bluuebunny/crossref_metadata_2025_split huggingface dataset:
Spectrophotometric Determination of Anions by Solvent Extraction with Metal Chelate Cations. XIV Determination of Iodide Ions with Tris(1,10-phenanthroline)iron(II)
Authors: Yamamoto Yuroku , Tarumoto Tsunehiko , Tsubouchi Masahiro 
Published: July 2006

Abstract
Iodide was extracted from the aqueous phase into nitrobenzene in a wide pH range of 3–9 by use of tris(1,10-phenanthroline)iron(II) chelate cations and then determined spectrophotometrically at 516 mμ. Beer’s law was effective up to 8.0×105 m of iodide in the aqueous phase. Standard deviation of the determination was 1.1% at 15°C. The color intensity of the extracted species in nitrobenzene was constant for at least 3 hr. The distribution ratio was 1.02 at 15°C and 0.83 at 26°C. No serious interferences by foreign anions were observed except for perchlorate, chlorate, and thiocyanate. Cations did not essentially interfere with the determination.
Studies of 8-Mercaptoquinoline as Chelating Agents. I. Sodium Salt of 8-Mercaptoquinoline
Authors: Mido Yoshiyuki , Sekido Eiichi 
Published: July 2006

Abstract
The infrared spectra of the sodium salt of 8-mercaptoquinoline and its related compounds have been measured in the region between 4000 and 400 cm−1. Some substituent-sensitive bands have been investigated in order to find a clue to further infrared studies of its metal chelates. The thermal stabilities of the sodium salt have been examined by thermal gravimetric analysis and by differential thermal analysis. It has been shown that the sodium salt can be dried at temperatures between 100° and 200°C without any thermal change, and that, at ca. 210°C in air, the abrupt increase in weight of the sodium salt may be due to the absorption of oxygen. The effect of hydration on the sodium salt is discussed on the basis of results with regard to X-ray diffraction patterns, infrared spectra, and weights. The sodium salt is proposed to crystallize with two moles of water and to combine inequivalently with two waters of crystallization.
Studies of 8-Mercaptoquinoline as Chelate Agents. II. Infrared Absorption Spectra of its Divalent Metal Chelates
Authors: Mido Yoshiyuki , Sekido Eiichi 
Published: July 2006

Abstract
The infrared spectra of divalent metal thiooxinates have been measured in the region between 4000 and 400 cm−1, and the relationships between these spectral bands and the characteristics of the metal-ligand bonding and the structures of the thiooxinates have been discussed. The plots of the frequencies of the metal-sensitive bands around 990 and 670 cm−1 against the atomic weight of the metal make it possible to classify these metal thiooxinates into two groups, one of which includes Cu-, Co-, Ni-, and Mn-thiooxinate, and the other, Cd-, Zn-, and Pb-thiooxinate. The deviation of the point for Zn-thiooxinate from the line belonging to thiooxinates with such metal atoms as have no available d-orbitals has been compared with the case of oxinates. Moreover, from the appearance of the 450 cm−1 band in the latter group, the structure of these thiooxinates may be tetrahedral. As for the frequencies of the two metal-sensitive bands mentioned above, those of Pd- and Pt-thiooxinate are the highest and that of Ag(I)-thiooxinate, examined for the sake of comparison, is the lowest. The possibility of the analytical application of the metal-sensitive band around 670 cm−1 has been discussed.
The Infrared Spectra and Normal Coordinate Treatments of L3Sn-Mn(CO)5 (L=Cl, Br, CH3, and C6H5)
Authors: Onaka Satoru 
Published: July 2006

