or under atmospheric conditions. On the other hand, the addition of phenol or alcohol lengthens the induction period. Further, on the basis of polarographic and spectroscopic studies of the induction period, it has been suggested that soduim disulfide is produced during this induction period. On the basis of these data, it seems reasonable to assume that, in the reduction of aromatic nitro compounds by sodium monosulfide, the reducing power of monosulfide is very small in itself, and that the nitro group is reduced by the disulfide produced by the radical oxidation of monosulfide. The formation of the sulfide ion radical and its dimerization appear to be responsible for the induction period of this reaction.
The Amperometric Determination of Thallium(III) and Silver(I) with Ascorbic Acid Using Two Polarized Indicator Electrodes
Authors: Singh D , Bhatnagar Uma
Published: July 2006

Amperometric determinations of thallium(III) and silver(I) with ascorbic acid have been carried out with two polarized electrodes at 100 mV. and 50 mV. respectively. A simple method for the successive determination of thallium(III) and silver(I) has been developed. At an acidity of 0.1 to 1.0 n with respect to sulphuric acid, only thallium(III) is reduced; silver(I) remains unaffected. After the completion of the reaction with thallium(III), the pH of the solution is adjusted to 6.5 to 7.0 and the silver(I) is titrated with ascorbic acid.
The Behavior of Polonium Evaporated from Fused Salt
Authors: Kamemoto Yuichiro , Yamagishi Shigeru
Published: July 2006

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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>Co>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

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

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

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

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

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

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

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

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.
Vibrational Analysis of Substituted and Perturbed Molecules. III.Green’s Function Determination of Force Constants for XY3 Planar Molecules
Authors: Wolfram Thomas , Bass C D , DeWames Roger E , Lynds L
Published: July 2006

Using the Green’s function formulae for isotopic frequencies of the XY3 molecule together with the spectral theorem, explicit formulae for the molecular force constants directly in terms of the vibrational frequencies have been obtained. The relationship between the Wilson force constants and the cartesian force constants is discussed and leads to the above formulae. The procedure is applied to the BCl3 and BBr3 molecules and force constants are obtained. A simple procedure for calculating the variations in the force constants with variations in vibrational frequencies is suggested.
The Diffusion of Gases at High Pressures. I. The Self-diffusion Coefficient of Carbon Dioxide
Authors: Takahashi Shinji , Iwasaki Hiroji
Published: July 2006

The self-diffusion coefficients of carbon dioxide were measured over a pressure range from 2 to 250 atm. at 25, 50, and 75°C. The measurements of self-diffusion through a plug of porous bronze were made using the radioactive tracer technique. The products of the density and the diffusion coefficient increase slightly with the density in the region of lower density, below about 10 mol./l., for both isotherms at 50 and 75°C, but they decrease in the region of higher density. These results agree with the results obtained by O’Hern et al., but not with Enskog’s dense gas theory, and not with the values calculated by the generalized chart of Slattery et al.
The Fluorination of Ethylene and Ethane
Authors: Nagase Shunji , Tanaka Kiyoshi , Baba Hajime , Abe Takashi
Published: July 2006

Ethylene and ethane were electrochemically fluorinated in an electrolytic fluorination cell equipped with a bubbler. Several fluorinated ethanes were obtained from these samples in reasonable total-yields with reasonable current efficiencies. The influence of operating conditions on the reaction was investigated. A probable mechanism was described for the formation of the characteristic procucts obtained in the fluorination reaction.
The Crystal and Molecular Structure of 8, 8-Dicyanoheptafulvene
Authors: Shimanouchi Hirotaka , Ashida Tamaichi , Sasada Yoshio , Kakudo Masao , Murata Ichiro , Kitahara Yoshio
Published: July 2006

