bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Heats of Mixing for Binary Mixtures. III. The Intermolecular Energy of Hydrogen Bonding between Alcohol and Several Other Polar Molecules
Authors: Murakami Sachio , Fujishiro Ryoichi 
Published: July 2006

Abstract
Calorimetric measurements of the heat of mixing have been made at 25.0±0.01°C for binary mixtures of n-butanol with polar liquids (acetonitrile, acetone, n-butyl ether, and n-butyl amine), and for binary mixtures of polar liquids with n-hexane. The calorimeter for measuring the heats of mixing was of twin type, and a thermomodule, HTM 0516 type (Sharp Electric Co., Ltd., Osaka) was used as the temperature-sensing device. By plotting the values of the heat of mixing, ΔHx1m, against the mole fraction of component 1, x1, and by extrapolating the curve to an infinite dilution (x1→0) for each system, the heats of mixing per mole of component 1 at an infinite dilution (\undersetx1→0limΔHx1m) were obtained graphically. By using the values of \undersetx1→0limΔHx1m obtained for these systems and by using the same treatment as that described in a previous paper [S. Murakami, K. Amaya and R. Fujishiro, This Bulltein, 37, 1776(1964)], the intermolecular hydrogen bond energies between alcohol and polar molecules were estimated; it was found that the strength of the hydrogen bond was in the following order: n-butyl amine&gt;n-butyl ether&gt;acetone&gt;acetonitrile. This agrees with the results obtained from the spectroscopic study.
Copolymerization Characteristics of Methyl Acrylate and Methyl Methacrylate. II. Analysis of Methyl Acrylate-Methyl Methacrylate Copolymers by Infrared Spectroscopy
Authors: Kotera Akira , Shima Mikiko , Akiyama Katsuo , Kume Masako , Miyakawa Machiko 
Published: July 2006

Abstract
The infrared absorption spectra of polymers and copolymers of methyl acrylate and methyl methacrylate have been measured, and then used as the basis of a spectrophotometric method for the analysis of the copolymers. The 6.73 μ band, which may be due to methyl (–C–CH3) vibration, was selected as the key band for measuring the methyl methacrylate component, while the 6.89 μ band was used as the standard. The monomer reactivity ratios for copolymerization of methyl acrylate-methyl methacrylate system have been determined to be r1=0.5±0.1, and r2=2.3±0.4 (M1 methyl acrylate, M2; methyl methacrylate) at 130°C. These values are in good agreement with those previously obtained by the deuterium tracer method. It has also been shown that the procedure used in this study is appropriate for the analyses of methyl acrylate-methyl methacrylate copolymers.
The Electronic Structures and Electronic Spectra of Some Aliphatic Nitroso Compounds
Authors: Tanaka Masashi , Tanaka Jiro , Nagakura Saburo 
Published: July 2006

Abstract
The electronic structures and electronic spectra of 1-chloro-1-nitrosocyclohexane, nitrosyl chloride, methyl nitrite and dimethylnitrosoamine were studied by making molecular orbital calculations and by measuring the electronic absorption spectra. Concerning 1-chloro-1-nitrosocyclohexane, the n→π* and π→π* bands were observed at 650 and 160 mμ respectively. The conjugation effect of electron donors such as Cl, OCH3 and N(CH3)2 upon the electronic spectrum of the nitroso group was studied. The intramolecular charge-transfer bands characteristic of the donor-acceptor interaction were found at 190, 210 and 230 mμ for nitrosyl chloride, methyl nitrite and N,N-dimethylnitrosoamine respectively. This shows that the intramolecular charge-transfer bands appear at longer wavelengths in the order of the increasing ability of the electron donors, Cl&lt;OCH3&lt;N(CH3)2. On the other hand, the n→π* bands shift to shorter wavelengths in the same order.
The Intramolecular Interaction between the N–H Group and π-Electrons. IV. The Energetics of the Interaction
Authors: Oki Michinori , Mutai Kiyoshi 
Published: July 2006

