bluuebunny/crossref_metadata_2025_split huggingface dataset:
Resonance Raman Spectra of Acid-Base Indicators. I. p-Aminoazobenzene Derivatives
Authors: Machida Katsunosuke , Kim Bak-Kwang , Saito Yutaka , Igarashi Kyoko , Uno Toyozo 
Published: July 2006

Abstract
Resonance Raman spectra between 1800 and 1000 cm−1 of methyl orange and a few other p-aminoazobenzene-type acid-base indicators have been investigated at various pH, and a marked spectral change has been observed on the transformation between the acid and the base forms of these indicators. The characteristic Raman frequencies have been assigned by referring to the spectra of related compounds and the deuteration effects. The spectra of the acid form are well elucidated on the basis of the quinoid-type structure.
The Relative Determination of the Soret Coefficients of Electrolytes. IV
Authors: Ikeda Toshio , Yamamoto Yasuki 
Published: July 2006

Abstract
The relative values of the Soret coefficients of 0.01 M aqueous solutions of symmetric tetraalkylammonium chlorides (R4NCl, R=Me, Et, n-Pr, n-Bu, and n-Am) were determined by measuring the initial thermoelectric power of “combined thermocells” made up of AgCl electrode systems, taking LiCl as a reference. The results obtained were found to be rather high, higher by about 20% than those previously found on the combined thermocells made up of calomel-electrode systems.
Dielectric Relaxation and Molecular Structure. VIII. Dielectric Relaxation of Alkyl Acetates in Benzene Solution
Authors: Koga Yoshinori , Takahashi Hiroaki , Higasi Keniti 
Published: July 2006

Abstract
Dielectric constants and losses at the microwave frequency of 96.52 GHz have been measured at 25°C for methyl, ethyl, n-butyl, isobutyl, s-butyl, t-butyl, n-amyl, isoamyl, n-hexyl, and n-octyl acetates in benzene solutions. Static dielectric constants, refractive indices and densities have also been measured. The effective mean relaxation times of normal alkyl acetates increase with increasing chain length of the alkyl radical, eventually approaching a steady value. The distribution parameters α of all these molecules seem to have appreciable values which may be due to various segment orientations by internal rotation.
Thermal Decomposition Reaction of Halogenoammineruthenium(III) Halide Complexes
Authors: Ohyoshi Akira , Hiraki Shunichi , Kawasaki Hideo 
Published: July 2006

Abstract
The thermal decomposition of halogenopentaammine- and cis-dmalogenotetraammineruthenium(III) complexes was studied by the techniques of thermogravimetry(TG), differential thermal analysis(DTA), and evolved gas analysis (EGA). The stoichiometry of the decomposition reaction was determined by the analysis of the reaction intermediates and products. The order of decreasing thermal stability, as well as order of temperature of massloss initiation, seems to be: [RuCl(NH3)5]Cl2&gt;[RuBr(NH3)5]Br2&gt;[RuI(NH3)5]I2 for monohalogeno complexes, and cis-[RuCl2(NH3)4]Cl&gt;cis-[RuBr2(NH3)4]Br&gt;cis-[RuI2(NH3)4]I for dihalogeno complexes. Trihalogenotriammine complexes were observed as intermediates for the cases of dichloro and bromo complexes, a simple decomposition reaction was found for the iodo complexes, and then the activation energy for the following reaction was determined: [RuI(NH3)5]I2→RuI3+5NH3, Ea=41.9 kcal/mol and cis-[RuI2(NH3)4]I→RuI3+4NH3, Ea=27.8 kcal/mol. The reaction mechanisms may be summarized as follows: (a) an electron-transfer mechanism, in which the ruthenium(III) was reduced by the ammonia molecule or the halide ion, (b) the thermal splitting of the ruthenium-ammine bond, and (c) the bond formation between the ruthenium(III) and the halide ion after the ion migration from the outersphere to the innersphere of the complex. The predominant factors which control these mechanisms may be the coordinate bond strength of the ruthenium(III) and various ligand species, the relative potential of electron transfer from the ligand to the ruthenium(III), and the ease of halide-ion migration from the outersphere to the innersphere of the complex.
Kinetic Studies of the Electron Transfer Reaction in Iron(II) and Iron(III) Systems. VI. Reaction in N,N-Dimethylformamide
Authors: Wada Goro , Sahira Yoshiko , Ohsaki Kyoko , Shinoda Fusako 
Published: July 2006

