bluuebunny/crossref_metadata_2025_split huggingface dataset:
S-Alkylthioamidium Salt. II. The Reactions of S-Alkylthioamidium Iodides with Mercuric Compounds
Authors: Yamaguchi Tatsuaki , Inomata Katsuhiko , Mukaiyama Teruaki 
Published: July 2006

Abstract
The reactions of S-alkylthioamidium iodides with some mercuric compounds have been studied. Mercuric carboxylates were found to react with S-alkylthioamidium iodides giving the corresponding acid anhydrides and amides in good yields along with alkylmercaptomercuric iodide. In addition, it was established that the reaction of mercuric cyanide with the iodides afforded α-dimethylaminomalononitriles by the elimination of alkylmercapto mercuric iodide. Further, α-morpholino-β-phenylacrylonitrile was obtained in 87% yield by treating S-ethylthiophenylacetomorpholidium iodide with silver cyanide.
Reaction of Allylbenzene with n-Butyllithium in Tetrahydrofuran
Authors: Okamoto Yoshio , Yuki Heimei 
Published: July 2006

Abstract
The reaction products between allylbenzene and n-butyllithium in tetrahydrofuran at 60°C were fractionated and investigated by elementary analysis, a molecular-weight determination, and a study of the IR, UV, and NMR spectra. The products were hydrocarbons and alcohols, the latter of which were formed by the reaction of the carbanions with tetrahydrofuran. The main products were 3-phenylheptene-2,5-methyl-6-phenyldecane, 5-phenyl-5-heptene-1-ol, 5-phenyl-5-vinylnonane-1-ol, and 5-phenyl-5-vinylnonane-1,9-diol. 3-Phenylheptene-1 was not obtained. In the resonance structures of allyl anions, a and b, Ph-\barCR–CH=CH2 (a) ↔ Ph–CR=CH–CH2− (b), the reaction with tetrahydrofuran took place only in the form a. The observed results are correlated with those of the anionic polymerization of trans-β-methylstyrene reported previously.
Condensation of Methylolmelamine
Authors: Sato Kenji 
Published: July 2006

Abstract
The condensation of methylolmelamine in the range of ca. pH 8–1 was investigated. An aqueous-dimethylsulfoxide (DMSO) solution (ca. 1 : 2, vol. ratio) was mainly used as the solvent, because it was revealed that the condensate in the latter stage of the condensation is soluble in DMSO solvent, and also that in this solvent methylolmelamine scarcely decomposes into a lower methylolmelamine liberating formaldehyde; then, the condensation mechanism of that methylolmelamine whose composition corresponds approximately to di-, tri-, and hexa-methylolmelamine, was investigated, not only in the early stage but also in the latter stage. It was found that the condensation rates of di- and tri-methylolmelamines (low methylolmelamines) in the early stage show maxima at ca. [HGl]/[methylolmelamine]=0.5 (molar ratio), i.e., at ca. pH= logK, where K is the equilibrium constant between the molecular form of the methylolmelamine and its conjugate acid, and that in hexa-methylolmelamine (high methylolmelamine) the above maximum appears at ca. [HCl]/[methylolmelamine]=0.5–1.0 (molar ratio). Also, the above maxima were found to shift toward smaller [HGl]/[methylolmelamine] (molar ratio) values as the condensation proceeded (the latter stage). From these results, a condensation mechanism was proposed for the early stage of the condensation.
Scission Probabilities of the Skeletal Bond of Aliphatic Ethers by Electron Impact
Authors: Hirota Kozo , Takezaki Jun’ichi 
Published: July 2006