Abstract
The infrared absorption spectra (2200–60 cm−1) have been measured for four analogous compounds, Cl3Sn–Mn(CO)5, Br3Sn–Mn(CO)5, (CH3)3Sn–Mn(CO)5, and Ph3Sn–Mn(CO)5. Normal coordinate analysis has been made for three molecules-Cl3Sn–Mn(CO)5, Br3Sn–Mn(CO)5, and (CH3)3Sn–Mn(CO)5- on the basis of a modified Urey-Bradley force-field. The calculated frequencies attain close agreement with validly-assigned frequencies. The force constant, K(Sn–Mn), for each molecule varies with the substituent on the tin atom, and increases in the order of: K(Sn–Mn) of Cl3Sn–Mn(CO)5&gt;K(Sn–Mn) of Br3Sn–Mn(CO)5&gt;K(Sn–Mn) of (CH3)3Sn–Mn(CO)5. The vibrational eigenvectors reveal that the Sn–Mn stretching vibrational modes are considerably coupled with other vibrational modes, especially with CMnC deformation and axial MnC stretching modes.
Studies on Cobaloxime Compounds. VI. Decomposition of Formic Acid with Cobaloximes and Cobalamins
Authors: Hohokabe Yorikatsu , Yamazaki Noboru 
Published: July 2006

Abstract
Catalytic activities of cobaloximes in the decomposition reaction of formic acid were compared with each other and with those of cobalamins. In the cobalamin series, the activity decreased in the order aquocobalamin (vitamin B12a)&gt;methylcobalamin&gt;cyanocobalamin (vitamin B12). In the cobaloxime series, the activity decreased in the order Co(OH)(DH)2(H2O)&gt;CoCl(DH)2(H2O)&gt;Co(CN)(DH)2(H2O)&gt;CH3Co(DH)2(H2O). Cobalamins had much greater activities than the corresponding cobaloximes. The reaction proceeded with uptake of oxygen. No hydrogen gas was evolved in the reaction. The reaction rate slightly decreased with the increase of pH between 6.0 and 7.0. The reaction rate changes with 0.39 power of formic acid concentration less than 1×103 m (comparable to that of cobaloxime), and becomes independent of the concentration greater than 1×103 m. It changed with 0.89 power of the concentration of hydroxoaquocobaloxime. Aquocobalamin was reduced to B12r in the presence of formic acid but not hydroxoaquocobaloxime in anaerobic conditions. The catalytic activities of cobaloximes lower than the corresponding cobalamins were attributed to the higher reduction potentials of the former.
The Separation and Concentration of Acetylacetonato Chelates Using a Benzene Column
Authors: Maruyama Kazuo , Mashima Micho 
Published: July 2006

Abstract
This paper is concerned with the application of the zone-melting technique to metal-chelate compounds. An organic solvent which is liquid at room temperature such as benzene, and several acetylacetonato and thenoyltrifluoroacetonato chelates as solutes were prepared. The effective distribution-coefficient k dependence on the molecular weight was revealed by the normal freezing technique. In the deployment process, the acetylacetonato chelates of Fe and Th were chosen as solutes because their k values were different. The experiment was carried out at 2 cm/hr, the rate of zone travel. When a 30-cm column was used, the “removal percentages” of Fe from Th were 41 and 85% for 3 and 5 zone passes respectively. However there was a 22% loss of Th in the latter case. Furthermore, a remarkable concentration was found, and it was shown that the concentration effect may be useful for micro-analysis. At this stage, a relatively large bubble of benzene was observed at the liquid and solid interface; therefore we can call this “three-phase zone-melting.”
Organic Photochemical Reactions. XIV. The Photocycloaddition of Acetone to Cyclooctene and 1,3-Cyclooctadiene
Authors: Shima Kensuke , Sakai Yoshiki , Sakurai Hiroshi 
Published: July 2006

Abstract
The photocycloaddition of acetone to cyclooctene (COE) or 1,3-cyclooctadiene (COD) yields isomeric cis-and trans-oxetanes in good yields. Kinetic studies of these reactions reveal that the photoaddition of acetone to COE proceeds via the attack of the triplet acetone on the ground state COE, while the addition to COD probably occurs by the attack of the excited singlet acetone on the ground state COD.
Pd(II) Complexes with 2,2′-Diaminobiphenyl
Authors: Onaka Satoru 
Published: July 2006