Abstract
The electron transfer reaction between Fe(II) and Fe(III) in N,N-dimethylformamide (DMF) was found to be influenced by the presence of perchloric acid, chloride ion, and water in the reaction system. This suggests that the reaction involves chemical species such as partially hydrated iron, its deprotonated iron, and FeCl2+ and FeCl2+. The individual rate constants in DMF, containing a small amount of water, are k0=33.6 M−1s−1 for Fe2+–Fe3+, k1=1.2×102 M−1s-−1 for Fe2+–FeCl2+, and k2=∼103 M−1s−1 for Fe2+–FeCl2+ at μ=0.20 M and 25°C. The formation constant for FeCl2+ was determined to be K1=(2.0±0.3)×104 M−1 at μ=0.20 M and 25°C. In the mixed solvents of DMF and water, the apparent rate constant exhibited a minimum at a certain water concentration. The activation parameters for the reactions Fe2+–Fe3+ and Fe2+–FeCl2+ are ΔH0\eweq=8.3 kcal/mol, ΔS0\eweq=−24 cal/deg·mol, ΔH1\eweq=4.5 kcal/mol, and ΔS1\eweq=−34 cal/deg·mol, respectively. The results are compared with those in H2O, D2O, and DMSO.
Photoreactions of N-Vinylcarbazole Induced by Metal Salts. VI. Cyclodimerization Catalyzed by Copper(II) Perchlorate in Aprotic Solvents
Authors: Asai Michihiko , Matsui Hiroshi , Tazuke Shigeo 
Published: July 2006

Abstract
Photocyclodimerization of N-vinylcarbazole(VCZ) catalyzed by Cu(ClO4)2·6H2O(Cu(II)) in tetrahydrofuran was investigated under irradiation at 365 nm. At [Cu(II)]0=10−2 M in air, when [VCZ]0 was less than 0.4 M, only 1,2-trans-dicarbazylcyclobutane(D) was formed, but when [VCZ]0 was higher than 0.5 M, rapid cationic polymerization commenced after about 0.3 M of VCZ had been converted to D. Any consumption of Cu(II) could not be detected in the course of reaction. The change of reaction course from dimerization into polymerization in the midway of reaction was presumably brought about by the consumption of oxygen. Kinetic expression for dimerization rate(Rd) was obtained as follows:
R_d∞I_0^I.0[VCZ]_0^I.0[Cu(II)]_0^0
The quantum yield for D production was much larger than 1, indicating production of D via chain mechanism.
A Study of the Interaction of Diethylcadmium with Lewis Bases as Solvents
Authors: Nakasugi Osami , Ishimori Michihiro , Tsuruta Teiji 
Published: July 2006

Abstract
The infrared spectra of diethylcadmium(CdEt2) in a variety of different solvents were measured. The affinity of CdEt2 toward oxygen and sulfur bases was studied by infrared frequency shifts of CdEt2. Linear relationships were observed for the plots of the two frequency shifts Δνa(C–Cd–C) of CdEt2 vs. Δνa(C–Zn–C) of ZnEt2 and Δνa(C–Cd–C) vs. Δν(O–D) of CH3OD. The deviation of the plots for the systems of CdEt2 with cyclic sulfides from the linear behavior was interpreted in terms of dative back-bonding from CdEt2 to sulfides. The enhanced reactivity of the Cd–S compound toward propylene oxide compared to that of the Cd–O compound was considered to result from a harder acid character of the Cd atom in the Cd–S compound caused by its back-bonding nature.
Effect of Pressure on the Rate of Solvolysis. Volume Parameters and Solvolysis Mechanism
Authors: Yamagami Chisako , Sera Akira , Maruyama Kazuhiro 
Published: July 2006