Crystals of 8, 8-dicyanoheptafulvene, C10H6N2, are monoclinic, with two molecules in a unit cell with the dimensions a=7.84, b=13.14, c=3.99 Å, and β=97.9°; the space group is P21⁄m. The intensities were recorded on multiple-film equi-inclination Weissenberg photographs and measured visually against a standard scale. A trial structure was constructed from the Patterson projections, P(u, v) and P(u, w), and a Harker section, P(u, 1/2, w). The atomic coordinates and anisotropic temperature factors were refined by the least-squares method. The final R factor for (hkl) reflections is 0.107. A considerable bond alternation in the conjugated seven-membered ring has been observed. The average long and short bond lengths in the ring are 1.44 and 1.34 Å respectively. The shortest C=C bond measures 1.31 Å, which is shorter than that in ethylene. The exocyclic C=C bond length is 1.42 Å, suggesting a considerable dipolar resonance structure, one which may be responsible for the stability of the compound. The C≡N bond length is 1.13 Å. The molecule deviates slightly from being planar; it lies nearly parallel to the (101) plane. All the intermolecular separations correspond to normal van der Waals interactions; the perpendicular distance between the molecular planes is 3.4Å. The thermal motion was interpreted in terms of rigid body vibrations, and the bond lengths and angles were corrected for the rotational oscillations.
Properties of Dilute Solutions of Polyurethanes. I. Linear Polymers
Authors: Sato Hiroshi
Published: July 2006

Polyurethanes were prepared from polycaprolactone, 4, 4′-diphenylmethane diisocyanate, and ethylene diamine. Two kinds of polymers were used for the present experiments. One contained polycaprolactone with the number-average molecular weight, \barMn, of 1.30×103, while the other contained polycaprolactone with an \barMn value of 2.80×103. Each polymer was fractionated from a dimethyl acetamide solution by progressive precipitation with a mixture of n-heptane and ethyl ether, and the fractions were characterized in terms of viscosity and sedimentation. The relations between the intrinsic viscosity and the molecular weight were found in DMF at 25°C to be:

[η]=5.52×10−4M0.66

for the polymer containing polycaprolactone (\barMn=1.30×103) and

[η]=7.71×10−4M0.62

for the polymer containing polycaprolactone (\barMn=2.80×103). The viscosities of the solutions of the polymers were measured in several solvents at different temperatures, and the polymer-solvent interaction parameters were obtained by using the Fixman theory for the expansion factor. The molecular-weight distribution of the polymer containing polycaprolactone (\barMn=1.30×103) was obtained from the distribution of the sedimentation coefficient, while the value of \barMw⁄\barMn was calculated from the distribution curve to be 1.95.
The Crystal Structures of l-Tryptophan Hydrochloride and Hydrobromide
Authors: Takigawa Takaji , Ashida Tamaichi , Sasada Yoshio , Kakudo Masao
Published: July 2006

The hydrochloride and hydrobromide of l-tryptophan crystallize in the monoclinic space group P21. The cell dimensions of the hydrochloride are: a=7.45, b=5.30, c=14.67 Å, β=98.80°, and those of the hydrobromide are: a=7.64, b=5.41, c=14.58 Å, β=100.47°. There are two molecules in the unit cell. The two compounds are isomorphous. The crystal structure of the hydrobromide was first determined by the heavy atom method with two-dimensional data, and then that of the hydrochloride was refined by three-dimensional least-squares procedure. The molecular and crystal structure is mainly discussed for the hydrochloride here. The average of six C–C bond lengths in the benzene ring is 1.396 Å, that of C–N bond lengths in the indole ring is 1.384 Å. In the carboxyl group, one C–O bond length, 1.147 Å and two O–C–C angles, 106.8° and 125.7° are significantly different from those reported for amino and carboxyl acids so far investigated. The molecule consists of two planes of the carboxyl group and of the indole ring, the planes making an angle of 70.6° with each other. As to the conformation about the C(α)–C(β) bond, C(γ) lies at the gauche position with both of the carboxyl and the amino groups. The molecules are arranged in double layers parallel to the ab plane; the polar layer is held together by a network of the three N–H··· Cl− hydrogen bonds, 3.17, 3.19 and 3.24 Å and one O–H···C1−, 3.04 Å, and in the non-polar layer, the indole rings are packed mainly by van der Waals forces, the shortest C···C and C···N contacts being 3.74 and 3.42 Å respectively.
The Oligomerization of Isoprene by Cobalt or Iron Complex Catalysts
Authors: Misono Akira , Uchida Yasuzo , Hidai Masanobu , Ohsawa Yoshiro
Published: July 2006

The reaction of isoprene by the catalyst systems composed of cobalt(III) or iron(III) ace-tylacetonate, an electron donor, and triethylaluminum was studied. It was found that isoprene is selectively dimerized to form a mixture of 1,5- and 2,5-dimethyl-1,5-cyclooctadiene by the catalyst prepared by the reaction of iron(III) acetylacetonate, 2,2′-dipyridyl, and triethylaluminum. The intermediate complex of the reaction was then examined by studying the effects of the molar ratio of the catalyst components on the reaction or by the measurement of the electronic absorption spectra of the reaction solution. The reaction of butadiene with the catalyst systems described above was also carried out and compared with that of isoprene.
Copolymerization of Vinyl Chloride and Ethylene Initiated by Trialkylboron-Peroxide Catalyst Systems
Authors: Misono Akira , Uchida Yasuzo , Yamada Kunikazu
Published: July 2006

