bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Magnetic Susceptibilities and ESR of Wurster’s Ions in Crystals
Authors: Tanaka Jiro , Inoue Motomichi , Mizuno Masagi , Horai Kazumi 
Published: July 2006

Abstract
The magnetic susceptibilities and the electron spin resonances of Wurster’s blue bromide, blue iodide, and red bromide have been measured over a wide temperature range. The results show that the paramagnetism of Wurster’s blue bromide above 210°K and of iodide can be explained by the linear Ising model, consistent with the crystal structure. Wurster’s blue bromide showed a deviation from the linear Ising model below 210°K; the dimer model is most appropriate for the explanation of the experimental data.
The intensities of the single ESR line are consistent with the results of the static susceptivility measurements. The hyperfine structures are not observed, perhaps because of the rapid movement of the triplet exciton. The magnetic results are explained in terms of the J-values, the origin of which are discussed on the basis of the interaction between the charge-transfer states and the singlet state. The values are resonably correlated with the interaction parameter, β, as estimated from the crystal structure and the electronic spectral measurements.
Steric Structure of l-Proline Oligopeptides. III. Calculated Absorption Spectra of l-Proline Oligopetides
Authors: Okabayashi Hirofumi , Isemura Toshizo 
Published: July 2006

Abstract
The electronic excited states in l-proline oligopeptides were derived from molecular-exciton theory. The dipole-dipole approximation was used in the calculation of transition energies. The calculated absorption spectra related to the conformation of l-proline oligopeptides were compared with observed ones. A satisfactory agreement between the calculated and observed results was obtained.
Base-catalyzed 1-3 Prototropic Isomerization of Cycloheptatrienes
Authors: Takahashi Kazuko , Yamamoto Hiroshi , Nozoe Tetsuo 
Published: July 2006

Abstract
The base-catalyzed proton migration (from the 7- to 2-position) and proton exchange (at the 7-position) of cycloheptatrienes carrying an electron-withdrawing group were studied in a medium of aqueous sodium hydroxide or alcoholic potassium hydroxide. The order of the effect of the various substituents upon the relative rates is approximately: CN&gt;CONH2&gt;COO−, Ph. The base-catalyzed prototropic isomerization proceeds through: i) the abstraction of a proton of the 7-position by the base, ii) the migration of the resulting carbanion to the allylic position (the rate-determining step), and iii) the recovery of a proton from the solvent. The kinetic study of the isomerization of 7-carboxycycloheptatriene (Ia) discloses the rate of the isomerization (k[the cycloheptatriene][base]) and the parameters (Ea=22.6 kcal/mol, ΔH\eweq=22.0 kcal/mol, ΔS\eweq=−15.4 e.u. at 60°). The structure of the cycloheptatrienyl anions formed as intermediates is discussed.
The Photosensitized Decomposition of Methyl Acetate at 77°K. A Kinetic Analysis of the Biphotonic Process
Authors: Mizutani Shigeru , Nakajima Yukihiko , Shimokoshi Kazuo , Sato Shin 
Published: July 2006

Abstract
The photosensitized decomposition of methyl acetate at 77°K has been investigated using an ESR technique. Naphthalene, α-naphthol, phenanthrene, anthracene, and benzophenone were used as sensitizers. When wavelengths longer than 2700Å were used, the formation of methyl radicals was observed except in the cases of anthracene and benzophenone. For the systems containing naphthalene, phenanthrene, and α-naphthol, the rate of the formation of methyl radicals was studied in detail and was found to obey the following relation:
R=αI^3/2C^1/2
Here, α is a proportional constant, I is the light intensity, and C is the solute concentration, which ranged from 5×10−5 to 2×10−3 mol l−1. Possible reaction mechanisms to explain the above relation were discussed; they include the biphotonic excitation of sensitizers, the triplet-triplet annihilation for the decay of the solute triplet, and the photolysis of the radicals produced in the photosensitization.
A Kinetic Investigation of Oxidation of Ethyl Methyl Ketone by Manganese(III) Sulphate
Authors: Banerji K K , Nath P , Bakore G V 
Published: July 2006