Abstract
The effect of pressure on the solvolysis rates of representative primary, secondary, and tertiary tosylates was investigated in three representative solvents—formic acid, aqueous acetone, and methanol. The calculated activation volumes for these reactions were found to depend on the substrate structure and on the nature of solvent in a systematic manner. The activation volumes for kc-like reactions were less negative than those for ks-like reactions. In the case of the nearly ks-like reactions, the activation volume was found to be governed by the partial molal volume of the initial state.
Kinetic Studies on the Hydrolysis of Ethyl Benzenesulfinates
Authors: Kobayashi Michio , Nishi Ritsuko , Minato Hiroshi 
Published: July 2006

Abstract
The rates of hydrolysis of ethyl p-substituted benzenesulfinates were determined in acidic and alkaline media; the rates were greater in the former with the sulfinates containing electron-releasing substituents, ρ=−0.54 (20°C); and in the latter with the sulfinates containing electron-withdrawing substituents, ρ=1.60. The mechanisms of the hydrolysis are discussed.
Hydrogen Exchange Reactions of Sulfilimines and Sulfoximines
Authors: Kobayashi Michio , Mori Akira , Minato Hiroshi 
Published: July 2006

Abstract
Alkyl phenyl sulfilimines, benzyl phenyl sulfilimine and the corresponding sulfoximines were found to exchange their α-hydrogens with deuteriums in heavy water when the medium was alkaline. No exchange was observed when the medium was acidic or neutral. The rates of exchange in a sulfilimine were greater than those of the corresponding sulfoximine. The kinetics of these H-D exchange reactions were investigated by use of pyridine as a catalyst, and the reaction mechanism was discussed.
Cationic Arylation. VII. Cationic Phenylation and Benzoyloxylation of Aromatic Compounds with Benzoyl Peroxide in Trifluoroacetic Acid
Authors: Kamigata Nobumasa , Minato Hiroshi , Kobayashi Michio 
Published: July 2006

Abstract
Benzoyl peroxide (BPO) was decomposed in benzene in the presence of trifluoroacetic acid. The thermal reaction is first order in BPO, and the activation energy and activation entropy are 18.7 kcal/mol and −26.3 e. u., respectively. The isomer distributions in the phenylation and benzoyloxylation of substituted benzenes determined indicate that the phenylation and benzoyloxylation are electrophilic substitution reactions. The reaction mechanisms are discussed.
The Action of Alkali on Inosine. The Formation of 5-Amino-1-β-d-ribofuranosyl-4-imidazolecarboxamide and 9-β-d-Ribopyranosyl Hypoxanthine
Authors: Suzuki Yoshihisa 
Published: July 2006

Abstract
On treating inosine with aqueous dilute alkali hydroxide (pH 10) over 100°C, three types of reactions have been found to occur in competition with one another: (1) the hydrolysis of the glycosidic bond to give hypoxanthine and d-ribose, (2) the opening of the pyrimidine ring at C-2 to give 5-amino-1-β-d-ribofuranosyl-4-imidazolecarboxamide, and (3) the isomerization of the ribose moiety to give mainly 9-β-d-ribopyranosyl hypoxanthine. The last two are newly-found reactions, and the products were isolated through column chromatography using Dowex 50W. The products are obtainable in yields of 30 and 10% respectively under optimum conditions. Hypoxanthine was cleaved in an alkaline solution to give 5-amino-4-imidazolecarboxamide, and 5′-inosinic acid was supposed to give 5-amino-1-β-d-ribofuranosyl-4-imidazolecarboxamide-5′-monophosphate. The ring-opening reaction at C-2 was not observed for adenosine or guanosine.
Synthesis of Alkoxythallium(III) Compounds of Olefins and Their Reaction with Copper Halides and Pseudohalides
Authors: Uemura Sakae , Zushi Kazuo , Tabata Akira , Toshimitsu Akio , Okano Masaya 
Published: July 2006

