bluuebunny/crossref_metadata_2025_split huggingface dataset:
Rate-controlling Processes in the Phosphidation of Copper by Phosphorus Vapor
Authors: Sasaki Yoshinori , Ueda Shiro 
Published: July 2006

Abstract
The phosphidation kinetics of a copper exposed to a phosphorus atmosphere from 1 to 10 Torr absolute pressure in the temperature range of 150–250°C have been determined with a closed system. The reaction rate in the earlier periods of time was linear and, subsequently, parabolic; therefore, it can be considered that the rate-determining process changes from adsorption to diffusion. The linear rate constants were expressed as a function of the phosphorus pressure on the basis of the Langmuir adsorption isotherm. The P4 molecule is chemically adsorbed as two —P=P—, whereas at higher temperatures and pressures the solubility process appears to be predominant. From the phosphorus distribution in cross sections of scaling films, it has been revealed that, in the adsorptoincontrolled regions, the phosphorus content is maintained at a constant concentration, corresponding to Cu3P, and that, in the diffusion-controlled regions, solid solutions more rich in phosphorus than Cu3P are formed at the outer layers. The faceted crystals of Cu3P have sometimes developed with an orientation of the (300) plane, depending on the reaction conditions.
Ternary Diffusion in the 20Ne–22Ne–CO2 System
Authors: Oishi Yasumichi , Sugisaki Masayasu , Kamei Yoshinobu , Shono Yasuyuki 
Published: July 2006

Abstract
Self-diffusion coefficients of CO2 of the binary system of Ne and CO2 were measured for the whole composition range at 25°C under 760 mmHg. The system was also analysed as a ternary system of 20Ne, 22Ne, and CO2. The isotope separation of 20Ne and 22Ne during the course of diffusion was measured and analyzed by means of the ternary diffusion equations obtained by an extension of Darken’s binary diffusion equation. The experimentally observed 22Ne/20Ne ratios agreed well with the values calculated by the equations. The results show that the concept of the intrinsic diffusion flux density, introduced by Darken for binary diffusion, is valid and applicable to ternary diffusion in the gaseous system.
Photochemistry of Acridines. XVIII. Photoreduction by Nonpolar H-donors and the Disproportionation of C-Radicals
Authors: Hoshino Mikio , Niizuma Shigeya , Koizumi Masao 
Published: July 2006

Abstract
It was found that the photoreduction of acridine in cyclohexane and toluene occurs via molecular and radical mechanisms. The T-energy transfer experiments using biacetyl as an energy acceptor have revealed that the molecular mechanism occurs in the T(n–π*) state, and the radical in the singlet excited state. The effect of the addition of piperylene on the quantum yield of photoreduction was investigated in cyclohexane, methanol, ethanol and isopropanol. The results have been interpreted on the following assumptions. 1) Complete T-energy transfer from acridine to piperylene. 2) No quenching action of piperylene on the singlet excited acridine. 3) Complete transformation of C-radicals of acridine to stable products by piperylene. The results have led to the conclusion that the C-radical undergoes disproportionation in cyclohexane, methanol and ethanol, while it is completely transformed to an acridan-type compound in isopropanol.
The Catalytic Exchange of Hydrogen-Deuterium on Copper-Nickel Alloy Plates after Various Surface Treatments
Authors: Takasu Yoshio , Yamashina Toshiro 
Published: July 2006

Abstract
The catalytic activities of nine copper-nickel alloys (5 cm2 in area) in hydrogen-deuterium exchange were examined at 1.5 Torr partial pressures of hydrogen and deuterium, using an ultra-high vacuum apparatus incorporated with an omegatron mass spectrometer for continuous gas analysis. Without any surface treatment, the activity was greatest on pure nickel, decreased gradually as the content of copper in the alloys increased and virturally vanished in the alloys containing copper more than 70%. The activity of each alloy sample was observed to be extremely enhanced by a slight surface treatment of oxidation-reduction (Po2=2.3 Torr at 500°C for 1 min, PH2=16 Torr at 300°C for 2 hr). The activity of the 85% copper alloy after the oxidation-reduction treatment was greatest, one hundred times that of pure nickel. Annealing for a short time in an ultra-high vacuum subsequent to the oxidation-reduction treatment caused the catalytic activity to decrease abruptly at a critical temperature (425°C). On the bases of the electron microscopic observations and the measurement of the surface roughness changed by the pre-treatments, the nature of active sites on copper-nickel alloys was discussed.
Infrared Absorption Intensities of Out-of-plane CH Bending Vibrations of Substituted Benzenes. IV. Solvent Effect on the Intensities of the Bands of Aniline
Authors: Higuchi Seiichiro , Kuno Eisaku , Tanaka Shigeyuki , Kamada Hitoshi 
Published: July 2006