Abstract
The oxidation of ethyl methyl ketone with manganese(III) sulphate has been studied. The main product of oxidation is acetaldehyde. The reaction is first order with respect to each manganese(III) and the ketone. The rate of oxidation is independent of acidity and is not affected by changes in solvent composition. Addition of manganese(II) also does not affect the rate. The energy of activation, the entropy of activation and free energy of activation at 35°C have values 20.5 kcal/mol, −3.50 e.u. and 21.6 kcal/mol respectively. The rate of enolisation, measured by bromination method, is less than that of oxidation under similar conditions. A mechanism involving an attack directly on the ketone by manganese(III) sulphate-complex has been suggested.
Electronic Absorption Spectra of Zero-Valent Tris-(2,2′-bipyridine) Metal Complexes
Authors: Kaizu Youkoh , Yazaki Takanori , Torii Yasuo , Kobayashi Hiroshi 
Published: July 2006

Abstract
Electronic absorption spectra of zero-valent tris(2,2′-bipyridine) metal complexes of the first transition metals from titanium to cobalt have been studied. These spectra give a criterion to determine whether the central metal atom or the ligand is trapping the electrons furnished by reducing reagents upon syntheses of the complexes, if the absorption spectra of the coordinating negative ions are fairly free from the influence of the configuration interactions by the “ligand-metal” charge transfer excited states and/or by the “metal-ligand” ones. The vanadium complex is concluded as a complex of the metal atom in zero oxidation state and neutral bipyridine molecules, where the ‘metal-ligand’ charge transfer bands are observed. The iron- and the manganese-complexes are ionic complexes of the metal ion in a non-zero oxidation state and the negative ions of bipyridine, where the (π-π*) absorption bands of coordinating bipyridine negative ion are observed. On the basis of their spectral character, the complexes of the other transition metals might be assigned to be a hybrid of the two typical electron traps given above.
Chemical Effects Associated with the β-Decay Process. V. Kinetic Studies of the Chemical Behavior of the 144Pr Formed by the Decay of the 144Ce(III)-Ethylenediaminetetraacetate and 144Ce(III)-trans-1,2-Diaminocyclohexane-N,N′-tetraacetate
Authors: Shiokawa Takanobu , Kido Hiroaki , Omori Takashi 
Published: July 2006

Abstract
The chemical effects associated with the β−-decay of 144Ce(III)-aminopolycarboxylate complexes have been further investigated. The chemical behavior of 144Pr was analyzed kinetically on the basis of the isotopic exchange-reaction mechanism. The formation of the intermediate complex produced by an intramolecular electron transfer of the 144Pr(IV)-aminopolycarboxylate following the β−-decay of 144Ce(III) complex was also confirmed. In the ethylenediaminetetraacetate and trans-1,2-diaminocyclohexane-N,N′-tetraacetate systems, the values for the bond-rupture of the daughter complex ions are fairly much larger than in the diethylenetriaminepentaacetate system, suggesting that a kinetically-excited intermediate complex decomposes to a free ion to some extent.
The Copolymerization of Alkylene Glycol Nitrate Acrylates and Methacrylates
Authors: Moriya Masafumi , Yamashita Tadataka 
Published: July 2006

Abstract
The copolymerization of alkylene glycol nitrate acrylates (ANA) and methacrylates (ANMA) [M2] with styrene [M1] has been carried out at 60°C. The alkylene glycol mononitrates used were ethylene, propylene, and butylene glycol mononitrates, abbreviated as EGN, PGN, and BGN respectively. For their acrylates and methacrylates, the following abridged notations are used: ENA and ENMA, PNA and PNMA, and BNA and BNMA respectively. The monomer reactivity ratios, r1 and r2, and the Alfrey-Price Q2 and e2 values for ANA and ANMA were evaluated as follows: r1=0.48, r2=0.08, Q2=0.49, and e2=1.00 for ENA; r1=0.41, r2=0.20,Q2=0.69, and e2=0.78 for BNA; r1=0.35, r2=0.49, Q2=0.99, and e2=0.53 for ENMA; r1=0.36, r2=0.50, Q2=0.98, and e2=0.51 for PNMA and r1=0.37, r2=0.40, Q2=0.90, and e2=0.58 for BNMA. The polar and steric effects of the ester side chain containing the nitrate group were discussed. ANA was copolymerized with some other divinyl monomers, and the resulting crosslinked copolymer were subjected to the swelling test.
Multidentate Ligand Substitution Reactions. XI. Substitution Reactions of Nickel(II) Complexes of Diethylenetriamine and Ethylenediaminemonoacetic Acid with Diethylenetriaminepentaacetic Acid and of Nickel(II) Complexes of Diethylenetriamine and Ethylenediamine with Cyclohexane-1,2-diamine-N,N,N′,N′-tetraacetic Acid
Authors: Kodama Mutsuo , Fujii Yuki , Ueda Teiko 
Published: July 2006