Abstract
The new palladium (II) complexes with 2,2′-diaminobiphenyl (DABP) have been synthesized under various conditions. The hexa-coordinated palladium complex, [Pd(DABP)2Cl2], has been prepared under a high pressure. The square planar diamagnetic complexes, [Pd(DABP)2]X2 (X=Cl, Br), have been synthesized under atmospheric pressure. As to the [Pd(DABP)2]Cl2 complexes, two isomers, the yellow complex and the yellow-green complex, are obtained according to the temperature at which the complexes are synthesized. Both the complexes, the yellow and the yellow-green complexes, are similar with respect to the powder X-ray diffraction pattern and the IR spectra in the region from 4000 cm−1 to 200 cm−1, but are somewhat different with respect to the stability to air, the thermal stability, and the solubility in chloroform.
Fourier Analysis of Alternating Current Polarography: Amplitude and Phase of Fundamental and Second Harmonic AC Polarographic Waves
Authors: Kojima Hiroyuki , Fujiwara Shizuo 
Published: July 2006

Abstract
The Fourier analysis of the instantaneous AC polarographic current was performed with a computer on-lined to a potentiostat. From the Fourier spectra, the amplitudes and phase angles of both the fundamental and the second harmonic AC polarographic waves were obtained. In the Cd(II) system, the current amplitude DC potential curves and phase angle-DC potential curves for the fundamental and the second harmonic AC polarographic waves were compared with the theoretical curves. The method is applicable to the accurate analysis of electrode reaction kinetics.
The Reaction of Nitriles with Phosgene. V. Cyclization Reactions of N-(α-Chlorobenzylidene)carbamoyl Chloride
Authors: Yanagida Shozo , Yokoe Masaaki , Ohoka Masataka , Komori Saburo 
Published: July 2006

Abstract
N-(α-Chlorobenzylidene)carbamoyl chloride (1) reacts with hydrazine hydrate to give 3-phenyl-1,2,4-triazolone (2), with sodium azide in the presence of water to give 5-phenyltetrazole (3), and with aliphatic nitriles in the presence of hydrogen chloride to give 6-chloro-2-phenyl-5-substituted-4(3H)-pyrimidones (5) and 4,6-dichloro-2-phenyl-5-substituted pyrimidines (6). However, the reaction of 1 with trichloroacetonitrile or pivalonitrile in the presence of hydrogen chloride did not give the expected triazines.
Photochemical Rearrangement of N-Substituted Benzylanilines
Authors: Ogata Yoshiro , Takagi Katsuhiko 
Published: July 2006

Abstract
Photochemical migration of an alkyl group from nitrogen to ortho and para positions in N-substituted benzylanilines (I) has been studied. Quenching study suggests that the rearrangement proceeds via a triplet state. The rate of disappearance of N-(p-tolyl)-α-phenethylamine (III) in photolysis was found to be 3×107–3×108sec−1. Substituted benzylanilines (I) were synthesized to estimate their quantum yields of photorearrangement. A plot of the σ value for a substituent in the migrating benzyl group vs. logarithm of relative rate gives a positive ρ value with various quantum yields for intersystem crossing (0.1–1); the ρ value indicates that electron-withdrawing substituents in the benzyl group accelerate the rearrangement. A reaction scheme is presented.
The Synthesis of 7-Isopropyl-2,4-dimethylazulene (Se-Guaiazulene) from 4-Isopropyltropolone
Authors: Nozoe Tetsuo , Takase Kahei , Fukuda Satoko 
Published: July 2006

Abstract
7-Isopropyl-2,4-dimethylazulene (Se-guaiazulene) (I) was synthesized from 4-isopropyl-7-methyltropolone (II), which had itself been derived from 4-isopropyltropolone. The tropolone, II, was then converted to 3-acetyl-5-isopropyl-8-methyl-2H-cyclohepta[b]furan-2-one (VI) via the p-tolylsulfonyloxytropone derivative derived from II. The application of the azulene synthesis to VI gave 3-cyano-7-isopropyl-2,4-dimethylazulene-1-carboxylic acid (VII), from which I was obtained by the removal of the carboxyl and cyano groups.
The Bromination of 2-Methoxytropone and Its Bromo Derivatives
Authors: Nozoe Tetsuo , Takase Kahei , Yasunami Masafumi 
Published: July 2006