Abstract
The thermodynamic parameters for the intramolecular interaction between the N–H group and the π-electrons in N-benzylanilines were determined from the temperature dependence of the N-H stretching absorptions. A comparison of the −ΔH’s with those for the O–H···π interaction indicates that there is no appreciable difference between the interactions involving the N–H and the O–H groups. The −ΔH’s are less than 2 kcal./mol., this figure being considered to be a borderline differentiating the X–H···π interaction from the ordinary hydrogen bond. The wave number shift accompanying the interaction cannot be a measure of the −ΔH in the N–H group, nor be indicative of the difference between two groups. The −ΔH was found to be closely related with the equilibrium constant in these derivatives.
Intramolecular Interaction between Hydroxyl Group and π-Electrons. XX. Conformationally-fixed o-Vinylphenols
Authors: Oki Michinori , Iwamura Hiizu , Onoda Takeru , Nishida Michiko 
Published: July 2006

Abstract
1, 2-Dihydro-5-hydroxy-8-methoxy-3-methylnaphthalene (III) was prepared, starting from 5,8-dimethoxy-α-tetralone, via 8-hydroxy-5-methoxy-2-methyl-1-keto-1,2,3,4-tetrahydronaphthalene. The O–H stretching absorptions (νo−h) and the ultraviolet absorptions of III, 1, 17 β-dihydroxy-4-methylestra-1,3,5(10), 9(11)-tetraene (IV), and the related naphthols were measured and compared with those of o-isobutenylphenol. IV showed a νo−h at 3532cm−1 which is assigned to the hydroxyl group taking part in the strong interaction with the π-electrons on the ethylenic group; it corresponds well in its location to the lowest frequency band of o-isobutenylphenol. The previous assignment of this band to the conformer II with the double bond syn to the hydroxyl was thus confirmed. III showed only a symmetric band at 3618cm−1, which was assigned to the free νo−h and could not be a model for the conformer with a νo−h at 3576cm−1, presumably because of the more planar structure for the overlap between the orbitals of the hydroxyl group and the ethylenic group.
Kinetic Studies of the Oxidation of Aldopentoses: l-Arabinose and d-Xylose Oxidized by Hexacyanoferrate(III) in an Alkaline Medium
Authors: Srivastava Rajendra Kumar , Nath Narendra , Singh M P 
Published: July 2006

Abstract
The kinetic studies of the oxidation of l-arabinose and d-xylose have been carried out using potassium ferricyanide in the presence of sodium hydroxide and sodium carbonate. The order of the reaction has been found to be zero with respect to ferricyanide and first with respect to the reducing sugar. The reaction rate is also directly proportional to the hydroxide ion concentration. The reaction also has a very small induction period.
Effects of Pressure on the Chemical Properties of the Solid Surface. III. The Catalytic Activity and the Structure of the Compressed Tungstic Acid
Authors: Ogino Yoshisada , Kawakami Takeshi , Matsuoka Toru 
Published: July 2006

Abstract
In order to investigate the surface properties of tungstic acid samples which had been compressed at pressures of 640–3840 kg./cm2, experimental studies concerning the catalytic activity for the vapor-phase hydration of propylene, the specific surface area, the pore structures, the surface acidities and the crystal structures were carried out. According to the experimental results, both the catalytic activity and the surface acidity became higher as the compressing pressure of the sample was increased, whereas the specific surface area remained practically constant. Further, a relation between the surface acidity and the crystal structure was deduced from X-ray diffraction studies. Namely, the crystal structure of the reduced sample approached the structure of H0.1WO3 from a WO3-like structure as the compressing pressure was increased. In other words, samples with higher compressing pressures had crystal structures of a higher proton content. In addition to the above results, the total pore volume, the mean pore radius, the apparent activation energy, and the frequency factor became smaller as the compressing pressure was increased. On the basis of these experimental results, it was deduced that the catalytic activities of the compressed samples are affected by intra-particle diffusion.
CHEMISTRY OF THIO-CHOLINE HALIDE (TRIMETHYLTHIO-ETHYL AMMONIUM HALIDE). NEW THIO-CHOLINE BROMIDE AND ITS DERIVATIVES. I
Authors: Harada Taichi 
Published: July 2006