Abstract
Mass spectra of eight aliphatic mono- and di-ethers have been measured with apparatuses of both ordinary and high resolution type, and scission probability of their skeletal bonds has been determined. By application of the molecular orbital theory on bond-scission by electron impact, the scission probability of the skeletal bonds has been evaluated, using only a few constants peculiar to the C–O bond so as to determine the molecular orbital. Comparison between theory and experiment has been found satisfactory on such ethers, even though they have lone-pair electrons in the inner part of the molecules. Thereby, scission of the skeletal bond has been shown explainable quite well by the primary processes in most ethers, except highly symmetric or large ethers.
Thermal Decomposition of Hexamethylene Tetramine
Authors: Iwakami Yoshitomo , Takazono Masao , Tsuchiya Toshikazu 
Published: July 2006

Abstract
In order to get information about the mechanism of the thermal decomposition of hexamethylene tetramine (hexa), hexa was decomposed thermally in a vacuum vessel, and the composition of the gas thus produced was determined with a mass spectrometer. The main products found were ammonia and a carbon-rich solid residue. The carbon in the carbon-rich residue seems to act as a catalyst for the decomposition.
Study of Motion of D2O in Ba(ClO3)2D2O by Transient NMR
Authors: Chiba Takehiko , Kakiuchi Yoshinobu 
Published: July 2006

Abstract
Deuteron spin lattice relaxation time T1 and the reorientation rate of D2O have been measured at various temperatures on a single crystal of Ba(ClO3)2D2O by transient nuclear magnetic resonance method. Temperature dependence of T1 is similar to that of corresponding proton resonance but three to four orders of magnitude smaller than the latter. From the slope of logT1 vs. 1/T curve, activation energy of reorientation of D2O of 6.5–6.8 kcal/mol is obtained in agreement with that from line width transition. Theoretical values of T1 minima were in good agreement with the observed. Direct measurement of reorientation rate is made by observing a signal recovery from saturation of one of the two deuteron sites of D2O due to the exchange with unsaturated spins at the other site. The Arrhenius plot of the reorientation rate down to −170°C determined in this manner smoothly connects to that derived from the line width transition. A revision of the previous treatment of line width change is described and the reorientation rates of Ba(ClO3)2D2O are re-evaluated according to this method. A satisfactory agreement is found among the conclusions from the three different types of experiment, T1, the line width transition and the directly measured reorientation rate. The motion is a random reorientation of D2O with a rate governed by an activation process of 7 kcal/mol.
Copper Catalyzed Oxidation of As(III) by Peroxydisulphate
Authors: Bhargava A P , Gupta Y K 
Published: July 2006

Abstract
A kinetic study of the oxidation of As(III) by peroxydisulphate catalyzed by Cu(II) has been made. The rate has been measured by estimating As(III) by the permanganate. The data follow the rate expression,
(Remark: Graphics omitted.)
A chain mechanism has been suggested in which the decomposition of peroxydisulphate is the chain initiating step. Cu(II) and As(III) participate in the chain propagating steps. Allyl acetate and Mn(II) inhibit the reaction. The mechanism also involves a complex formation between Cu(I) and As (III) with an equilibrium constant, K2, having a value of about 1475 m−1at 35°C. Energy and entropy of activation have been found to be 24190 calories and +10.46 e. u. respectively.
Distribution of Some Minor Elements in Sulfide Ores from the Hitachi Mine, Ibaraki Prefecture, Japan
Authors: Hamada Shuichi , Sato Ryuji , Shirai Toshiaki 
Published: July 2006

Abstract
The contents of some minor elements in copper-bearing ores from the Fujimi ore deposit No 5, the Hitachi mine, were determined. The selenium content in 46 samples was found to vary from 0.5 to 117 ppm. Though selenium seems to be concentrated in the ores rich in chalcopyrite, that is not always the case, as there are pyrite-rich ores with higher selenium contents than those rich in chalcopyrite. The average value of the atomic ratio of Se/S in the pyrite ores was calculated to be 3.48×10−5; this value was larger than those found for the ores from the Minenosawa and the Chichibu mines, and about the same as those found for the ores from the Nakase, the Ashio, and the Hanaoka mines. The variations with depth in the atomic ratios of Se/S and Co/Ni are closely related to each other. The atomic ratio of Se/S increased with an increase in that of Co/Ni. It has been concluded that selenium is concentrated in the pyrite ores of the high-temperature-type rather than in those of the low-temperature-type. The mercury content was small in general, but a large content of mercury was observed at the depth where the values of the atomic ratios of Se/S and Co/Ni were at their maxima.
Spectroscopic Studies of Mixed Amine Carbonyl Complexes of d6 Structure. II. Solvent Effect on the Ultraviolet and Visible Absorption Spectra of Diamine-tetracarbonyl Complexes of Chromium(0), Molybdenum(0) and Tungsten(0)
Authors: Saito Hide , Fujita Junnosuke , Saito Kazuo 
Published: July 2006