Abstract
The reaction of 2-methoxytropone and its bromo derivatives with bromine was examined in various solvents. The treatment of 2-methoxytropone or 5-bromo-2-methoxytropone with bromine in methanol gave an addition product, 2,6-dibromo-7,7-dimethoxy- (II) or 2,4,6-tribromo-7,7-dimethoxy-2,4-cycloheptadien-1-one (XIV) respectively, together with the substitution products. On the contrary, the treatment of 2-methoxytropone with bromine in anhydrous ethanol, chloroform, or carbon tetrachloride gave a reddish complex compound. In aqueous ethanol or acetic acid, however, it gave 3,5,7-tribromotropolone. A possible reaction mechanism involving the nucleophilic attack of a methanol molecule on 2-methoxytropones at the 2-position is presented to account for the formation of the addition products.
Linear Conjugated Systems Bearing Aromatic Terminal Groups. IV. The Syntheses of Some Diarylacetylenes
Authors: Akiyama Shuzo , Nakasuji Kazuhiro , Nakagawa Masazumi 
Published: July 2006

Abstract
The syntheses of 1,1′-, 9,9′-, and 1,9′-dianthryl-, 2,2′-, 3,3′-, and 9,9′-diphenanthryl-, 1,1′-and 2,2′-dipyrenyl-, and 6,6′-dichrysenylacetylenes according to the pyrolytic reactions of the corresponding β-ketoalkylidenetriphenylphosphorane derivatives (intramolecular Wittig reaction) were described.
The Reaction of Dihalotetramethylbenzenes with Fuming Nitric Acid as a New Convenient Route to Some Dihalotrimethylbenzylic Compounds
Authors: Suzuki Hitomi , Nakamura Kiyomi , Takeshima Michiko 
Published: July 2006

Abstract
Products obtained by the nitration of three isomeric dichloro and dibromotetramethylbenzenes with fuming nitric acid have been investigated. 3,6-Dihalo-1,2,4,5-tetramethylbenzene (dihalodurene) gave mainly 3,6-dihalo-2,4,5-trimethylbenzyl nitrate or 1,2-bis(nitrooxymethyl)-3,6-dihalo-4,5-dimethylbenzene, depending on the reaction temperature and the amount of nitrating agent. 4,6-Dihalo-1,2,3,5-tetramethylbenzene (dihaloisodurene) yielded a mixture of 3,5-dihalo-2,4,6-trimethylbenzyl nitrate and 2,6-dihalo-3,4,5-trimethylbenzyl nitrate, the latter in somewhat greater amount. 5,6-Dihalo-1,2,3,4-tetramethylbenzene (dihaloprehnitene) gave 5,6-dihalo-2,3,4-trimethylbenzyl nitrate as the sole nitrooxylation product. The reaction affords a new convenient route to precursors of various polysubstituted benzylic compounds hitherto not easily obtained by ordinary methods. Physical properties of some dihalotrimethylbenzylic compounds (chloride, nitrate, acetate, alcohol, and bisbenzyl ether) have been recorded.
Nitration of Pentamethylnitrobenzene, Pentamethylbenzoic Acid and Its Methyl Ester, Pentamethylacetanilide, and Pentamethylphenol and Its Methyl Ether. Orienting Effect of the Substituents for the Side-chain Nitrooxylation
Authors: Suzuki Hitomi , Nakamura Kiyomi 
Published: July 2006

Abstract
The nitration of a series of the titled pentamethylbenzene derivatives has been investigated in order to know the orienting effect of substituent groups for the side-chain nitrooxylation. The nitrooxylation was found to occur almost exclusively at the methyl groups adjacent to the electron-withdrawing substituents (NO2, COOH, and COOCH3), while with the compounds containing electron-donating groups (OH and OCH3) the main reaction led to the conversion into cyclohexadienone, with the concomitant formation of small amounts of meta-nitrooxylated product. Pentamethylacetanilide underwent side-chain nitrooxylation along with some deacetylation. The location of the nitrooxymethyl group seems to be most likely ortho and meta, the latter being predominant.
An Acoustical Study of the Kinetics of Intermolecular Hydrogen Bonding and the Applicability of the Hammett Rule
Authors: Yasunaga Tatsuya , Nishikawa Sadakatsu , Tatsumoto Nobuhide 
Published: July 2006