Abstract
1. Thio-choline bromide was prepared by heating bromocholine bromide with 2-thio-uracil or 4-methyl-2-thio-uracil with water in a closed tube or pressure bottle at 150°C and 170°C. for two and five hours respectively. The compound is hygroscopic in nature, and is very soluble in both alcohol and water. It decomposes at 243°C. on heating. Its isoelectric point was found to be 7.00.
2. By heating with hydrobromic acid the compound is easily oxidized to its disulphide, which is a syrupy and less pronounced ionizable substance, in aqueous solution.
3. On treating an aqueous solution of this compound, with an excess of silver oxide, and neutrallizing with hydrobromic acid and heating on the steam bath, an insoluble white asbestos-like crystalline substance was formed. It appears to be the following formula:
(Remark: Graphics omitted.)
The compound is slightly soluble in alkaline solution. It decomposes at 214°C.
ON THE PROMOTER ACTION IN THE CATALYTIC OXIDATION OF METHANE WITH STEAM
Authors: Kubota Bennosuke , Yamanaka Tatsuo 
Published: July 2006

Abstract
In the catalytic oxidation of methane with steam in the presence of nickel, the promoter action of several metallic oxides were investigated.
It was found that the largest quantity of CO2 was obtained by employing the catalyst promoted with Al2O3, whilst when water vapour was regulated the catalyst promoted with MgO gave the largest yield of CO.
These results might possively lead one to suppose that the reaction may be looked upon as taking place successively in the manner:
(Remark: Graphics omitted.)
and as the beneficial effect of promoters in these reactions may be to transfer water molecules to the reaction centers of the catalyst where the action of water on methane is carried out, the products may be determined according to the adsorbing intensity of water molecules and the size of the promoter. Thus it seems to us that the results we obtained are quite in good agreement with Balandin’s “ Multipletthypothese.”
ELECTRONIC CONCEPTION IN ORGANIC CHEMISTRY. III. DISSOCIATION AND SEMIHYDROBENZOIN REARRANGEMENT OF αα-DIMETHYL-β-ACETYL GLYCOL
Authors: Migita Masao 
Published: July 2006

Abstract
In order to see the effect of the carbonyl group, action of hot dilute and cold concentrated sulphuric acid on αα-dimethyl-β-acetyl glycol was studied.
This keto-glycol was found to undergo semihydrobenzoin rearrangement and dissociation into acetone and acetol simultaneously. The primary product of the semihydrobenzoin rearrangement of this glycol being decomposed during the subsequent treatments, only the secondary products, methyl-isopropyl ketone, could be isolated. The dissociation of dimethylacetyl-glycol was started not only by acid, but also by alkali. These results can be easily deduced from the electronic interpretation given in previous papers.
That the dissociation of dimethyl-acetyl glycol takes place merely by distillation was directly proved by identifying acetol by a new method.
Methods to identify acetone, methyl-ethyl ketone, methyl-isopropyl ketone, acetol and dimethyl-acetyl glycol with limited quantity of the sample in presence of one another, were carefully studied and established.
The Thermal Decomposition of Hexamminenickel(II) Complexes
Authors: Tanaka Nobuyuki , Kagawa Masahiro , Kamada Minoru 
Published: July 2006

Abstract
From the thermogravimetric analysis, hexamminenickel(II) complexes were confirmed to decompose in two or three steps through lower ammine intermediates NiXm·nNH3: n=2, 1 and m=2 for X=Cl; n=2 and m=2 for X=I, Br; n=4 and m=2 for X=NO3 and n=2, 1/2 and m=1 for X=SO4. The diffuse reflectance spectra of these intermediates have been measured in a range between 5000 to 27000 cm−1, and they suggested that these intermediates may be polymers in which nickel ions were octahedrally coordinated with ammonia molecules and bridging halogen atoms. The infrared absorption spectra of these intermediates obtained in a range between 5000 and 60 cm−1 are also reported.
The Selective Reduction of Aromatic Compounds by Electrolysis. I. Reduction of Naphthalene by Electrolysis
Authors: Misono Akira , Osa Tetsuo , Yamagishi Takamichi 
Published: July 2006

