bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electronic Structures, Electronic Spectra, and Aromatic Characteristics of Peri-Condensed Tetracyclic Nonbenzenoid Aromatic Hydrocarbons Containing a Naphthalene Nucleus
Authors: Yamaguchi Hiroyuki , Nakajima Takeshi 
Published: July 2006

Abstract
The ground-state electronic properties and electronic spectra of pyracylene (I), acepleiadylene (II), and dipleiadiene (III) have been studied by using the semi-empirical SCF LCAO-π-MO method, which allows for bond order-bond length correlation at each iteration. It is shown that the I and III molecules do not belong to, respectively, the pentalenoid and heptalenoid systems, as was expected from the HMO energy diagram. The predicted chemical reactivities, diamagnetic anisotropics, and electronic spectra for I and II are in good agreement with the available experimental data. The calculated C–C bond lengths indicate that the I, II, and III molecules are all both aromatic and polyolefinic. The upfield shift of the NMR spectrum and the unusually low value of the first half-wave potential for I can be well explained in terms of, respectively, the diamagnetic anisotropy and the energy of the lowest vacant SCF MO, calculated by using the predicted equilibrium configuration that corresponds to the aromatic model (Ia).
Studies of Organic Peroxides. XI. The Reaction of Benzoyl Peroxide with Secondary Amines in Binary Mixed Solvents
Authors: Hasegawa Shigeo , Kashino Setsuo , Mukahi Yoshinobu 
Published: July 2006

Abstract
The rate constants of the reaction of benzoyl peroxide with some typical secondary amines, namely, diphenylamine, N-methylaniline, and piperidine, were measured in benzene-nitrobenzene binary mixed solvents. The reaction rates of diphenylamine and N-methylaniline are little influenced by the compositions of the solvents, while the reaction of piperidine proceeds more rapidly in nitrobenzene than in benzene. The isokinetic relationship holds for the reaction of piperidine in the binary mixed solvents. The isokinetic temperature is calculated to be 265°K. The analysis of the behavior of these reactions in the mixed solvents leads to the conclusion that, in the cases of diphenylamine and N-methylaniline, there are no specific interactions between the activated complexes and solvent molecules, whereas in the case of piperidine the activated complex is weakly solvated with the polar nitrobenzene. The reaction of benzoyl peroxide with N-methylaniline and N-n-butylaniline was also studied in benzene. These amines have a higher reactivity than would be expected from their basicity. This higher reactivity is probably due to the resonance stabilization of the activated complex besides the formation of a lessionic activated complex.
A Polarographic Study of the Complex Formation Equilibria of the Lead(II) Ion with Aspartic and Iminodiacetic Acids
Authors: Kodama Mutsuo , Takahashi Sozo 
Published: July 2006

Abstract
In this experiment, we studied the complex formation equilibria of the lead(II) ion with aspartic acid and iminodiacetic acid by using the polarographic method. In acetate buffer solutions (5.80&gt;pH&gt;3.70), the lead(II) ion forms one normal complex, PbX0, and two mixed ligand complexes involving the acetate ion, PbX(Ac)−and PbX(Ac)22−, with aspartic acid. On the other hand, with iminodiacetic acid, it forms a normal complex, PbX0, and only one mixed ligand complex, PbX(Ac)−. By observing the effects of the concentrations of the hydrogen ion, the acetate ion, and aspartic acid or iminodiacetic acid on the half-wave potential of the lead(II) ion, their formation constants were determined to be as follows:
(Remark: Graphics omitted.)
Derivatographic Studies on Transition Metal Complexes. IV. Deaquation-Olation of Hydroxoaquo Cobalt(III) Complexes with Aminotricarboxylic Acids.
Authors: Tsuchiya Ryokichi , Uehara Akira , Kyuno Eishin 
Published: July 2006

Abstract
Thermochemical functions of the deaquation-olation on K[Co(OH)L4(H2O)] type complexes in the solid phase were determined by means of derivatography and UV spectral measurements and the mechanisms were discussed on the basis of the results. In the above formula, L4, denotes nitrilotriacetate (nta), nitriloisopropionicdiacetate (nipda), d,l-α-amino-n-butyric-N,N-diacetate (α-abda), l-leucine-N,N-diacetate (lda), l-valine-N,N-diacetate (vda), d-α-phenylglycine-N,N-diacetate (pgda), or d,l-α-phenylalanine-N,N-diacetate (pada) ions. These complexes were found to liberate one mole of coordinating water upon heating and to turn into the olated compound bridged with two OH groups at the same time. From an estimation of enthalpy change and activation energy for the reaction, it was found that the reaction is apt to take place more easily as the structural complexities of chelating agents increase and that the reaction always proceeds in the first order. We might conclude that the evolution of coordinating water is the rate-determining step in the reaction.
Derivatographic Studies on Transition Metal Complexes. V. Thermal cis, trans-to-trans, cis Isomerization of [CoCl2(NH3)2en]ClO4 in Solid Phase
Authors: Tsuchiya Ryokichi , Nakata Yasuo , Kyuno Eishin 
Published: July 2006