Abstract
Absorption bands, especially metal to amine charge transfer bands of bipyridyl- and phenanthroline-tetracarbonyl chromium (0), molybdenum (0) and tungsten (0) are shifted in various solvents by less than 4500 cm−1. The shift is discussed in accordance with McRae’s equation, which was derived with the point-dipole approximation. The solvents can be classified into two groups, the alcohol and the ester group. When three constants corresponding to (1) the interaction between induced dipoles of the solute and of the solvent, (2) the interaction between permanent dipole of the solute and induced dipole of the solvent, and (3) the interaction between permanent dipoles of the solute and of the solvent, are duely chosen for the two groups of solvent individually, the experimental values are satisfactorily accounted for. Short range interactions, such as hydrogen bonding can be ignored.
A Kinetic Study of the Free-Radical Bulk Polymerization of Ethylene
Authors: Machi Sueo , Sakai Takashi , Suganuma Fujio , Kagiya Tsutomu 
Published: July 2006

Abstract
The bulk polymerization of ethylene was carried out under mild conditions, i. e. pressures of from 183 to 400 kg/cm2 and temperatures of from 30 to 140°C, using azobisisobutyronitrile as an initiator. In polymerization at the low temperature of 40°C, both the polymerization rate and the molecular weight of the polymer formed increased with the reaction time. At the above temperature, the polymerization rate was shown to be proportional to the amount of initiator, and the molecular weight was found to be independent of it. Furthermore, both the polymerization rate and molecular weight were found to be proportional to the 2.5th power of ethylene fugacity. The dependencies of the polymerization rate and the molecular weight on the reaction time decrease with the rise in reaction temperatures from 30 to 100°C. A kinetical discussion indicated that the rate of termination is almost zero at 30–40°C, but that it increases with the temperature. The polymerization rate and the molecular weight were shown to be proportional to the 0.8 and 0.2th powers of the amount of the initiator. The activation energy of the initiation reaction was evaluated to be ca. 27 kcal/mol.
Mechanism of the Gas-phase Oxidation of Propylene in a Propylene-excess Atmosphere under Pressure
Authors: Masai Mitsuo , Echigoya Etsuro , Morikawa Kiyoshi 
Published: July 2006

Abstract
The mechanism of the oxidation of propylene is studied through the addition of t-butyl hydroperoxide, acetaldehyde, or propionaldehyde to the reactant (propylene and oxygen), and also through the direct addition of the products of the (C3H5Br+O2 or CH3CHO+O2) reaction to propylene. The following conclusions are reached: acetaldehyde and not propionaldehyde is responsible for chain-branching, acetaldehyde is formed from the allyl peroxy radical alone, propylene oxide is formed mainly by the reaction of the acetyl peroxy radical with propylene, the allyl peroxy radical probably contributes to the formation of propylene oxide, propionaldehyde, and acrolein in an equal extent, and the recombination of radicals is highly retarded in this propylene-excess system. On the basis of the data obtained, a plausible reaction scheme is proposed.
Reactions of Triethylaluminum with α,β-Unsaturated Carbonyl Compounds
Authors: Baba Yoshio 
Published: July 2006