Abstract
The direct electro-reduction of naphthalene was investigated in various solvents, mainly in an acetonitrile-water solution using supporting electrolytes containing tetraethylammonium and tetra-n-butylammonium cations. The main reduction product was 1,4-dihydronaphthalene, though small amounts of 1,2-dihydronaphthalene and tetralin were also detected. Under optimum conditions, the selectivity and the current efficiency of the formation of 1,4-dihydronaphthalene were 98% and 86.4% respectively. It was found that the water concentration and the solvent had a significant influence on the reduction products and the current efficiency. 1,4-Dihydronaphthalene is mainly formed through the step-by-step addition of two electrons and protons. In addition, 1,4-dihydronaphthalene may be formed by the protonation of the dianion formed by the disproportionation of the anion radical. Further, it was proposed that the formation of the tetraethylammonium radical might partly occur by means of the electron transfer from the anion radical of naphthalene to the tetraethylammonium cation, besides the direct electron transfer to the cation from the electrode.
A New Synthesis of Substituted 8-Aminopurine Derivatives
Authors: Yoneda Fumio , Higuchi Masatsugu , Matsumura Takafumi , Senga Keitaro 
Published: July 2006

Abstract
The treatment of 6-amino-5-nitrosopyrimidines with Vilsmeier-type reagents (substituted formamides and phosphorus oxychloride) afforded substituted 8-aminopurines; the treatment of 6-amino-4-hydroxy-2-methyl-5-nitrosopyrimidine gave 2-chloromethyl-8-dimethylamino-6-hydroxypurine.
Synthesis of Alanosine
Authors: Isowa Yoshikazu , Kurita Hideaki , Ohmori Muneki , Sato Masanari , Mori Kaoru 
Published: July 2006

Abstract
Dl-2-Ammo-3-(N-tosyl-N-benzyloxyamino)propionic acid (Dl-V) was synthesized starting from ethyl 2,3-dibromopropionate and N-tosyl-O-benzylhydroxylamine. l-2-Benzoylamino-3-(N-benzoyl-N-hydroxyamino)propionic acid anilide (l XIV) obtained via the enzymatic resolution of Dl-2-benzoylamino-3-benzyloxyaminopropionic acid (Dl-IX) was converted by acid hydrolysis to l-2-amino-3-hydroxyaminopropionic acid (l-II). The nitrosation product of the amino-hydroxyamino acid (l-II) was identical with alanosine (l-I).
Reaction of Mo5+ Formed on Supported Molybdena Catalysts with Oxygen or Water
Authors: Akimoto Masamichi , Echigoya Etsuro 
Published: July 2006

Abstract
Reactivity of Mo5+ formed on supported molybdena catalysts with oxygen or water was investigated by means of ESR spectroscopy. Mo5+ formed on the alumina carrier could not be oxidized with gaseous oxygen even at 450 °C and was poisoned by water at 200 °C losing its ESR signal. The Mo5+ formed on the titania carrier disappeared by reaction with either oxygen or water. The mechanism for the reactions was investigated and the different reactivities of Mo5+ with oxygen as regards carrier effect on the structure were discussed.
Effect of Additives on Thermal Decomposition of Basic Magnesium Carbonate
Authors: Amita Kayoko , Hashizume Genzo 
Published: July 2006