Abstract
The complex, cis,trans-[CoCl2(NH3)2en]ClO4, regardless whether its state is monohydrate or anhydride, was isomerized to trans,cis-form by heating in a solid phase. In the kinetic study on perchlorate in a closed system, it was found that the isomerization of the hydrated compound proceeded through a second order reaction with respect to the remaining fraction of the starting compound with the activation energy, E≠=29.5 kcal mol−1, while that of the anhydrous one proceeded through a first order reaction with E≠=51.4 kcal mol−1. On the other hand, derivatographic analyses showed that the enthalpy change in the dehydration partly including isomerization was ΔH=13.9 kcal mol−1 for the monohydrated perchlorate and the activation energy was E≠=39.9 kcal mol−1, whereas the enthalpy change of isomerization of the anhydrous perchlorate was ΔH=−2.1 kcal mol−1. From the results, it is believed that the “Aquation-anation” mechanism on the crystal surface is predominant in the isomerization for the hydrate, but it proceeds through some intramolecular reactions for the anhydride.
Synthesis of Iron-Titanium Oxides under Hydrothermal Conditions
Authors: Matsuoka Kiyoshi 
Published: July 2006

Abstract
The solid solutions in the system FeO-Fe2O3-TiO2 were synthesized under hydrothermal conditions up to 700°C and 2.5 kb (PH2O). The results of X-ray diffraction, chemical and thermomagnetic analyses indicated that the products always consisted of magnetite-ulvöspinel or hematite-ilmenite solid solutions and, in some cases, rutile was also formed. The presence of the solid solutions of magnetite and ulvöspinel indicates a reducing atmosphere during the treatment. When PH2O increased from 1 kb to 2.5 kb, the FeO contents in the products decreased.
119Sn-Mössbauer and 1H- and 55Mn-NMR Spectroscopic Studies of a Series of Compounds, R3−xXxSn-Mn(CO)5
Authors: Onaka Satoru , Sasaki Yukiyoshi , Sano Hirotoshi 
Published: July 2006

Abstract
The electronic configuration around the tin atom for a series of organotin-manganese compounds, R3−xXxSn–Mn(CO)5, has been studied by 119Sn-Mössbauer and 1H- and 55Mn-NMR spectroscopies. All the results obtained from these spectroscopic measurements show that the Mn(CO)5 group is a stronger electron donor than the methyl, phenyl, or halogen group and that the tin-manganese bond prefers the sσ-character whereas the tin-halogen bond prefers the pσ-character. The relationship between the 55Mn-chemical shift and the 119Sn-isomer shift indicates some σ-electron withdrawal from manganese to tin. The phenyl group reduces the magnitude of quadrupole splitting more than the methyl group; this fact may be due to the mesomeric effect of the phenyl group through the π-bond between tin and ligand atoms. The relationship among the 119Sn-isomer shift, the 1H-chemical shift, and the coupling constant J(119Sn-1H(CH3)) is also shown.
The Determination of Tin in Tin Metal and in Zircaloy by Precise Coulometric Titration
Authors: Yoshimori Takayoshi , Matsubara Ikuko , Tanaka Tatsuhiko , Yoshida Kazuo , Tanaka Kazuo , Tanabe Toyokazu 
Published: July 2006

Abstract
The purities of tin metals are determined directly by precise coulometric titration. The sample is dissolved with hydrochloric acid in a nitrogen atmosphere. The solution is then introduced into a hot antimony column. The reduced tin(II) ions are titrated with electrolytically-generated iodine. The titration is accomplished in a special cell by the use of which any disturbance of atmospheric oxygen is avoided. The titration efficiency under these acidic media was decreased when the current density was increased more than several mA/cm2. The results obtained by two different analysts for the sample of the pure tin metal (5-nine) were 99.996 and 99.991%. The standard deviations of the results were 0.025 and 0.016% respectively. The tin in the other tin metals and in Zircaloy samples was determined satisfactorily without the use of any experimental factor.
The Preparation and the Structure of (1,9-Diamino-1,4,6,6,9-pentamethyl-3,7-diazanona-3-ene) (l-propylenediamine)nickel(II) Perchlorate
Authors: Ito Haruko , Fujita Junnosuke 
Published: July 2006