Low-pressure copolymerization was carried out in a water-methanol mixture (1 : 1 by weight) at 0°C. It was found that, when hydroperoxides were used as cocatalysts, triethylboron and tri-rc-butylboron were active as catalysts, while triphenylboron was inactive. As cocatalysts,, hydroperoxides were more active than disubstituted peroxides. The highest catalytic activity was observed when the cocatalyst/catalyst molar ratio was 0.4. The initiating radical has been suggested to be the hydroxy radical, and the initiating mechanism has been discussed briefly. The yield and the reduced specific viscosity of the copolymer decrease rapidly with an increase in the ethylene content of the monomer mixture. The monomer reactivity ratios were: r1(vinyl chloride) = 4.16 and r2(ethylene) = 0.05. This indicates that the copolymerization reaction proceeds via a normal radical mechanism. The resulting copolymer shows characteristic absorption peaks at 750 cm−1 in the infrared spectrum and at 8.37 τ in the NMR spectrum.
The Chlorine Quadrupole Resonances of Ethane Derivatives
Authors: Kondo Seiichi
Published: July 2006

The temperature broadening of the chlorine quadrupole resonance line-width was studied in three ethane derivatives (1, 1, 1-trichloroethane, hexachloroethane and 1, 1, 1, 2-tetrachloro-2, 2-dimethylethane) below the plastic crystalline phases. Most of the resonance frequencies observed at the temperature of liquid nitrogen were equal to those reported in the literature. The energies of activation (2.2, 2.6 and 4 kcal./mol. respectively for the three compounds mentioned above) were obtained from the line-width versus temperature curves in the low temperature phases. It was suggested, considering the smallness of the energies of activation, that the vibrational rotation of the molecule as a whole rather than the internal axial rotation may exist in those phases.
The Catalytic Hydrolysis of Oligophosphates by Ethylenediamine-Copper(II) and Poly-l-lysine - Copper(II) Complexes
Authors: Moriguchi Yoshiki
Published: July 2006

The hydrolysis of some oligophosphates (tetra-, penta- and hexaphosphates) has been studied at 45°C in the absence and in the presence of a metal complex, and the relation between the nature of the complex catalyst and the composition of the degradation products has been investigated on oligophosphates as substrates, especially on pentaphosphate. In the presence of the Cu(II)-en (1:1) complex, the intermediate chain of pentaphosphate is attacked to produce trimeta- and pyrophosphates as the main products; the hydrolytic reaction is apparently of a first-order kinetics which depends on the concentration of the catalyst. The Cu(II) - Poly-Lys complex shows a strong catalytic activity and attacks pentaphosphate exclusively, thus producing orthophosphate as the main product. The optimum conditions for the catalytic effect on the hydrolysis of pentaphosphate are as follows: 1) the ratio of the NH2 repeat unit of Poly-Lys to a mole of pentaphosphate ([-NH2]i/[P5]i) is about 1.6 at pH 8, the concentration of Cu(II) being constant; 2) the molar ratio of Cu(II) to the NH2 repeat unit of Poly-Lys ([Cu]i/[-NH2]i) is 1.0: 3) the activity reaches a maximum at about pH 10. Attempts have been made to explain these results on the basis of the structure of the Cu(II) - Poly-Lys complex.
Studies of Scandium in Various Solutions. III. The Solvent Extraction and Complex Formation of Scandium(III) with Acetylacetone and Thenoyltrifluoroacetone
Authors: Sekine Tatsuya , Koizumi Akira , Sakairi Mitsuo
Published: July 2006

The distribution of scandium(III) at a tracer concentration was determined between chloroform with acetylacetone or thenoyltrifluoroacetone and 0.1 m aqueous perchlorate solutions at 25°C. The change in the distribution ratio of the metal ion with the change in the chelating acid concentration or with the change in the hydrogen-ion concentration was explained in terms of the extraction of the tris chelate complexes into the organic phase and the formation of the primary complexes in the aqueous phases. The equilibrium constants in these systems were determined graphically, by a curve-fitting method to be as follows:

Kex=[ScA3]org[H+]3⁄[Sc3+][HA]3org

K 1=[ScA2+]⁄[Sc3+][A−]

(Remark: Graphics omitted.)
A Geochemical Study of Iodine in Volcanic Gases
Authors: Honda Fumihiro , Mizutani Yoshihiko , Sugiura Tsutomu , Oana Shinya
Published: July 2006

Volcanic gases from several active volcanoes in Japan have been analyzed for iodine and chlorine: Showashinzan (I=0.025–0.20 mg.I/kg.H2O, Cl=238–1830 mg.Cl/kg.H2O), Iwatesan (I=0.053–0.19, Cl=2720–3360), Issaikyoyama (I=0.030–0.087, Cl=104–213), Nasudake (I=0.16–3.9, Cl=188–9460), Yakedake (I=0.58–0.93, Cl=1250–1730), Kuju-Ioyama (I=0.13–1.3, Cl=266–8000), Kirishima-Ioyama (I=0.036–0.84, Cl=200–4200), and Miharayama (I=0.45–1.5, Cl=1640–2180). Each volcano has a characteristic I/Cl ratio. Analyses have also been made of hot-spring waters from the environs of Nasudake, Kuju-Ioyama, and Kirishima-Ioyama. It is indicated that the hot-spring waters are similar in I/Cl ratio to the volcanic gases from the same area.
Studies of the Chemiluminescence of Several Xanthene Dyes. IV. Theoretical Considerations
Authors: Kamiya Isao , Iwaki Ryojirô
Published: July 2006

On the basis of the results shown in the previous papers, the following reaction scheme was proposed for the chemiluminescent reaction. Hydrogen peroxide decomposes spontaneously to the radical (R·). A portion of the radical then reacts with the dye molecule (E) to produce an energy-rich intermediate (ME*): E+R·→ME* The energy-transfer takes place from ME* to an unoxidized dye, so the dye is excited electronically: ME*+E→E*+··· However, most of the ME* is decomposed by non-radiative processes. E* is deactivated by fluorescence emission processes (E*→E+hν) or quenching processes (E*+E→E+E). According to this reaction scheme, most of the experimental results can be explained reasonably. It is expected that further experimental evidence, such as the detection of an intermediate, will verify the theory.
Mineral Acids as Photoinitiators of Vinyl. Polymerization in Aqueous Media
Authors: Saha Mihir K
Published: July 2006

A few mineral acids, namely hydrochloric, hydrobromic and sulfuric acid, have been used as photoinitiators for the polymerization of methyl methacrylate in aqueous media in the presence of ultraviolet light. The endgroups incorporated in the resulting polymers have been determined by the application of the sensitive “Dye Techniques” lately developed in our laboratory. On the basis of the endgroup results, attempts have then been made to explain the mechanism of such polymerization, and also the nature of the initiating species involved.
The Polarographic Behavior of Tris(1,10-phenanthroline)cobalt Complexes and the Univalent Phenanthroline-Cobalt Complex.
Authors: Morinaga Kenichi , Nakano Kunio , Saito Shigeru , Nakamura Keizo
Published: July 2006

The oxidation-reduction behavior of tris(1,10-phenanthroline)cobalt complexes at a dropping mercury electrode has been studied by the d. c. and a. c. polarographic methods. The trivalent cobalt-phenanthroline complex ion is reduced in two steps in 1 m sodium sulfate in a quite similar way as the trivalent cobalt-dipyridyl complex ion. Both electrode processes, cobalt(III)→cobalt(II) and cobalt(II)→cobalt(I), are considered to be reversible. The univalent cobalt-phenphenanthroline complex has been obtained as a black powder by the reduction of the divalent cobalt complex with sodium borohydride; the atomic ratio of nitrogen to cobalt has been found to be close to six. The ethanolic solution is brown-black, in remarkable contrast with that of the corresponding dipyridyl complex, deep blue.
The Synthesis of Sulfoxides by the Oxidation of Sulfide with the Bromine Complex of 1, 4-Diazabicyclo(2, 2, 2) octane
Authors: Oae Shigeru , Ohnishi Yutaka , Kozuka Seizi , Tagaki Waichiro
Published: July 2006