Abstract
The effect of eleven halides on the thermal decomposition of basic magnesium carbonate (4MgCO3·Mg(OH)2·4H2O) has been studied by means of thermogravimetry (TG), differential thermal analysis (DTA) and gas chromatography. The size of crystallite of magnesium oxide prepared by heating the carbonate containing halide was determined by X-ray diffractometry, the oxides being studied by transmission electron microscopy. The thermal decomposition of basic magnesium carbonate was influenced by the addition of beryllium chloride tetrahydrate, magnesium chloride hexahydrate, calcium chloride hexahydrate and magnesium bromide hexahydrate. The DTA curve was changed with the amount of additive, i.e., three endothermic peaks (at about 300, 430, and 530 °C) and an exothermic peak (at 490 °C) turned to only two endo-thermic peaks in the case where the molar ratio of an additive to the carbonate exceeded 0.005, the peak at higher temperature becoming sharp with shift toward lower temperature. The results of TG of basic magnesium carbonate corresponded to those of DTA. Gas chromatographic data showed that the composition of evolved gas varied with temperature. The activation energies of decarbonation and dehydration were obtained by gas chromatography by use of Freeman-Carroll’s technique. Increase in the amount of additive caused a decrease in the activation energy of decarbonation, but not in that of dehydration except for magnesium bromide hexahydrate. The size of crystallite of magnesium oxide prepared by calcination at 600 °C for 2 hr, increased with the increase in the amount of additive.
A Study of Solute–Solvent Interaction in Solvents of Medium Dielectric Constant from the Apparent Molal Volume Data. I
Authors: Gopal Ram , Agarwal D K , Kumar Rajendra 
Published: July 2006

Abstract
A study of the apparent molal volume (φv) of some common salts and the tetraalkylammonium iodides in DMSO has been reported in this communication. All the salts studied here, including those containing the larger R4N+ ions, have a positive slope in the φv vs. \sqrtC curves, indicating a strong ionic interaction, apparently due to the medium dielectric constant of the solvent. This dielectric constant also promotes ion-association at higher concentrations and thus mutual penetration of the R4N+ ions is prevented. As a result, no negative slope in the φv vs. \sqrtC curves of the larger R4N-iodides is observed in this solvent. The effect of temperature on the limiting apparent molal volume, φ°, reveals that the ion-solvent interaction is comparatively stronger in the non-hydrogen bonded solvents like DMSO and DMF than that in strongly hydrogen-bonded solvents like NMA and NMP. Addition of a CH2-group to each of the four R-chains of the R4N+ ion increases its volume by about 70 ml per mole in DMSO, DMF, and NMA.
The Bromination of p-Nitrophenol in Acetic Acid
Authors: Sridhar N , Rajaram J , Kuriacose J C 
Published: July 2006

Abstract
Bromination of aromatic substrates like p-bromophenol, anisole, etc. by molecular bromine in acetic acid follows the rate expression, Rate=k[ArH][Br2]+k′[ArH][Br2]2. For the bromination of p-nitrophenol in acetic acid, variable orders in bromine and p-nitrophenol have been observed on varying the concentrations of reactants. A rate expression of the type, Rate=k[ArH][Br2]+k′[ArH][Br2]2+k″[ArH]2[Br2] has been proposed. The observations conform to a general mechanism for bromination provided a bromine molecule, a substrate molecule or solvent molecules can be the electrophile in the rate determining step, depending upon the conditions employed for the reaction.
The Simultaneous Detection of Gas Phase Atoms and Free Radicals Produced in a Microwave Discharge by ESR Spin Trapping Methods
Authors: Janzen Edward G , Kasai Toshio , Kuwata Keiji 
Published: July 2006

Abstract
The simultaneous detection of gas phase atoms and free radicals produced in a 2450 MHz discharge is demonstrated by use of a previously described technique called spin trapping. The atoms or radicals are allowed to react with phenyl N-t-butyl nitrone to give relatively stable nitroxide radicals. The ESR spectra of these nitroxides provide the analytical data for identification of the atoms or radicals trapped.
Photovoltaic Effect of Aromatic Diamine in Solution
Authors: Imura Takeshi , Takagi Seishi , Kawabe Kazuo 
Published: July 2006