Abstract
The infrared absorption intensities of out-of-plane CH bending and ring out-of-plane deformation vibrations of aniline have been measured in an acetone solvent mixed with various quantities of acetic acid. When such solvents are used, new peaks attributable to aniline interacting with the acid appear as shoulders of each of the original bands. A marked decrease in the sums of the intensities of the above two modes (Ao) has been observed for the bands of aniline interacting with the acid. It is demonstrated that the degree of such a decrease in intensity depends on the molar ratios of aniline and the acid. When there exists enough the acid in comparison with aniline, the values of Ao become minimum. On the other hand, when the numbers of the exsiting acetic acid molecules are much smaller than those of aniline, the values of Ao are considerably greater than those in the former case. In this case, a farily long time is needed until the interaction reaches an equilibrium state. Finally, when a very large amount of the acid is added, the bands attributable to aniline interacting with the acid are no longer observed. An attempt has been made to interpret these phenomena in terms of the state of the aggregation of aniline, acid and acetone molecules in the solutions.
Properties of Water in Macromolecular Gels. IV. Proton Magnetic Resonance Studies of Water iu Macromolecular Gels
Authors: Aizawa Masuo , Mizuguchi Jun , Suzuki Shuichi , Hayashi Shoichi , Suzuki Teruo , Mitomo Noriko , Toyama Hiroshi 
Published: July 2006

Abstract
Electrochemical and dilatometric studies have indicated that at least three states of water exist in macromolecular gels. The properties of each state of water in gels such as agarose gels were investigated by highresolution and broadline PMR over the temperature range from +50 to −60°C. The linewidth of water protons in gels was found to depend markedly on the water content of gels, and the linewidth vs. water content curve gave two inflection points. One of the inflection points can be attributed to the so-called bound water, but the other cannot be explained unless three states of water are assumed in gels. Three kinds of transition temperatures were confirmed by anomalous changes in the PMR linewidth below 0°C. The so-called bound water exhibited no transition temperature between 0 and −20°C, and free water gave the transition temperature at 0°C. Moreover, the transition temperature of a quantity of water was distributed in the range from 0 to −20°C. On the basis of the transition temperature, the properties of water in macromolecular gels are discussed.
Molecular Vibrations, Conformational Analyses, and Force Fields of Normal and Monodeuterated (Methylthio)methanethiol
Authors: Ohsaku Masaru , Shiro Yuji , Murata Hiromu 
Published: July 2006

Abstract
(Methylthio)methanethiol, CH3SCH2SH, and (methylthio)methanethiol-d1, CH3SCH2SD, were prepared, and their infrared spectra were obtained in the gaseous, liquid, and solid states. The obtained spectra have been assigned. The frequency shifts by D-substitution, gaseous-liquid transition, and liquid-solid transition have also been discussed. The normal coordinates of these thiols have been treated by a modified Urey-Bradley force field. The force constants used in the computation have been transferred from those previously reported, but we adjusted them to produce the experimental wave numbers. The calculated wave numbers correspond well with those observed. The stable molecular conformations of the normal and deuterated species have been determined by the aid of the normal coordinate treatment. In the gaseous and liquid states, at least three to four forms from among TT, TG, GT, GG, and GG′ have been confirmed to exist. In the solid state, though, CH3SCH2SH or GH3SCH2SD exists in only one form: GG.
Order of Quencher Participation in Photochemistry. II. Quenching Action of Ethanol on the Photoreduction of p-Aminobenzophenones
Authors: Hoshino Mikio , Koizumi Masao 
Published: July 2006