1, 4-Diazabicyclo(2, 2, 2)octane readily forms an addition complex with two moles of bromine. This complex has been found to be an excellent oxidizing agent for the selective oxidation of various sulfides to the corresponding sulfoxides when the reaction is performed in an aqueous medium. The bromine-addition complexes of pyridine and quinoline have also been found to be useful for the same purpose. The reaction has been shown to be a superb way of incorporating 18O into sulfoxides.
Some Reactions of the Glycidyl Esters of Sulfonic Acids
Authors: Nakabayashi Nobuo , Masuhara Eiichi , Iwakura Yoshio
Published: July 2006

1-Chloro-2-hydroxypropyl sulfonates are obtained by the reaction of glycidyl sulfonates with hydrochloric acid at room temperature. They are converted into 1,3-dichloro-2-propanol by the action of hydrochloric acid at 100°C, or into epichlorohydrin by that of bases. The reaction of glycidyl sulfonates and sodium carboxylates affords glycidyl carboxylates. In the preparation of glycidyl carboxylates, glycidyl sulfonates act as a direct alkylation agent for sodium carboxylates. The addition of amines to the epoxide is carried out at first in the reaction of glycidyl sulfonates and amines. The adducts are converted into glycidyl amines by the action of sodium hydroxide, or into N-[β-hydroxypropylene(α,γ)]-ammonium sulfonates by the isomerization, by heating them or letting them stand for a long time. The latter is an intermediate used in preparing 1,4-dioxane derivatives in the presence of sodium hydroxide.
Intramolecular Interaction between Hydroxyl Group and π-Electrons. XIX. Steric Effects on the Interaction in o-(1-Alkenyl)phenols
Authors: Oki Michinori , Iwamura Hiizu
Published: July 2006

Nine o-(1-alkenyl)phenols, o-HOC6H4CR1=CR2R3, have been prepared and their ultraviolet absorptions and the O–H stretching bands (vO-H) in the infrared absorption measured in an effort to explore the effect of the substituents, R1–R3, on the strength of the intramolecular interaction between the OH group and the π-electron system. The K-band of the styrene chromophore at 240–250 mμ is lost in the samples involving R1, which is bulkier than methyl. As the size of R1 increases from H, by way of Me, Et, and i-Pr, to t-Bu, the angle of the twist between the planes made by the benzene ring and the ethylenic group must increase; this trend is nearly parallel with the amount of the interacting vO-H in the infrared spectrum. The phenomenon is interpreted mainly by means of the favorable overlap between the O–H group and π-orbitals. o-Isobutenylphenol shows a νO-H triplet at 3610, 3576 and 3539 cm−1. The latter two bands are assigned to the hydroxyl group interacting with π-electrons on the vinyl group intramolecularly. A tentative explanation has been developed which attributes the two interacting bands to the presence of two interacting conformations. The solvent effect on the ultraviolet absorptions is in accord with this explanation.
A New Synthesis of Polyhydroxydihydroflavonols
Authors: Oyamada Taichiro , Baba Hajime
Published: July 2006

An alkaline hydrogen peroxide oxidation of chalcones with methoxymethoxyl groups in the 2′-position and in other positions gave the corresponding poly(methoxymethoxy)chalcone oxides; these were then, in turn, easily converted into polyhydroxydihydroflavonols, with a simultaneous splitting of all the O-methoxymethyl groups, by warming with acid. The general applicability of the new method was illustrated by the synthesis of the following hydroxydihydroflavonols: 3,7-dihydroxy- (m.p. 170–171°C),3,4′-dihydroxy- (m.p. 214–216°C),3,4′-dihydroxy-3′-methoxy- (m.p. 217–218°C),3,4′,7-trihydroxy- (m.p. 214–215°C), and 3,3′,4′,7-tetra-hydroxyflavanone (dl-fustin, m. p. 217–218°C). The first four new compounds were identified by converting them into known methyl ethers, while the last one was identified by comparing it with natural dl-fustin. Their structures were also confirmed by infrared and ultraviolet spectra.
The Mass Spectra of Chalcones, Flavones and Isoflavones
Authors: Itagaki Yasuhiro , Kurokawa Tadashi , Sasaki Shin-ichi , Chang Chin-Te , Chen Fa-Ching
Published: July 2006

The fragmentation of flavonoid compounds by electron impact has been studied and the following results described: 1) Chalcones gave the usual fragmentation pattern; however, 2′-hydroxy chalcones showed complex spectra according to the isomerization of chalcone to flavanone. 2) The fragmentation pathways of flavones were decided by comparison with many kinds of halogen-substituted flavones. 3) Isoflavone gave the M-1 ion as the base peak, and no loss of CO was observed.