Abstract
The reactions of triethylaluminum and its various ether adducts with α,β-unsaturated ketone, aldehyde, ester, and methyleneanthrone have shown that the addition occurs mainly at the 1,2-positions of the carbonyl function, and not at the 1,4-positions as has been observed in the Grignard reaction. The mode of addition was discussed in view of the reactivity of the organometallic compound and the steric factor of the unsaturated carbonyl compounds.
On the Structures of Alkali Polyaluminates
Authors: Yamaguchi Goro , Suzuki Kazutaka 
Published: July 2006

Abstract
Besides the so-called β-Al2O3 (R2O·11Al2O3; R=Na or K), there have been found two kindred compounds with approximate formulas, R2O·7Al2O3 (β′-Al2O3) and R2O·5Al2O3(β″-Al2O3). The structure determination of the latter two compounds was undertaken; the results are compared with the structure of β-Al2O3 in the present paper. These three structures are composed of spinel layers of the same configuration. The structures of β and β′ are very similar to each other, both equally bearing a layer-stacking according to a two-fold screw symmetry, while β″ differs from these two in exhibiting another way of layer-stacking, according to a three-fold screw symmetry.
Dihydroxyquinoxaline Studies. Solubility, Ionization Constant, and Chelating Behavior
Authors: Oguchi Shoshichi 
Published: July 2006

Abstract
The solubility, ionization constant, and chelating behavior of dihydroxyquinoxaline,. mainly 5,8-dihydroxyquinoxaline (5,8-DHQ) derivatives, have been measured and will be discussed. The introduction of a hydroxyl group into quinoxaline greatly lowers the solubility. The order of the decreasing solubility of 2,3-disubstituted 5,8-DHQ in water (at 20°C) is: O(CH2)2OC2H5&lt;H&lt;OH&lt;CH3&lt;C6H5&lt;OC2H5&lt;Cl&lt;SH&lt;SC2H5. For 5,8-DHQ the introduction of electron-repelling groups into 2,3-positions raises both the pKNH and pKoH values, while the introduction of electron-attracting groups into the same positions lowers both pKNHand pKoH. 5,8-DHQ, and its derivatives form colored precipitates with metal ions, but some derivatives which have pKNH values lower than zero fail to show any precipitation or coloration. 6,7-DHQ forms precipitate, and the precipitation colors distinctively with Cr(III) or Fe(II). The composition and stability constant (K) of copper(II) chelates of 5,8-DHQ and its derivatives in a dioxane-water (10 : 90 v/v) solution were studied spectrometrically. The copper chelate of 5,8-DHQ had a metal: ligand ratio of 1 : 1 and a logK value of 6.28 at pH 4.0. The structures of these copper chelates will be proposed.
Study on Fragmentation Process of Thymidine by Mattauch-Herzog Geometry High Resolution Mass Spectrograph
Authors: Tsunakawa Sukenari 
Published: July 2006

Abstract
High resolution mass spectra of thymidine were studied by Mattauch-Herzog geometry mass spectrograph. The element map of it was presented and the fragmentation processes were shown by solid or dotted lines on the map. The spectra were measured with higher accelerating voltages (about 0.1%) in order to obtain many metastable peaks on the photographic plate. By a single focusing mass spectrometer ten metastable peaks were measured and “intentionally defocused” high resolution spectra gave twenty five diffused peaks with slight shifts to the high mass region though no metastable peaks were observed under normal operating conditions.
The n→π* Bands of Phenyl Carbonyl Compounds, α-Diketones, and Quinones at Low Temperatures
Authors: Kuboyama Akira , Yamazaki Ryuichi , Yabe Sanae , Uehara Yoshio 
Published: July 2006