Abstract
The kinetics of substitution reactions of nickel(II) complexes of diethylenetriamine and ethylenediaminemonoacetic acid with diethylenetriaminepentaacetic acid and those of diethylenetriamine and ethylenediamine with cyclohexane-1,2-diamine-N,N,N′,N′-tetraacetic acid were studied systematically by using the polarographic technique. All the reactions studied were found to be first-order with respect to the attacking group and also first-order with respect to the nickel(II) complex of diethylenetriamine, ethylenediamine, or ethylenediaminemonoacetic acid with a 1-to-1 composition. From a comparison of the relative rate constants determined experimentally with those calculated on the basis of a postulated reaction intermediate, the reaction mechanism was described in detail. All the reactions were concluded to proceed through the mixed ligand complex reaction intermediates which are characterized as having two nitrogen (amino) groups of displaced ethylenediamine, diethylenetriamine, or ethylenediaminemonoacetate ions bonded to the nickel(II) ion. This finding is contrary to the observation obtained by Rorabacher and Margerum from their kinetic study of the exchange reaction of the ethylenediaminetetraacetate anion with nickel(II) complexes of triethylenetetramine and tetraethylenepentamine.
Intramolecular Electron-transfer Reactions of Ethylenediaminetetra-acetatocobaltate(III) and Its Related Complexes in Solid State
Authors: Nagase Kenzo , Tanaka Nobuyuki 
Published: July 2006

Abstract
Electron transfer from a ligand to a central cobalt(III) in solid state was investigated by following the change of the valence state of coblat(III) to cobalt(II). The reaction was carried out in a vacuum as a function of sample amount, temperature and nature of a ligand and an outer-sphere cation. The electron-transfer reaction followed the first-order rate law. An outer-sphere cation had a slight effect on the reaction of the complex ion. The kinetic parameters obtained for potassium ethylenediaminetetraacetatocobaltate(III) (Ea=38 kcal/mol, A=1014) differed greatly from those for potassium propylenediaminetetraacetatocobaltate(III), potassium cyclohexanediaminetetraacetatocobaltate(III) and potassium trimethylenediaminetetraacetatocobaltate(III) (Ea\simeq 22 kcal/mol, A\simeq106). The kinetic behavior of the pentadentate complex, potassium hydrogen halogenoethylenediaminetetraacetatocobaltate(III), was compared with that of the hexadentate complex, potassium ethylenediaminetetraacetatocobaltate(III).
Trimethylenediamine Complexes. II. Some cis-trans Isomeric Pairs of Diacidobis(trimethylenediamine)cobalt(III) Complexes
Authors: Kawaguchi Hiroshi , Kawaguchi Shinichi 
Published: July 2006

Abstract
Isomeric pairs of cis- and trans-dinitro-, diisothiocyanato- and cyanosulfito-bis(trimethylenediamine)cobalt(III) complexes, and cis-nitronitritobis(trimethylenediamine)cobalt(III) nitrite were synthesized. Their electronic and infrared spectra were compared with each other to assign their structures. The cis-diisothiocyanatobis(trimethylenediamine)cobalt (III) complex was resolved into optically active isomers by means of potassium antimony(III) (+)-tartrate. The circular dichroism spectra of this dissymmetric complex were measured and discussed in relation to its absolute configuration which was recently determined by X-ray analysis.
Oxidative Coupling Reaction of Phenols with Dichromate
Authors: Tanaka Hiroo , Sakata Isao , Senju Ryoichi 
Published: July 2006