Abstract
Rate and equilibrium constants for the hydrogen-bond dimerization of benzoic acid and meta- and parasubstituted compounds in N,N-dimethylformamide have been determined by the measurement of the ultrasonic absorption in the 15–95MHz frequency range at 20°C, and the Hammett rule for the rapid monomer-dimer reaction has been examined. The forward and backward rate constants are 0.67×108 sec−1 and 2.8×107 sec−1 m−1 for para-toluic acid, 0.90×108 sec−1 and 1.9×107 sec−1 m−1 for meta-toluic acid, 1.6×108 sec−1 and 1.5×107 sec−1 m−1 for benzoic acid, 2.1×108 sec−1 and 2.4×107 sec−1m−1 for para-chlorobenzoic acid, and 3.3×108sec−1 and 1.6×107 sec−1m−1 for metachlorobenzoic acid respectively. The forward and backward activation enthalpies for benzoic acid are 8.4 kcal/mol and 3.3kcal/mol respectively. Using the substituent constants in Jaffe’s table, the reaction constants in the Hammett rule are calculated to be 1.2 and −0.33 for the forward and backward reactions respectively.
Electronic Structures of Tris(2,2′-bipyridyl) Complexes of Transition Metals in Lower Oxidation States
Authors: Hanazaki Ichiro , Nagakura Saburo 
Published: July 2006

Abstract
The electronic structures of various transition metal complexes with 2,2′-bipyridyl in low oxidation states are studied theoretically by the composite system method. The results show that the excess electrons are not localized on the metal ion but are transferred to some extent to the ligand antibonding π-molecular orbitals with the lower oxidation states of complex ions. The present theory can explain reasonably and systematically the observed magnetic moments and ESR spectra of the complexes, the simple one-electron treatment being inappropriate for a theoretical explanation of their magnetic properties. According to the present treatment, their electronic absorption spectra can be explained satisfactorily from a qualitative point of view as the overlapping of the π–π* transition bands in the ligands with the metal-ligand charge-transfer transition bands.
Mixed Monolayers of Poly(methyl acrylate) and Its Saponified Polymer
Authors: Hironaka Seiichiro , Kubota Takashi , Meguro Kenjiro 
Published: July 2006

Abstract
A film balance study of the mixed monolayers with various ratios of poly(methyl acrylate) and its saponified polymer or of the monolayers themselves was carried out on distilled water, and the mixed monolayers were compared with individual monolayers of the saponified polymers. These mixed monolayers expanded more than individual saponified polymers at the same degree of saponification, giving larger limiting areas. Their limiting areas deviated from the linearity between the limiting area and the degree of saponification, in contrast to the fact that the limiting areas of individual monolayers decreased linearly with an increase in the degree of saponification. This fact can be considered to be due to interactions between the side chains of the ploymers.
CNDO Calculations of Electronic Structures and Spectra of Nonalternant Conjugated Hydrocarbons
Authors: Tajiri Akio , Ohmichi Naoto , Nakajima Takeshi 
Published: July 2006

Abstract
The energetically most favorable geometrical structures with respect to C–C bond-length variation of fundamental nonalternant conjugated hydrocarbons have been examined using CNDO/2 approximation with its original parameterization. It was found that all the molecules examined should exhibit a marked bond alternation, accompanied with a molecular-symmetry reduction in the case of pentalene and heptalene. The predicted molecular dipole moments are in good agreement with the available experimental values. The electronic spectra have been calculated using a modified version of the CNDO/2 method proposed by Del Bene and Jaffe, with a new parameterization. The results are found to be in good agreement with experiment.
Magnetic and Thermal Properties of Crystals Including Isolated Clusters. II. Heat Capacity of Co3(C5H5)3S2 from 15 to 270 K and Mechanism of Phase Transition
Authors: Sorai Michio , Kosaki Akio , Suga Hiroshi , Seki Syûzô , Yoshida Toshikatsu , Otsuka Sei 
Published: July 2006