Abstract
Some new alkoxythallium(III) compounds of olefins, C6H5C(R1)(OR3)CH2Tl(OCOR2)2 [I], are prepared from styrene and α-methylstyrene with thallium(III) acetate and isobutyrate in various alcohols. I(R1=H) reacts with copper(I) iodide, bromide, chloride, cyanide and thiocyanate to afford the corresponding alkyl halides and pseudohalides, C6H5CH(OR3)CH2X [II], in various organic solvents, acetonitrile being the solvent of choice for the purpose of preparing II. The addition of potassium salt has a remarkable effect in improving the yield of II. The halo- and pseudohalodethallation occur at the position where thallium is attached previously to alkyl carbon. An ionic concerted intermolecular scheme is proposed as a reaction mechanism for the preparation of II. The data of NMR and IR spectra of I are briefly discussed.
The Reduction of Methyl Acetate with Several Hydrosilanes under γ Irradiation
Authors: Nakao Ren , Fukumoto Tsugio , Tsurugi Jitsuo 
Published: July 2006

Abstract
The reduction of methyl acetate with chlorinated hydrosilanes, HSiCl3−nRn(R=CH3 or OCH3, n=0–2), and triethylsilane under γ irradiation has been studied. The hydrosilanes other than triethylsilane reduce the ester to ethyl methyl ether. The reaction rate is proportional to the hydrosilane concentration and is independent of the methyl acetate concentration. The results indicate that the rate-determining step in the reduction reaction is the hydrogen abstraction from the hydrosilanes. The reactivities of the chlorinated hydrosilanes in the reaction increase with the progressive chlorine substitution on the silicon atom and may be due to the susceptibility of each H–Si bond toward free radicals, (Remark: Graphics omitted.).
Chemistry of Nitrosoimines. VI. Attempted Syntheses of Some Resonance Stabilized Nitrosoimines and Their UV Spectra
Authors: Akiba Kin-ya , Matsunami Satoru , Eguchi Chikahiko , Inamoto Naoki 
Published: July 2006

Abstract
1,1,3,3-Tetrasubstituted 2-nitrosoguanidines, the attempted syntheses and UV spectra of which are reported, are unstable, and decomposed into the corresponding ureas and nitrogen, only 2-nitroso-1,1,3,3-tetraphenylguanidine (1f) being obtained as a pure compound. The reaction of 1f with phenyl isocyanate gave pentaphenylguanidine, probably through 1,4-cycloaddition.
Mechanisms for the Reaction of Phenol with Methanol over the ZnO–Fe2O3 Catalyst
Authors: Kotanigawa Takeshi 
Published: July 2006

Abstract
It was confirmed from the infrared spectra of phenol chemisorbed on ZnO–Fe2O3 that the surface species were characterized by a loss of O–H stretching (3250 cm−1) and by in-plane bending vibration (1370 cm−1) as well as by a phenol ring vibration (1472 cm−1) and a shift of the C–O stretching mode from 1230 cm−1 to 1248 cm−1. From these data, phenoxide surface species were proposed. Furthermore, the dissociative adsorption of phenol was discussed by taking account of the acidity and basicity of the catalyst. That is, in the case of the adsorption, phenol was thought to sit on the acid and the base site. Based on the above discussion, a mechanism for the selective methylation at the ortho position of phenol was proposed. On the other hand, it was found from the infrared spectrum that a surface species similar to zinc formate appears on the chemisorption of methanol. Therefore, it may be possible to consider that methanol adsorbed on the base site decomposes via formate-like surface species to form carbon dioxide, carbon monoxide, and hydrogen.
The Pore Structure of the ZnO–Fe2O3 Catalyst
Authors: Kotanigawa Takeshi , Yamamoto Mitsuyoshi 
Published: July 2006

Abstract
With regard to the ZnO–Fe2O3 catalyst used for the selective methylation at the ortho position of phenol, the pore structures of the catalysts prepared by five processes were studied. The pore structures of these catalysts were determined by converting the detailed nitrogen desorption isotherm data to the pore-volume distribution. These catalysts had two types of pores, a micropore at about 20 Å and a macropore at 80 Å or more. These pores were sensitive to the sintering conditions. The micropore sizes were independent of the calcination temperature, but the macropore sizes were made proportionally larger with a rise in the calcination temperature. The macropore sizes were related to the particle sizes of the zinc ferrite formed by the solid reaction of ZnO with Fe2O3.
The Electronic States of 2,5-Dibromo-3,6-dichloro-1,4-benzo-quinone and Its Anion Radical as Studied Means of Their Infrared Spectra
Authors: Iida Yoichi 
Published: July 2006