Abstract
The effect of the addition of ethanol (quencher of the reaction) on the photoreduction of p-aminobenzophenone (NH2BP) and dimethyl-p-aminobenzophenone in cyclohexane and in ether has been studied. The order of quencher participation for ethanol has been found to be two for the former and one for the latter. The results were interpreted to be due to the formation of intramolecular C–T state during excitation, promoted by the attachment of one ethanol (or ether) molecule to the NH2-group and one ethanol molecule to O=C of NH2BP.
Heat Capacities of Antimony Trichloride and Tribromide
Authors: Takeyama Kuniko , Atoda Tetsuzo 
Published: July 2006

Abstract
Heat capacities of liquid antimony trichloride and tribromide saturated with their respective vapors were determined with an adiabatic calorimeter as follows: 35.2 cal K−1mol−1 in the range, 90–210°C, for trichloride, and 34.6 cal K−1mol−1 in the range, 130–270°C, for tribromide.
Electronic Spectra and Structures of Organic π-Systems. III. Electronic Spectra of Nitrocyclopentadienide Anion and Formylcyclopentadienide Anion
Authors: Yoshida Zen-ichi , Kobayashi Tsunetoshi , Konishi Akihiko 
Published: July 2006

Abstract
The electronic spectra of sodium nitrocyclopentadienide and sodium formylcyclopentadienide have been measured in several solvents. The electronic states of these compounds have been calculated by variable integrals methods I and II (modified Pariser-Parr-Polpe method). The longest wave-length strong absorption band of nitrocyclopentadienide (304 mμ) or formylcyclopentadienide (280 mμ) in isooctane has been assigned to the superimposed band of two intramolecular chage-transfer transitions from the five-membered ring to the nitro or formyl group. Agreement between the calculated and observed transition energies in isooctane is satisfactory.
The Kinetics of Electron-transfer Reactions between Oxalato-Cobalt(III) Complexes and Iron(II) in Acid Aqueous Solutions
Authors: Ohashi Kousaburo 
Published: July 2006

Abstract
An investigation of the Fe2+ reductions of Co(ox)(NH3)4+, Co(ox)(en)2+, Co(ox)(trien)+, Co(ox)(dip)2+, Co-(ox)2(en)−, and cis-Co(ox)2(NH3)2− has been carried out spectrophotometrically. The rate constants of Co(ox)N4+-type complexes increase in this order: Co(ox)(phen)2+&gt;Co(ox)(dip)2+&gt;Co(ox)(NH3)4+&gt;Co(ox)(en)2+&gt;Co(ox)-(trien)+, and these of Co(ox)2N2−-type complexes, cis-Co(ox)2(NH3)2−&gt;Co(ox)2(en)−. The variation in reactivity is mainly ascribed to a change in the enthalpy of activation. The rate constants of Co(ox)(NH3)4+, Co(ox)(en)2+, cis-Co(ox)2(NH3)2−, and Co(ox)33− increase with the values of the hal-wave potential of the polarographic reduction (CoIII→CoII) and with the decrease in the wave number of the maxima of the absorption spectra of the complexes.
Stereoselectivity in Mixed Tris-type Complexes of Cobalt(III) with Glycine and l-Glutamic Acid
Authors: Kawasaki Kiyoshi , Shibata Muraji 
Published: July 2006

Abstract
The following ten complexes have been isolated from a reaction mixture of the [CoCO3(gly)2]− ion and l-glutamate in the presence of active charcoal: mer-[Co(gly)2l-glutH] (two isomers), mer-Cogly(l-glutH)2], mer-Λ-[Co(l-glutH)3],fac-Λ and Δ-[Co(gly)2(l-glutH], fac-Λ and Δ-[Cogly(l-glutH)2], and fac-Λ and Δ-[Co(l-glutH)3]. These complexes have been characterized by various spectral data. The Δ/Λ ratios in the fac isomers have been estimated to be ca. 60/40, 68/32, and 75/25 for the bis(glycinato), bis(l–glutamato) and tris(l–glutamato) complexes respectively, while no appreciable stereoselectivity has been found in the corresponding mer isomers.
Derivatographic Studies on Transition Metal Complexes. VIII. Thermal Deaquation-Anation Reaction of cis-[CoX(H2O)N4]Y2 Type Complexes in Solid Phase
Authors: Tsuchiya Ryokichi , Suzuki Masatatsu , Kyuno Eishin 
Published: July 2006