Abstract
The positions and intensities of the n→π* absorption bands in solutions at 77°K (in the rigid glass state) and at 201°K (in the liquid state) have been studied in comparison with those at room temperature. At 201°K the positions and intensities are similar to those at room temperature. At 77°K some distinct facts have been found in EP (ether-isopentane (1:1) mixture) which are different from those which hold in the liquid state: 1) In desoxybenzoin the absorption is remarkably weak in intensity. 2) In some α-diketones and β-naphthoquinone, the n→π* bands shift greatly to the blue. 3) In β-naphthoquinone the absorption is remarkably strong in intensity. Discussions of the obtained results have been presented.
Studies of the Interaction between the Hexyl Anion and Alkali Metal Ions
Authors: Motomizu Shoji , Tôei Kyoji , Iwachido Tadashi 
Published: July 2006

Abstract
The Hexyl(2,4,6,2′,4′,6′-hexanitrodiphenylamine) anion forms ion-pairs with alkali metal cations to some extent in an aqueous solution. The association constants of these ion-pairs were determined both in nitrobenzene by conductivity measurements and in water by the solvent extraction method. The association constants in nitrobenzene (KoMR) decrease in the following order: Li&gt;Na&gt;K&gt;Rb&gt;Cs. The plot of log KoMR against the ionic potential of the alkali metal ions was found to be linear. In nitrobenzene saturated with water, however, the constants vary from 2 to 4. In water the asscoiation constants (KaMr) vary from about 10 to 400, and the value increases as follows: Li&lt;Na&lt;K&lt;Rb (&lt;Cs). A plot of log KaMR against the reciprocal of the effective diameter of the hydrated alkali metal ions was found to be linear.
The Spectrophotometric Determination of Palladium with Chromazurol S
Authors: Ishida Ryoei 
Published: July 2006

Abstract
A simple spectrophotometric method for the determination of palladium was studied, using chromazurol S as a reagent. Palladium (II), in a slightly acidic or a nearly neutral solution, reacts with chromazurol S to form blue or red complexes, each consisting of one molecule of the reagent and one atom of palladium. The maximum absorption wavelengths of blue and red complexes are respectively 596 mμ and 500 mμ, against the reagent blanks. The color development of the blue complex formed in a slightly acidic medium is more sensitive, therefore, it was applied to the spectrophotometric determination of palladium. Several conditions for the color development were investigated; a calibration curve was made under the optimum conditions; and the influences of coexisting ions were also investigated. The blue complex gives a maximum absorbance at 596 mμ in the pH range from 4.3 to 5.3. About a 2-fold excess of the reagent over the palladium concentration is necessary in order to obtain the maximum color intensity. The color development is almost instantaneous, and the absorbance remains constant for at least 4 hr. The order of the addition of reagents has no effect upon the absorbance. The color system obeys Beer’s law over the concentration range up to 70 μg of palladium per 10 ml. The molar extinction coefficient at 596 mμ is 18600, which corresponds to a sensitivity index of 0.0058 μg/cm2 for an absorbance of 0.001. Sulfate, chloride, fluoride, phosphate and acetate ions do not interfere with the color reaction. Thiosulfate ion and polycarboxylate ions such as oxalate, citrate and EDTA etc. bleach the color of the complex. Cations such as Sc(III), Y(III), Th(IV), U(VI), Be(II), Al(III) and Cu(II) ions cause an over-estimation of palladium; the interference by these cations except copper, however, could be eliminated by the addition of appropriate amounts of either sodium fluoride or sodium phosphate as masking agent.
Catalysis in Peptide Synthesis with Active Esters. II. Effects of Concentrated Carboxylic Acids on the Aminolysis of Benzyloxycarbonyl-l-phenylalanine p-Nitrophenyl Ester in Dioxane
Authors: Nakamizo Nobuhiro 
Published: July 2006