Abstract
On treatment in an aqueous solution with dichromate, p-cresol and creosol readily undergo nuclear oxidative coplig. The yields of dimeric and trimeric and trimeric cresols and of dimeric ketone are of the same order as the yields of the previously-recorded preparation by one-electron-transfer oxidants. When manganese sulfate is added, these yields are tripled. The probable mechanism of the coupling reaction of phenols with dichromate is discussed.
Photoreaction of Acetoacetate
Authors: Tada Masaru , Kokubo Tadayoshi , Sato Tadashi 
Published: July 2006

Abstract
Methyl acetoacetate was irradiated in the presence of cyclohexene to afford methyl 3-cyclohexyl-3-hydroxybutyrate (VIII), methyl 3-cyclohexenyl-3-hydroxybutyrate (IX), two oxetanes (Xa and Xb), and cyclohexene dimers. In contrast to acetylacetone, acetoacetate behaves as a saturated ketone rather than as an α,β-unsaturated ester on photoreaction. We concluded that the n-π* excitation of the enol-form of β-dicarbonyl compound is responsible for photo-cycloaddition, and no effective n–π* excitation is accesisble on irradiaron of the enol-form of acetoacetate, since the enol form of acetoacetate has its n–π* and π-π* absorptions in the same region.
A Study of Acyl Migration in Gallacetophenones
Authors: Kurosawa Kazu 
Published: July 2006

Abstract
3,4-Diacetoxy-2-hydroxyacetophenone, 3,4-dibenzoyloxy-2-hydroxyacetophenone and 3,4-bis(p-nitrobenzoyloxy)-2-hydroxyacetophenone gave corresponding 2,3-diacyl-4-methoxyacetophenones on treatment either with diazomethane or with dimethyl sulfate in the presence of potassium carbonate in acetone. Structure determination of the methylation product and also the methylation reaction of 3,4-dimethanesulfonyloxy-2-hydroxyacetophenone and 3,4-bis(p-toluenesulfonyloxy)-2-hydroxyacetophenone are reported.
Reaction of Olefin-Palladium(II) Chloride Complexes with Amides
Authors: Hirai Hidefumi , Sawai Hiroaki 
Published: July 2006

Abstract
Ethylene-palladium(II) chloride complex reacts with pyrrolidone and ε-caprolactam to produce N-vinylpyrrolidone and N-vinyl-ε-caprolactam, respectively. The yield of N-vinylpyrrolidone increases with increasing reaction temperature up to 120°C and decreases above 120°C owing to conversion of N-vinylpyrrolidone to an oily polymer through thermal polymerization. By addition of quinone, the yield increases remarkably at 25°C and 90°C. Pyrrolidone - palladium(II) chloride complex, which is too stable to react with ethylene at 25°C, reacts at 120°C to give N-vinylpyrrolidone. Open chain amides such as N-ethylacetamide, acetanilide and acetamide also react with ethylene - palladium(II) chloride complex, though the corresponding N-vinylamides cannot be obtained. The reaction of a styrene - palladium(II) chloride complex with pyrrolidone was also investigated.
Reactions of Haloferrocenes. III. The Reaction of Haloferrocenes with Copper(I) Benzenethiolate, Thiocyanate, Acetate, and Benzoate
Authors: Sato Masaru , Motoyama Izumi , Hata Kazuo 
Published: July 2006

Abstract
Iodoferrocene reacted with copper(I) benzenethiolate in boiling pyridine to give ferrocenyl phenyl sulfide in a quantitative yield. The reaction of iodoferrocene with copper(I) thiocyanate gave diferrocenyl disulfide. The behavior of copper(I) acetate and benzoate toward haloferrocene was found to be different from those of the other copper(I) salts: the reactions in boiling pyridine gave the corresponding ferrocenyl ester, together with a small quantity of ferrocene, while the reaction in boiling toluene produced biferrocenyl as the main product. The reaction mechanism of the ferrocenyl ester and biferrocenyl formations was discussed.
Studies on Fluorene Derivatives. XXVI. Radical Reactions in the Copyrolysis of Thermally-reactive Tribiphenylenepropanes
Authors: Suzuki Kazuo , Minabe Masahiro , Kubota Shozo , Isobe Taro 
Published: July 2006