Abstract
The deaquation-anation reaction of cis-[CoX(H2O)N4]Y2 type complexes, where X is chloride or bromide ion, N4 is tetraammine or bis(ethylenediamine), and Y is chloride, bromide or nitrate ion, was investigated by means of both derivatographic and isothermal methods. Some of these reactions were found to include the stereochemical changes, the structure of reaction products formed by deaquation-anation reaction being considerably affected by the counter ionic species: the chloride complexes, where Y=Cl, were deaquated with retention of cis-structure, whereas the bromide complexes, where Y=Br, underwent cis-to-trans stereochemical change. According to the isothermal measurement in the isomerization of cis-[CoCl(H2O)en2]Br2·H2O, cis-[CoCl(H2O)en2]-Br(NO3) and cis-[CoBr(H2O)en2]Br2·H2O, these rates were found to obey the first-order rate law and the activation energies, Ea, were obtained to be 38±5, 68±6 and 37±5 kcal mol−1 and the enthalpy changes, ΔH, 13.5±2.0, 7.5±2.0 and 13.3±2.0 kcal mol−1 for the respective complexes.
Electronic Spectra and Structures of Organic π-Systems. IV. Electronic Spectra of Nitropyrroles
Authors: Yoshida Zen-ichi , Kobayashi Tsunetoshi , Yamada Hidenori 
Published: July 2006

Abstract
The electronic spectra of 2-nitropyrrole and 3-nitropyrrole have been measured in various solvents and compared with the values calculated by the variable integrals method II. Agreement between the observed and the calculated transition energies is satisfactory. From eigenvectors of both nitropyrroles, the localization of molecular orbitals to the moiety of molecule has been discussed. The π-electon densities and π-bond orders of both molecules have also been calculated.
Reactions of Cuprous Acetate with Organic Halides
Authors: Kawaki Takao , Hashimoto Harukichi 
Published: July 2006

Abstract
Cuprous acetate was prepared from phenylcopper and acetic acid, and its reactivity for organic halides was investigated. The mixed anhydrides containing an acetyl group are formed easily from cuprous acetate and acyl halides. The reaction of cuprous acetate with CH3I, C2H5I, CH2=CHCH2Br, and PhCH2Cl in acetonitrile gives the corresponding ester. The addition of ethylenediamine converts the above reaction to a reductive coupling reaction, resulting in bibenzyl (50% yield) from benzyl chloride and 1,5-hexadiene (95–98% yield) from allyl chloride or bromide. The reaction of cuprous acetate-ethylenediamine with aryl bromide or iodide in DMF gives a reductively dehalogenated product, i.e., the corresponding hydrocarbon, in a small yield.
The N1→N2 Migration of the s-Triazinyl Group of 4-Substituted N1,N1-Bis-(s-triazinyl)-o-phenylenediamines
Authors: Nakamura Kenji , Nohara Noboru , Matsui Kohji 
Published: July 2006

Abstract
Several 4-substituted N1-[bis-(diethylamino)-s-triazinyl]-N1-(dimethoxy-s-triazinyl)-o-phenylenediamines were synthesized, and the migrations of the s-triazinyl group were investigated in these compounds. In methanol, every 4-substituted N1,N1-bis(s-triazinyl)-o-phenylenediamine gave only 4-substituted N1-[bis-(diethylamino)-s-triazinyl]-N2-(dimethoxy-s-triazinyl)-o-phenylenediamine by the migration of the dimethoxy-s-triazinyl group; the rearrangement was assumed to proceed through an intramolecular nucleophilic attack by the ortho amino group upon the ring carbon of the dimethoxy-s-triazinyl group. However, in the presence of a small amount of acid, the N1→N2 migration of the bis(diethylamino)-s-triazinyl group occurred preferentially, and two kinds of rearranged products were obtained. The kinetics of the rearrangement have also been studied spectrophotometrically in methanol, and the effects of the substituents on the rearrangement have been discussed.
The Stereochemistry of Nucleophilic Addition. V. The Reformatsky Reaction of 2-Phenylpropanal with Methyl α-Bromopropionate
Authors: Matsumoto Takashi , Hosoda Y\={u}kei , M\={o}ri Kiyomi , Fukui Kenji 
Published: July 2006