Abstract
Photovoltaic behaviors are described of N,N,N′,N′-tetramethyl-p-phenylenediamine dissolved in various polar solvents. Positive photovoltage is observed on the illuminated electrode in highly polar solvents such as methanol and acetonitrile, and none in moderately polar ones such as ethanol and acetone. The influence of a few electrode metals on photovoltage has been examined. The electromotive force increases with the work function of metals from tantalum to platinum. Conditions for the appearance of photovoltage are discussed and the photo-ionization process of the aromatic diamine is considered.
Reductions of Cobalt(III) Complexes by Iron(II) Chelates. I. The Kinetics and Mechanisms of the Reductions of Acidopentaamminecobalt(III) Complex Ions by Iron(II) Chelates of Nitrilopolycarboxylic Acids
Authors: Kurimura Yoshimi 
Published: July 2006

Abstract
Kinetic studies have been made of the reactions of FeEDTA2− with complex ions of the Co(NH3)5X2+ (X=F−, Cl−, Br−, I−, NO3−, NCS−, and N3−) type. The pattern of reactivity suggests that FeEDTA2− reacts with Co(NH3)5X2+ mainly through an innersphere mechanism. The variation in the rate of the reactions of FeIIZm− (Z=EDTA, CyDTA, EDTA-OH, and DTPA), in which the Z ligand is varied, with Co(NH3)5Cl2+ can be explained in terms of the steric effect, the charge effect, and the stabilization effect.
Thermal and Spectrophotometric Studies of 8-Mercaptoquinoline-5-sulfonic Acid and Its Sodium Salt
Authors: Sekido Eiichi , Tanaka Junichi , Masuda Yoshitaka 
Published: July 2006

Abstract
Thermal and spectrophotometric studies of 8-mercaptoquinoline-5-sulfonic acid and its sodium salt synthesized by an improved method are reported. In order to determine the best formula for the weighing of organic reagent, the thermal stabilities of 8-mercaptoquinoline-5-sulfonic acid and its sodium salt and the amount of water of crystallization were examined with a thermal balance. It was found that the disodium dihydrate was of the best form. The ultraviolet and visible absorption spectra in aqueous-ethanol solution were measured, the tauto-meric constant Kt between neutral and zwitterion forms being estimated and acid dissociation constants obtained spectrophotometrically. The absorption spectra and the equilibrium constants of the reagents were compared with those of 8-mercaptoquinoline, 8-hydroxyquinoline and 8-hydroxyquinoline-5-sulfonic acid.
Stability of Fused Rings in Metal Chelates. X. Structures and Stability Constants of the Copper (II) Complexes of Tripeptides Composed of Glycine and/or β-Alanine
Authors: Yamauchi Osamu , Nakao Yasuo , Nakahara Akitsugu 
Published: July 2006

Abstract
On the basis of comparative studies of the equilibria involving copper(II) and triglycine (G·G·G), glycylglycyl-β-alanine (G·G·β-A), glycyl-β-alanylglycine (G·β-A·G), or β-alanylglycylglycine (β-A·G·G), the structures of the complexes formed at various pH values and the structure-stability relationship between the fusedring chelates have been discussed in reference to the equilibrium constants determined by potentiometric titration at 25°(μ=0.1 (KNO3)) and the properties of the copper(II) chelates isolated. For each tripeptide, the stability constant K1 for the 1: 1 complex and the constants for the deprotonation reactions Kc1 and Kc2 were calculated by the method of non-linear least-squares. For G·G·G, G·G·β–A, and G·β–A·G, the equilibrium indicating the formation of a protonated complex was detected at pH 3.5–4.5. The relatively small difference in the logK1 values (5.25–5.60) and the logKc1 values (5.23–5.36) and the larger difference in the −logKc2 values (5.54–6.73) have been interpreted in terms of the steric requirements around copper(II) in the fused-ring chelates. Relative stabilities of the fused-ring systems in the deprotonated chelates have been inferred from the K1Kc1Kc2 values to be in the order 5-6-5(G.β-A·G-Cu(II))\simeq6-5-5(β-A·G·G-Cu(II))&gt;5-5-6(G·G·β-A-Cu(II))&gt;5-5-5(G·G·G–Cu(II)).