Abstract
The pyrolyses of thermally-reactive tribiphenylenepropanes (mp 293°C (dec) or 257°C (dec)) in the presence of thermally-reactive 2,7,2′,7′,2″,7″-hexabromotribiphenylenepropane (mp 318–320°C (dec)) were investigated. Hydrocarbons, 2′,7′,2″,7″-tetrabromotribiphenylenepropane, 2,7-dibromo-9,9′-bifluorenyl, and -bifluorenylidene were obtained as pyrolysates from the respective thermal reactions, probably from intermolecular radical disproportionation reactions. In addition, 2,7,2′,7′-tetrabromo-9,9′-bifluorenyl, -bifluorenylidene, 2,7-dibromo-fluorene, and -fluorenone from hexabromotribiphenylenepropane, and 9,9′-bifluorenyl, -bifluorenylidene, fluorene, and fluorenone from tribiphenylenepropanes were formed by intramolecular reactions attributed to radical formation in the pyrolysis of each substrate. The pyrolyses of both tribiphenylenepropanes,. 9,9′-bifluorenyl and 2,7,2′,7′,2″,7″-hexabromotribiphenylenepropane, were observed in a differential scanning calorimeter. The thermogram of tribiphenylenepropane (mp 257°C) is similar to that of 9,9′-bifluorenyl; the first endothermic peak corresponds to the melting point, and the second, broad one seems to be due to the slow formation of 9,9′-bifluorenylidene from 9,9′-bifluorenyl by means of a dehydrogenation process. In the thermogram of tribiphenylenepropane (mp 293°C), the first endothermic peak is the melting point, while the second, small one is probably caused by the overlapping of exothermic and endothermic peaks due to radical reactions during the formation and pyrolysis of tribiphenylenepropane (257°C). The thermal homolyses of solid tribiphenylenepropane isomers or those in a silicon oil solution were examined by ESR, which confirmed the radical formation in the pyrolyses.
The Resolution and Rotations of trans-2-Aminocyclohexanecarboxylic Acids and Derivatives
Authors: Nohira Hiroyuki , Ehara Kenji , Miyashita Akira 
Published: July 2006

Abstract
Optically active trans-2-aminocyclohexanecarboxylic acids [(+)-1 and (−)-1] have been prepared by a preferential crystallization of racemic N-benzoyl trans-2-aminocyclohexanecarboxylic acid [(±)-2]. Active 2 have been used for preparation of such active trans-1,2-disubstituted cyclohexanes as (+)-, and (−)-ethyl trans-2-aminocyclohexanecarboxylate [(+)-3 and (−)-3], (+)-, and (−)-trans-2-aminocyclohexanemethanol [(+)-4 and (−)-4], (+)-trans-2-bromomethylcyclo-hexylamine hydrobromide [(+)-5], and (+)-trans-2-methylcyclohexylamine [(+)-6]. Amine-nitrous acid reaction of these cyclohexylamines to give the corresponding hydroxy compounds (7, 8, 9) has also been examined. It was confirmed that the signs of optical rotations of these hydroxy compounds are the same as those of the starting amines. It has been shown that observed molecular rotations of these active 1,2-disubstituted cyclohexanes are in agreement, in sign and order of magnitude, with those calculated following Brewster’s procedures presented in 1959 and in 1967.
Synthesis of Some New Fungicides
Authors: Choubey V N , Singh H 
Published: July 2006

Abstract
A number of 2-arylimino-3-aryl-4-thiazolidones and their 1,1-dioxides and 5-phenylazo derivatives have been prepared. The structure of these thiazolidones was confirmed by studying their hydrolysis products. Some of these thiazolidones were screened for their fungicidal activity against Aspergillus niger by agar-growth method and found to be more appropriately fungistatic and not fungicidal.
Studies of Ester-Containing Surfactants. Preparation and Properties of Sodium Sulfoalkyl Alkanoates
Authors: Hikota Takeshi 
Published: July 2006