Abstract
The Reformatsky reaction of 2-phenylpropanal (I) with methyl α-bromopropionate gave the diastereomeric methyl 3-hydroxy-2-methyl-4-phenylvalerates, IIa, IIb, IIe, and IId, in a 5 : 24 : 16 : 55 ratio. The configurations of these β-hydroxy esters were assigned by the following experiments. The reduction of IIa–IId with LiAlH4 gave the corresponding diols, IIIa–IIId, which were then converted to the monotosylates, IVa–IVd. The further reduction of IVa or IVc and IVb or IVd with LiAlH4 gave the epimeric 2-methyl-4-phenyl-3-pentanols, V and VI respectively. Since V and VI were also obtained as minor and major products (20 : 80 ratio) of the Grignard reaction of I with isopropylmagnesium iodide, the configurations of the C-3 and C-4 positions in IIa–IId were assigned. The Wittig reaction of I with carbomethoxyethylidenetriphenylphosphorane gave methyl 2-methyl-4-phenyl-2-cis-pentenoate (VII) and its trans-isomer (VIII), which were then reduced to the corresponding alcohols, IX and X respectively. The cis-hydration of IX gave IIIc and IIId, while a similar treatment of X gave IIIa and IIIb. From this experiments, the relative configurations from the C-2 position to the C-3 position in IIa–IId were also assigned. These configurational assignments of IIa–IId were further confirmed by the ozonization of IIa–IId.
Electronic Spectra and Structures of Organic π Systems. V. SCFMO Calculations of Some Fulvenes and Fulvalenes with the Variable Integrals Methods
Authors: Yoshida Zen-ichi , Kobayashi Tsunetoshi 
Published: July 2006

Abstract
The electronic states of fulvene, 6-vinylfulvene, 6-aminofulvene, 6,6-dialkoxyfulvene, 6-amino-6-alkoxyfulvene, heptafulvene, 8-vinylheptafulvene, sesquifulvalene, and fulvalene have been investigated with the variable integrals methods. The effect of bond alternation is taken into account in the SCF procedure. Agreement between the calculated and observed transition energies is satisfactory.
Studies of the Synthesis of Furan Compounds. XXVIII. Syntheses and Steric Configurations of 3-(5-Nitro-2-furyl)-2-(2-furyl)acrylonitrile and Its Bromine Derivatives
Authors: Kato Yasuhiko , Kuboyama Takashi , Hirao Ichiro 
Published: July 2006

Abstract
In continuing a previous report concerning the syntheses and steric configurations of 3-(5-nitro-2-furyl)-2-(2-furyl)acrylic acid derivatives, trans and cis 3-(5-nitro-2-furyl)-2-(2-furyl)acrylonitrile and their related compounds have been synthesized. The isomerization was involved in the conversion of cis-3-(5-nitro-2-furyl)-2-(2-furyl)acrylamide (I) to trans-3-(5-nitro-2-furyl)-2-(2-furyl)acrylonitrile (II) upon the treatment of phosphoryl chloride. II was converted to its cis isomer (III) by treating it with hydroxylamine, hydrazine hydrate, or hydrochloric acid. II and III were treated with bromine at 5–10°C in carbon tetrachloride to afford dibromo compounds, (3S : 5S and 3R : 5R)-(IV) and (3S : 5R and 3R : 5S)-3-(5-nitro-2-furyl)-3-bromo-2-(5-bromo-2,5-dihydro-2-furylidene)propionitrile (V) respectively. When the bromination was carried out at a higher temperature (70–73°C), a monobromo compound, cis-3-(5-nitro-2-furyl)-2-(5-bromo-2-furyl)acrylonitrile (VI), was obtained from both II and III. VI was also produced by heating IV or V in refluxing acetone. The structures and configurations of these compounds were discussed on the basis of their experimental and spectral data.
Compounds Related to Acridine. VIII. Reaction of 9-Vinylacridine with p-Substituted Nitrosobenzenes
Authors: Tsuge Otohiko , Torii Akiyoshi 
Published: July 2006