Abstract
A new purple complex of (1,9-diamino-1,4,6,6,9-pentamethyl-3,7-diazanona-3-ene) (l-propylenediamine)nickel(II) perchlorate and the known yellow complex, (octamethyl-1,4,8,11-tetraazacyclotetradecadiene)nickel(II) perchlorate, were obtained by the reaction of tris(l-propylenediamine)nickel(II) perchlorate and acetone without any irradiation by ultraviolet light. The structure of the purple complex was estimated from its absorption and circular dichroism spectra in acetonitril and in an aqueous solution, and from its infrared spectrum in the solid state. The complex was found to take an octahedral [NiN6]-type structure in acetonitril and a planar [NiN4]-type structure in aqueous solution. The (1,9-diamino-1,4,6,6,9-pentamethyl-3,7-diazanona-3-ene)nickel(II) perchlorate and (1,9-diamino-1,4,6,6,9-pentamethyl-3,7-diazanona-3-ene)(ethylenediamine)nickel(II) perchlorate complexes were also prepared.
Studies of the Interaction between the Picrate Ion and Alkali Metal Ions
Authors: Yamane Mitsuo , Iwachido Tadashi , Tôei Kyoji 
Published: July 2006

Abstract
Alkali metal picrates in an aqueous solution are extractable by nitrobenzene. The investigations of the equilibria in and between the aqueous and organic phases show that the larger the association constants in the aqueous phase and the dissociation constants in the organic phase, the greater the extractability of the salts. The extremely low extractability of alkali metal picrates can be well explained in terms of such equilibrium constants.
A Study of the Catalytic Partial Oxidation of Hydrocarbons. VI. The Effect of Molybdenum Addition to the Vanadium Oxide Catalyst on the Oxidation of Butene to Maleic Anhydride
Authors: Ai Mamoru 
Published: July 2006

Abstract
In the present work, the vapor-phase partial oxidation of cis-2-butene was carried out using V2O5-MoO3 catalysts with different compositions, at 350°C, and at a butene content of 0.65% in air, in order to elucidate the effect of the addition of MoO3 to the V2O5 catalyst on the selectivity and the mechanism for maleic anhydride formation. Two types of catalytic specificities were found, depending upon the Mo content: in the range of less than 20 atom% Mo, the specificity was similar to that of V2O5 alone, while in the range of more than 50 atom% Mo, a different specificity was observed, one which gave 1.2 times the yield of maleic anhydride than did V2O5 alone or the Mo-poor catalysts. The increase in the selectivity of butene to maleic anhydride which occurred when a large amount of MoO3 was doped is considered to be caused by the increase in the selectivity of the C4H4O→MA step, not in that of the C4H8→C4H6 or C4H6→C4H4O step. The selectivity of the side pathway in the C4H8→C4H6step was so great that no satisfactory maleic anhydride yield from butene can be expected by the use of the V2O5-MoO3 catalyst.
Effective Intramolecular Hydrogen Abstraction by the Sulfonamide Radical
Authors: Ohashi Takehisa , Takeda Shinichi , Okahara Mitsuo , Komori Saburo 
Published: July 2006

Abstract
To study the reactivity of the sulfonamide radical in various reaction systems, the photodecomposition of N-t-butyl and N-methyl-N-chloroalkanesulfonamides was investigated. In benzene, the competitive hydrogen abstraction by the chlorine atom occurred to an appreciable extent and the participation of the chlorine atom was retarded with N2-flow control. In an aqueous solution (AcOH-H2O, t-BuOH-H2O), the quantitative conversion to γ-and δ-chloroalkanesulfonamide was observed; this was thought to be due to the intramolecular hydrogen abstraction by the sulfonamide radical and to the lowering of the reactivity of the chlorine atom because of the solvation by H2O. In an acid solution (AcOH-H2O-H2SO4), a higher preference for 1,5 hydrogen transfer was found; this was caused by the protonated sulfonamide radical. The formation ratio of γ- to δ-chloroalkanesulfonamide in several solvents was determined, and the reactivity of the sulfonamide radical was discussed. From the reaction products obtained, several aliphatic sultams were synthesized.
The Kinetics of the Reaction of Thiol Acids with Anilines
Authors: Hirabayashi Yoshio , Mizuta Masateru , Kojima Masana , Horio Yukio , Ishihara Hideharu 
Published: July 2006