Abstract
A series of sodium sulfoalkyl alkanoates, RCOO(CH2)jSO3Na, were prepared by means of sodium isethionate, propane sultone, and butane sultone with normal primary fatty acid composed of 10, 11, and 12 carbon atoms respectively. The effects of the position of the ester group on the Krafft point, the critical micelle concentration (CMC), the surface tention, and the other surface and colloidal properties of these surfactants were investigated. For a given number of carbon atoms, moving the ester group from the ionic head to a more central position in the hydrocarbon chain increased the CMC value and the calcium ion stalbility, and decreased the emulsion stability and the stability to hydrolysis. However, the wetting time was not strongly influenced by the position of the ester group in these compounds. The Krafft point of these surfactants decreased as the ester group was moved to a more central position.
Studies of the Aggregation of Dyes. The Scope of Application of the Maximum-slope Method
Authors: Hida Mitsuhiko , Sanuki Teruko 
Published: July 2006

Abstract
The maximum-slope method, previously suggested by one of the authors has proved to be more advantageously applied to the determination of the aggregation constant (Kn) and the degree of aggregation (n) in a dye solution than is Zanker’s method. Changes in the spectra of the aqueous or ethanolic solutions of Rhodamine 6G, 3,6-diaminoacridine and thionine were studied as their concentration increased by means of both the maximum-slope method and Zanker’s method. The aggregation characteristics obtained by these two methods were then compared with each other and discussed.
Magnetic Circular Dichroism of Iron Tetraphenylporphins
Authors: Kobayashi Hiroshi , Shimizu Masayuki , Fujita Ichiro 
Published: July 2006

Abstract
The magnetic circular dichroism of iron tetraphenylporphins was measured. Since the ground state of the open-shell iron porphin is degenerate and several charge-transfer excited states exist near the 1Q and 1B states, the A term as well as the B and C terms are very important for describing the MCD of the iron porphin, whereas the MCD at the 1Q and 1B bands, which arise from the pure degenerate (π,π*) excitations in D4h porphin assumed for zinc tetraphenylporphin, is ascribed to the A term. The MCD of carboxyhemoglobin, oxyhemoglobin and also deoxyhemologin was observed and compared with that of the synthesized iron porphins.
Aromatic Sulfonylation. I. Kinetics and Kinetic Isotope Effects in the Sulfonylation
Authors: Kobayashi Michio , Minato Hiroshi , Kohara Yoshio 
Published: July 2006

Abstract
p-Toluenesulfonylation of toluene, chlorobenzene and bromobenzene in the presence of aluminum chloride was investigated in methylene chloride at 0–20°C. The rate was equal to k3[TsCl][AlCl3][ArH]. Kinetic hydrogen isotope effects were found for p-deuteriotoluene (kH⁄kD=2.8) and p-deuteriochlorobenzene (kH⁄kD=1.98). Infrared studies indicated that not a sulfonyl cation but TsCl-AlCl3 complex was present in the medium. Substitution took place exclusively at para positions for halobenzenes, but 13.4% ortho and 86.6% para isomers were obtained for toluene. Partial rate factors for para positions were 52.5(PhCH3), 0.224(PhCl) and 0.164(PhBr). A plausible reaction mechanism was proposed, in which the abstraction of proton from the σ-complex was rate-determining.
Spreadability of Ovalbumin Monolayers at Air-water Interface
Authors: Ishii Toshio , Muramatsu Mitsuo 
Published: July 2006

Abstract
The spreading processes of ovalbumin have been studied quantitatively at air-water interface with either no additive or a small amount of hydrochloric acid for controlling subphase pH. Limiting area which is obtained by extrapolating force(F)-area(A) curve to F=0, increases with time, t, which has elapsed after the application of protein solution at the surface of subphase. Near the isoelectric point, the spreading processes are completed instantaneously to give the equilibrated value of limiting area which is found to be 0.83 m2/mg. The processes are much slower at both sides of the point, but the limiting area in equilibrium is found to be the same as in the case of isoelectric pH. It has also been shown that the processes are expressed in terms of two first-order reactions.