Abstract
The infrared spectra (400–4000 cm−1) of neutral 2,5-dibromo-3,6-dichloro-1,4-benzoquinone and its anion radical were measured in order to observe the appreciable frequency differences between their corresponding bands. The vibrational assignments were made and the simple Urey-Bradley force fields were determined for both the neutral 2,5-dibromo-3,6-dichloro-1,4-benzoquinone and its anion radical. The differences in the molecular and electronic structures between these two molecules were investigated on the basis of these experimental and theoretical results. The half-occupied molecular orbital of the anion radical was found to belong to the bg irreducible representation.
Radiation Synthesis of Ethylamine from Ethane–Ammonia Systems. Effect of Nitric Oxide Addition
Authors: Shimizu Saburo , Ikezoe Yasumasa , Sato Shoichi 
Published: July 2006

Abstract
Formation of ethylamine was observed in the γ-radiolysis of the ethane–ammonia system: the maximum G value was 0.5. Using oxygen as a radical scavenger, it was found that the ethylamine was formed via radical and ion intermediates. Addition of excess nitric oxide suppressed the ethylamine yield, but G(C2H5NH2) increased to 1.2 on addition of an optimum amount. This was attributed to the reduction of acetaldoxime by hydrogen atoms or alkyl radicals, after acetaldoxime had been formed by the reaction between ethyl radicals and the nitric oxide added as a scavenger.
Molten-state Absorption Spectra of Weakly Interacting Donor-Acceptor Mixtures
Authors: Aihara Jun-ichi 
Published: July 2006

Abstract
Absorption spectra of equimolecular mixutres of bulky electron donors, such as triphenylamine, and typical electron acceptors, such as sym-trinitrobenzene (TNB) and chloranil, in the molten state are reported. Though the components do not interact in the solid, the melts display distinct charge-transfer absorption bands in the visible region.
An EMF Study of Certain Orthoferrites: YFeO3, GdFeO3 and SmFeO3
Authors: Yamauchi Shigeru , Fueki Kazuo , Mukaibo Takashi , Nakayama Chiaki 
Published: July 2006

Abstract
The EMF of a solid electrolyte galvanic cell on the formation of orthoferrites, LnFeO3, was measured for Ln=Y, Gd and Sm at 1200–1400 K. The free energy change of the (1/2)Fe2O3+(1/2)Ln2O3→LnFeO3 reaction was calculated.
A New Optically Active Co(II) (salen) Type Complex Containing a Pentadentate Schiff-Base Ligand
Authors: Aoi Haruhiko , Yoshikawa Sadao 
Published: July 2006

Abstract
A new optically active square-pyramidal cobalt(II) complex, N,N′-bis(salicylaldehyde)-2-(S)4-S-methyl-4-thio-1,2-butanediiminatocobalt(II), was synthesized. The structure of this complex was examined.
Tetracyanoethylene Complexes of Ni(0) and Co(−1) Containing Isocyanides and Nitrosyl
Authors: Kawakami Katsuhiko , Ishii Kazuhiro , Tanaka Toshio 
Published: July 2006

Abstract
The magnetic equivalence of the isocyanides in Ni(RNC)3(TCNE) and Co(NO)(RNC)2(TCNE) is more likely to be due to the free rotation of TCNE in solution than to the dissociative exchange of ligands.
A Convenient Method for the Preparation of Aminoethyliminodiacetatocobalt(III) Complexes
Authors: Kuroda Kashiro , Ohtsuka Shuji , Matsumoto Noriko 
Published: July 2006

Abstract
Sodium dinitro(aminoethyliminodiacetato)-cobaltate(III) has been obtained by the oxidation of an aqueous mixture of cobalt(II) chloride, sodium nitrite, and a reaction product between ethylenediamine and sodium monochloroacetate. Several other complexes with the tetradentate ligand have also been derived from the dinitro complex.
Catalytic Function of Metal Salts on the Reduction of Pyridine-2-carbaldehyde by 1-Benzyl-1,4-dihydronicotinamide
Authors: Shirai Masamitsu , Chishina Taizo , Tanaka Makoto 
Published: July 2006