Abstract
Studies have been made of the kinetics of the reactions of thiol acids (thiostearic acid and thioacetic acid) with anilines, such as aniline and p-methoxy-, p-ethoxy-, p-methyl-, m-methyl-, p-chloro, m-chloro-, and m-nitrosubstituted anilines, in a chlorobenzene solution. The rate is given by k(RCO–SH) (X-C6H4-NH2). The activation energy for the reaction of thiostearic acid with aniline is 5.3 kcal/mol. The Hammett plots give a straight line, with a value of ρ=−2.40 for the reactions of thiostearic acid or thioacetic acid with the anilines; the mechanism of the reaction of thiol acids with anilines is discussed.
Studies on Heteroaromaticity. LII. Syntheses and Reactions of α-Acetylenic Ketones Containing Nitrofuran Ring
Authors: Sasaki Tadashi , Yoshioka Toshiyuki 
Published: July 2006

Abstract
2-(5-Nitro-2-furyl)-1-phenyl- (IVa), -p-methylphenyl- (IVb) and -(2-furyl)-acetylene (IVc) were prepared by condensation of nitrofurfural with the corresponding aryl methyl ketones, followed by bromination and dehydrobromination. Addition of aniline and cyclohexylamine to IVa afforded simple adducts Va and VIa respectively. Treatment of IVa,b with hydroxylamine, hydrazine hydrate, semicarbazide and benzamidine gave isoxazoles (VIIIa,b), pyrazoles (VIIIa,b), 1-carbamidopyrazoles (IXa,b) and pyrimidines (Xa,b) respectively. When treated with benzonitrile oxide at room temperature, IVa afforded isoxazole XIa together with furoxan, but the thermal 1,3-dipolar reactions of IVa,b with 5-nitro-2-furocarbonitrile oxide afforded exclusively isoxazoles XIIa,b. For comparison, 5-nitro-2-furfurylidenebenzophenone (IIa) was treated with benzonitrile oxide at room temperature to afford an isomeric mixture of the isoxazolines XIIIa and XIVa together with furoxan. Similar treatment of 5-nitro-2-furfurylideneacetone afforded similar results affording a mixture of XV and XVI together with furoxan. When treated with phenacylpyridinium ylide, IVa,b afforded pyrrocolines XVIIa,b. The structural elucidation of the products was carried out on the basis of the spectral data.
Syntheses of 1,2,3-Trisubstituted 4-Aminoimidazolium Salts
Authors: Chinone Akiko , Sato Sigeru , Ohta Masaki 
Published: July 2006

Abstract
The salts of new mesoionic compounds of imidazole ring system having imino group at 4 position were synthesized by the reaction of amidines with haloacetonitriles. The resulting 4-amino-1,2,3-triphenylimidazolium salt was treated with sodium hydroxide to give an intermediate, N-cyanomethyl-N,N′-diphenylbenzamidine, which gave the salt of mesoionic imidazole with dry hydrogen bromide. 1,2,3-Trisubstituted 4-aminoimidazolium salts were treated with acetic anhydride or with picric acid or with silver perchlorate to give acetylated derivative, picrates and perchlorates, respectively.
An Interpretation of Mass Spectra of Disubstituted Benzenes by Simple LCAO MO Calculation. I
Authors: Tajima Susumu , Wasada Nobuhide , Tsuchiya Toshikazu 
Published: July 2006

Abstract
A part of the mass spectra for derivatives of aniline and anisole was interpreted using the results of MO calculation. Compounds studied were: aniline derivatives: o-, m-, and p-compounds of anisidine, aminophenol, chloroaniline, nitroaniline, aminobenzoic acid, and aminoaeetophenone; and anisole derivatives: o-, m-, and p-compounds of anisidine, methoxyphenol, chloroanisole, nitroanisole, methoxyben zoic acid, and methoxybenzaldehyde. The intensities of certain fragment ions in the mass spectra of these compounds were compared with the results of simple LCAO MO calculation for these compounds. A simple relation was found between the intensity and the partial bond order for a frontier electron of the bond ruptured.
Purity Determination of Organic Compounds by a Newly Designed DTA Apparatus
Authors: Mashiko Yo-ichiro , Shinoda Takako , Enokido Hisae 
Published: July 2006

Abstract
An apparatus of differential thermal analysis has been designed and constructed for the purpose of determining the purity of organic compounds with as small an amount of sample as possible, within a short time and yet with an accuracy of better than ±0.001 mol%. Degussa platinum thermometers were used. They were calibrated with a precision of better than ±0.004° against a standard platinum resistance thermometer. Methods for determining the impurities in samples on the basis of irreversible thermodynamics have been developed. The results were compared with those obtained by using an adiabatic calorimeter of our laboratory and by the National Bureau of Standards. The apparatus proved to be useful in determining the purity of about 1 ml of samples, whose melting points lie in the temperature range −200°C–+200°C within an accuracy of ±0.004 mol% in about 1.5 hr.
Normal Coordinate Treatment and Force Constants of Alkanonitriles
Authors: Fujiyama Tsunetake 
Published: July 2006