Abstract
The kinetics of the aminolysis reaction of benzyloxycarbonyl-l-phenylalanine p-nitrophenyI ester with glycine t-butyl ester in dioxane were studied in the presence of high concentrations of several carboxylic acids. Bell-shaped curves were obtained when the rate constants observed for the trimethylacetic acid-, acetic acid-, and monochloroacetic acid-catalyzed reactions were plotted against the logarithms of the reciprocals of the acid concentrations. Cyanoacetic acid and trichloroacetic acid did not accelerate, but, rather, retarded the reaction. In the mathematical derivation the catalyst apparently exhibits no accelerating effect, if k0K&gt;kcat, where k0 and kcat are the uncatalyzed and the true catalyzed rate constants respectively, and where K is the acidbase equilibrium constant between the nucleophile and the catalyst in a given solvent. The true catalyzed rate constants, kcat, from which the effect of the protonation of the nucleophile had been eliminated were estimated for the trimethylacetic acid- and acetic acid-catalyzed reactions. The fact that the kcat value (63m−2 min−1) for trimethylacetic acid, the weaker acid, was greater than that (53m−2 min−1) for acetic acid strongly supports the bifunctional, concerted mechanism presented in the preceding paper.
Spectrophotometric Studies of the Copolymer of l-Tryptophan and l-Glutamic Acid in an Aqueous Solution
Authors: Ohnishi Akio , Hayashi Katsuya , Noguchi Junzo 
Published: July 2006

Abstract
The synthetic copolymer of l-tryptophan and l-glutamic acid exhibited two specific bands, around 292 mμ and 234 mμ, in the difference spectrum at pH 4.68 vs. pH 7.60 in a 0.1m phosphate buffer. The former, that at 292 mμ, might be caused by the red shift of the ordinary absorption band around 280 mμ, and the latter, that at 234 mμ, by the red shift of the far-ultraviolet absorption band, around 220 mμ, of the tryptophanyl residue in the copolymer. This specific peak at 234 mμ in the difference spectrum of the tryptophan copolymer may be distinguished from that at 222 mμ, which is due to the hyperchromisity (n→π* transition) of the amide group in the peptide bond reported with poly-l-glutamic acid. The peak at 230–235 mμ appearing in the difference spectrum between native and denaturated proteins may be due to the same red shift (π→π* transition) of the far-ultraviolet absorption band of the tryptophanyl residue as that shown by the tryptophan copolymer. The difference in absorption at 234 mμ was five times larger than that at 292 mμ, and both of them increase proportionally with a lowering of the pH. The relation between the difference absorption and the pH was quite similar to that between the helical content and the pH. The relative fluorescence intensity of the tryptophanyl residue was also depressed with a lowering of the pH, and the profile of the pH-dependence curve on the fluorescence intensity was almost identical with the titration curve of the copolymer. Therefore, it may be said that the appearance of the difference spectrum at 234 mμ corresponds to the formation of the α-helix in polypeptide and that the protonation of the glutamyl residue induces the quenching of the fluorescence of the tryptophanyl residue.
The Optical Resolution and Circular Dichroism of Cobalt(III) Complexes of the [Co(O–O)2(O–N)]2− Type
Authors: Yamasaki Kiyoshi , Hidaka Jinsai , Shimura Yoichi 
Published: July 2006

Abstract
Four cobalt(III) complexes of the tris-chelate type containing two dicarboxylate anions and one aminocarboxylate anion have been newly prepared and separated into their optical isomers by a chemical resolution method: they are bismalonatoglycinato-, bismalonato(l-alaninato)-, bisoxalato(l-alaninato)- and bisoxalato(β-alaninato)-cobalt(III) complexes. The diastereomeric isomers of bisoxalato(l-alaninato)cobalt(III) complex have also been separated by the solubility difference between their barium salts. The absorption spectra, circular dichroism spectra and rotatory dispersion of these complexes have been measured and discussed in relation to the splitting of the d–d transition bands. The absolute configurations of the complexes have been inferred from their circular dichroism spectra. The additivity of configurational and vicinal contributions to the optical activity has been substantiated for the bisoxalato- and bismalonato-(l-alaninato)-cobalt(III) complexes, and some considerations concerning the less stereospecific formation of the l-alaninato diastereomeric isomers have been made in relation to the additivity.