Abstract
A catalytic function of metal salts on the reduction of pyridine-2-carbaldehyde by 1-benzyl-1,4-dihydronicotinamide was discussed kinetically. The reduction rate was affected not only by the nature of metal cation but by that of counter anion.
Magneto-chemistry and Infrared Spectra of Ammonia and Primary Aliphatic Amine Complexes of Copper(II) Chromate
Authors: Sengar Babu Ram S , Narain Gopal 
Published: July 2006

Abstract
Complexes of divalent copper of the type CuCrO4·4Am and CuCrO4·2Am·2H2O with Am=ammonia or primary aliphatic amine, have been prepared and characterized. All the compounds reported are paramagnetic and values of μeff in the range 1.77–1.86 B.M. The assignment of the vibrational bands of the ligands and their shifts in frequency on co-ordination with copper(II) ion are discussed.
Amperometric Titration of Lead with Potassium Dithiotrihydroxymethyl Aminomethane and Its Determination in Presence of Mercury and Silver
Authors: Deshmukh G S , Chaudhuri H , Mahanti H S 
Published: July 2006

Abstract
Amperometric titration of lead with potassium dithiotrihydroxymethyl aminomethane at −0.2 V (vs. SCE) in ammoniacal ammonium tartrate-potassium nitrate base electrolyte (pH 8.0) has been carried out with a dropping mercury electrode. Lead has also been estimated in binary solutions with silver and mercury. The accuracy of the procedure is comparable to that obtained with classical methods.
A Novel Route to Menthyldiphenylphosphine
Authors: Tanaka Masato , Ogata Ikuei 
Published: July 2006

Abstract
As evidence of a novel, configurationallystable Grignard reagent, menthyldiphenylphosphine (MDPP) has been obtained by the reaction of diphenylphosphinous chloride with the Grignard reagent derived from menthyl chloride.
Epoxide Rearrangement II. Isomerization of 1-Methylcyclohexene Oxide over Solid Acids and Bases
Authors: Arata Kazushi , Akutagawa Susumu , Tanabe Kozo 
Published: July 2006

Abstract
The reaction of 1-methylcyclohexene oxide over solid acids and bases at 108 °C was found to give five main products, 2-methylcyclohexanone (III), 1-methylcyclohexanol (IV), 2-methyl-2-cyclohexene-1-one (V), 2-methyl-enecyclohexanol (VIa), and 2-methyl-2-cyclohexene-1-ol (VIb), with a small amount of 1-methylcyclohexene (I) and unidentified compound (II). The ketone (III) was formed predominantly over zeolite, SiO2–Al2O3, H2SO4/SiO2, AlCl3, and BBr3, while the allyl alcohol (VI) was given by Al2O3 and TiO2. HCl/SiO2 and solid H3PO4 calcined at 400–900°C gave both products, III and VI, in the same amounts, though the latter calcined at 200–300°C formed almost 100% ketone. Solid lithium perchlorate was surprisingly active for the formation of ketone, but other metal per chlorates and lithium salts were quite inactive. Alkaline earth metal oxides and NaOH/SiO2 were almost inactive. The catalytic activity and selectivity as well as the reaction path and mechanism are briefly discussed mainly in connection with acid-base property of solid catalysts.
Electron Scavenging Study on the Photobleaching of Trapped Electrons in 3-Methylhexane Matrices at 77 K
Authors: Oka Koichi , Yamazaki Hideo , Hatano Yoshihiko 
Published: July 2006

Abstract
The effect of addition of sulfur hexafluoride as an electron scavenger on quantum efficiency was investigated for the decay of trapped electrons in 3-methylhexane matrices at 77 K during photobleaching in the wavelength range 700–1900 nm. Since the quantum efficiency for the decay of trapped electrons in pure matrices is independent of the initial concentration, almost all the recombination of liberated electrons with the cations is geminate. The increase in quantum efficiency for the decay of trapped electrons by the addition of the electron scavenger SF6 was analyzed quantitatively. The quantum efficiency for the photoliberation of trapped electrons from the trapping sites may be about unity. The liberated electrons in the absence of the electron scavenger are retrapped or neutralized. The ratio of the former process to the latter at a wavelength greater than 1500 nm is much larger than that at a shorter wavelength. The wavelength dependence of the ratios of the electron scavenging process to these processes has also been discussed.