Abstract
Heat capacity of Co3(C5H5)3S2 was measured between 15 and 270 K. A phase transition was discovered at 192.5±0.1 K with the transition enthalpy and the entropy of 5253.4 J mol−1 and 28.894 J K−1 mol−1, respectively. The transition entropy is well described as the sum of the configurational entropy of Rln8 due to cyclopentadienyl rings and the magnetic contribution of Rln4. The transition behavior is satisfactorily accounted for in the whole temperature region investigated in terms of the cooperative coupling between the orientational motion of the rings and the electronic states of a molecule on the basis of the Chesnut exciton model modified by the present authors. The model proposed here is to take both the temperature dependences of the energy parameters and the inversion of the spin state at higher temperatures into account. The measurements of infrared spectra and proton magnetic resonance were made as a function of temperature. These results are favorable to the present model. The electron spin resonance experiment also confirmed the present model.
The Formation Constants and Composition of Tetraethylenepentamineheptaacetato Nickel(II) Complexes measured by a Potentiometric Titration Method
Authors: Masuda Yoshitaka , Hirai Yukiko , Sekido Eiichi 
Published: July 2006

Abstract
Stability constants for nickel(II) complexes of tetraethylenepentamineheptaacetic acid (TPHA: H7L) were determined by the pH titration method. In an aqueous solution (μ=0.1) three uninuclear complex species, NiH2L, NiHL, and NiL, and a binuclear compound, Ni2L seem to exist. The structures of uni- and bi-nuclear chelates are discussed with their visible absorption spectra. Formation of the hydroxo complex was not observed on the titration curves. In the present investigation no evidence was found for species of Ni2HL either. The formation constants of the complexes stated above have been calculated as follows, (at 25±0.1°C). logKML=16.18, logKMHL=10.00, logKMH2L=6.16, logKM2L=17.35 and logKML2=27.78.
Polarographic Study of the Rates of the Dissociation Reactions of the Cobalt(II)-Acetylacetonate Complex and of the Nickel(II)-Acetylacetonate, -Glutamate, -Aspartate, and -Iminodiacetate Complexes
Authors: Kodama Mutsuo , Nunokawa Hisao , Oyama Noboru 
Published: July 2006

Abstract
The cobalt(II)-acetylacetonate complex and the nickel(II)-acetylacetonate, -glutamate, -aspartate and -iminodiacetate complexes were found to give kinetic waves due to the dissociation of these complexes at the electrode surface preceding the electron-transfer step. From the experimental examination of the nature of the kinetic current and a theoretical consideration, the mechanism and the rate constants of the dissociation of these complexes at the mercury-electrode surface were determined. The dissociation reactions were found to proceed through the following mechanism:
MX22−m\ightleftharpoonsMX2−m+Xm− rapid
MX2−m\oversetkd\ightleftharpoonsM2++Xm− slow
M++2e−+Hg=M(Hg)
The rate constants, kd′s, for the dissociation reactions of cobalt(II)-acetylacetonate complex and of nickel(II)-acetylacetonate, -glutamate, -aspartate, and-iminodiacetate complexes at 25°C were estimated to be 9.30, 0.56, 0.69, 1.21×10−2, and 2.5×10−4 sec−1 respectively. From a comparison of the rate constants, the dissociation of nickel(II)-aminopolycarboxylate complexes was concluded to proceed invariably through a reaction intermediate in which the leaving aminopolycarboxylate anions is bonded to the nickel(II) ion through one nitrogen and one oxygen atoms (Glycinate intermediate). In the formation reactions of cobalt(II)- and nickel(II)-acetylacetonate complexes in a 1:1 ratio, the dissociation of coordinated water from the metal(II) ion is rate-determining (water-loss mechanism).