Abstract
Force constants of the Urey-Bradley type are calculated for a series of alkanonitriles. The calculation covers the mononitriles: CH3CN, CH3CH2CN, (CH3)2CHCN, (CH3)3CCN, and the dinitriles: NCCH2CN, NCCHDCN, NCCD2CN, trans-NCCH2CH2CN, gauche-NCCH2CH2CN. The results show that the force constants can be transferred from molecule to molecule as a group. It is also shown that a group of force constants is characteristic of a corresponding chemical structure or a substituent.
Polarized Absorption Spectra of Single Crystals of Ion Radical Salts. II. K(TCNQ) and Cs2(TCNQ)3
Authors: Hiroma Shoji , Kuroda Haruo , Akamatu Hideo 
Published: July 2006

Abstract
Polarized absorption spectra in the 10–40 kK region were observed on single crystals of the ion radical salts of tetracyano-p-quinodimethane (TCNQ), potassium·(TCNQ) and cesium2·(TCNQ)3. The crystal spectra are shown to be markedly different from the solution spectra of the monomer and dimer of TCNQ ion. It is shown that the 7.8 kK band of K(TCNQ) and the 11.1 kK band of Cs2(TCNQ)3 are charge-transfer bands associated with the transfer of an electron from a TCNQ− ion to the neighboring TCNQ− ion. The first-order and second-order effects were calculated on the local-excitation bands in order to explain the general feature of the observed spectra.
Studies on Salt Solution Aerosols. V. The Effect of Surface Active Substance upon the Droplet Size of an Aqueous NaCl Solution Aerosol
Authors: Ueno Yasuo , Sano Isamu 
Published: July 2006

Abstract
An aqueous NaCl solution (10%) containing a surface active substance was dispersed to a mist with a Dautrebande type atomizer. The influence of the surface active substance on the droplet size and mass concentration of the mist during aging was studied. We examined ethyl alcohol, acetic acid, ethyl acetate, acetone, glycerine, and a commercial nonionic surfactant. From the results it was found that at an early stage of aging, the droplet number present in mist was inversely proportional to the fourth power of droplet size.
The Catalytic Oxidation of Hydrogen on Titanium Dioxide; Anatase and Rutile
Authors: Onishi Yoshito 
Published: July 2006

Abstract
To clarify the reaction mechanism of catalytic oxidation of hydrogen on titanium dioxide, the rate of catalytic oxidation of hydrogen by oxygen and the reduction rate of titanium dioxide by hydrogen have been measured by a static method in temperature range of 400–650°C at 10−2 mmHg. The results were compared with those of carbon monoxide which were reported in the previous papers. The oxidation reactions of hydrogen on anatase and rutile were first order with respect to hydrogen and independent of the oxygen pressure. The oxidation rate was almost the same as the reduction rate of titanium dioxide by hydrogen. The activation energy was 29.2 kcal/mol for anatase and 17.8 kcal/mol for rutile, and the difference between these values for two crystal forms was nearly equal to that of the oxidation of carbon monoxide. Therefore, it may be considered that the mechanism of oxidation of hydrogen is analogous to that of carbon monoxide. The electric conductivity of the catalyst during the oxidation of hydrogen was larger than that in oxygen at the same temperature, and was still larger than that during the oxidation of carbon monoxide except for a few cases on anatase. There were close correlations between the electric conductivity and the amount of active oxygen of the catalyst and the reduction rate constant of titanium dioxide by both hydrogen and carbon monoxide.
Electron Donor-acceptor Complexes between Group IV Tetrahalides and Methylbenzenes
Authors: Hatano Masahiro , Ito Osamu 
Published: July 2006

Abstract
The charge-transfer bands of the loose complexes between Group IV tetrahalides (chlorides and bromides) and methylbenzenes were observed, and the electron affinities of these tetrahalides were systematically evaluated from these observed charge-transfer bands. The semi-empirical molecular orbital calculations (the extended Hiickel method) for these tetrahalides revealed that the tetrahalides interact with the benzene ring using the vacant molecular orbital involving the empty d atomic orbital of the halogen atom in the tetrahalides. Moreover, the meanings of the electron affinities estimated in this study were discussed in terms of the molecular orbitals, by comparing them with the values of the electron affinities evaluated by other methods.