Abstract
In the presence of hydrochloric acid, 9-vinylacridine reacts with nitrosobenzenes having electron-donating groups such as p-nitroso-N,N-dialkylaminoaniline and p-methylnitrosobenzene to yield a four-membered oxazetidine, as the first example of a non-fluorinated oxazetidine ring system. A new 2:2 adduct, to which the perhydro-1,2,7-oxadiazepine structure is assigned tentatively, is formed in the reaction of 9-vinylacridine with nitrosobenzene or p-chloronitrosobenzene under similar conditions.
Calculation of Infrared Band Intensities of Various Chlorinated Ethanes
Authors: Tanabe Kazutoshi , Saëki Shinnosuke 
Published: July 2006

Abstract
Infrared absorption intensities of fundamental bands of three molecular species, CH3CCl3, CD3CCl3 in the vapor phase, and C2Cl6 in dilute solution in carbon disulfide have been measured. From the intensity data of four kinds of chlorinated ethanes C2H6, C2D6, CH3CCl3, CD3CCl3, the least number of common intensity parameters has been determined using the least squares method. Intensities of C2Cl6 calculated using the determined values of intensity parameters have been compared with the observed intensities in solution. It has proved that for almost all electro-optical parameters, it is possible to determine values commonly applicable to various chlorinated ethanes, while for μCH and δμCH⁄δrCH, it is not possible to find commonly applicable values, as in the case of chlorinated methanes.
Photochemical Reactions of 3-Alkyl-4-phenylsydnones
Authors: Huseya Yoshiharu , Chinone Akiko , Ohta Masaki 
Published: July 2006

Abstract
Photochemical reaction of 3-cyclohexyl-4-phenylsydnone (4) in nitrogen atmosphere afforded 2-cyclohexyl-4,5-diphenyl-1,2,3-triazole (5), 1,2-biscyclohexylazo-1,2-diphenylethylene (6) and 4-cyclohexyl-2-phenyl-Δ2-1,3,4-oxadiazoline-5-one (7). The results showed that the reaction of 4 in the presence of carbon dioxide, carbon disulfide and dimethyl acetylenedicarboxylate proceeded via nitrile imine intermediate. Irradiation of 3-t-butyl-4-phenylsydnone (11) afforded 1-benzoyl-2-t-butyl-4-phenyl-1,2-diazetidine-3-one (12). Variation of the absorbance of 4 at the longest wavelength with irradiation was affected by 1,3-pentadiene, but not that of 11. This shows that the excited triplet state is responsible for the photochemical reaction of 4.
Adsorption of N-Vinyl-2-pyrrolidone at the Mercury/Solution Interface
Authors: Yoshida Tadashi , Ohsaka Tetsuya , Yamamoto Hajime 
Published: July 2006

Abstract
The adsorption of N-vinyl-2-pyrrolidone (NV2P) or the monomer of polyvinylpyrrolidone (PVP) at the mercury/solution interface was examined by means of differential capacity vs. potential relations (C-E curves). The usual C-E curve obtained in 1 n sulfuric acid was similar to that of the saturated aliphatic compounds. However, in 1 n sodium sulfate or sodium hydroxide potential dependence of Cmin (minimum differential capacity) was observed as a result of π-electron interaction of adsorbed molecules. The adsorption behavior in 1 n sulfuric acid followed the Langmuir isotherm. The peculiar behavior in 1 n sodium sulfate or sodium hydroxide was explained by means of the Frumkin isotherm with the potential dependence of interaction constant (g), which varied linearly with potential in a range more negative than ca. −0.6 V (SCE) in contrast to nearly constant values in a more positive range. At a relatively high bulk concentration, there was a slight deviation from the Frumkin isotherm and the standard free energy of adsorption (ΔG0) vs. θ3⁄2 plot revealed a sharp break in the same way as pointed out by Gonway and his co-worker. The Cmin value of NV2P coincided approximately with that of its polymer of PVP in aqueous sulfuric acid, sodium sulfate or sodium hydroxide, respectively. The results are utilized for the discussion on the configuration of adsorbed PVP at the interface.