bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthetic Studies of Cobalt Carbonyl by Noble Metal Catalysts. II. The Investigation of Reaction Conditions
Authors: Usami Seiji , Nishimura Kotaro , Koyama Takeo , Fukushi Saburo 
Published: July 2006

Abstract
The reaction conditions of cobalt carbonylation catalyzed by palladium have been investigated. Polar solvents have, with some exceptions, been shown to be superior to nonpolar solvents. The fact that the total pressure of synthesis gas and the partial pressure of hydrogen, especially the latter, have a great effect on the initiation temperature of reaction suggests that the presence of hydrogen is very important in the present reaction. The low reactivity and poor yield in the reactions of Raney cobalt indicate that a low-valency intermediate in the course of the cobalt-carbonylation reaction of cobaltous compounds may be somewhat different from the Raney-type Co(0). The initial step of the reaction seems to be affected only a little by various additives e. g., water, triphenyl phosphine, lead naphthenate, and sodium hydroxide. The data previously available suggest that a palladium catalyst may primarily promote the reduction of Co (II) to Co(0) by activating hydrogen. The test of the lifetime of a palladium-on-carbon catalyst for a month indicates that there is no apparent decrease in the catalytic activity within this period.
Photoinduced Reactions. XXXIII. Photochemical Reaction of a para-Quinone Methide
Authors: Matsuura Teruo , Ogura Katsuyuki 
Published: July 2006

Abstract
The photochemistry of a quinone methide (Ia) was investigated. Ia was unchanged on photolysis of an alcoholic solution (0.0064 m) with a high-pressure mercury lamp (Pyrex filter). However irradiation of a highly dilute solution of Ia or a sensitized reaction (acetophenone) gave an alcohol adduct (IIe in methanol and IIf in isopropyl alcohol) which might be formed via triplet excited state(s) of Ia. The methanol adduct IIe was also formed by the irradiation of Ia in methanol with a low-pressure mercury lamp through quartz. In this case the formation of He appears to be initiated by photochemical decomposition of methanol.
Studies on Hydrogenolysis. LIV. Catalytic Hydrogenolysis of Optically Active 2-Methyl-2-phenylaziridine
Authors: Sugi Yoshihiro , Mitsui Sekio 
Published: July 2006

Abstract
In order to obtain further information about the catalytic hydrogenolysis of benzyl-type compounds, the hydrogenolysis of optically active 2-methyl-2-phenylaziridine (I) over several group VIII transition metal catalysts was investigated in ethanol under ordinary pressure and at room temperature. 2-Phenylpropylamine (II) was obtained as the main product over all the catalysts. The configuration of II was inverted over the palladium catalyst. However, the hydrogenolysis over the platinum catalyst occurred with a significant retention of the configuration. Further, in the case of Raney nickel and Raney cobalt catalysts, the configurations of II were retained with the low stereoselectivities, and a small amount of 2-phenyl-2-propylamine (III) was also produced in addition to II. These results are attributable to the free-energy difference at the transition states to form π-benzyl intermediates, which depends on the affinity of these metals for the nitrogen lone-pair, the catalyst hindrance, and other factors. The SN2-type reaction is favored over the palladium catalyst. On the other hand, the SNi-type reaction is favored over platinum, Raney nickel, and Raney cobalt catalysts, where the radical-cleavage reaction will participate in addition to the SNi-type reaction over the latter two catalysts. The differences in behavior between styrene imines and styrene oxides on the catalyst surface were also discussed.
The Effect of Organic Additives on the Autoxidation of Benzene and Toluene in the Aqueous Phase and the Kinetic Analysis
Authors: Hotta Hiroshi , Suzuki Nobutake , Isoda Kazuo 
Published: July 2006

Abstract
The effect of organic additives on the autoxidations of benzene and toluene was studied at 180°C in a ferrous sulfate aqueous solution. The additives were benzene, toluene, ethylbenzene, cumene, cyclohexene, cyclohexane, n-hexane, t-butyl alcohol, isopropyl alcohol, and ethyl alcohol. The yields of the phenol and benzaldehyde produced were measured as functions of the initial volume fraction of the additive. The yields decreased with the addition of a trace of the additive, and the yields increased still more with further addition. In order to interpret these results, the general expression for the yield of the main product was derived by the Gale-Wagner method and was analyzed numerically by using the IBM 7044. The mole fraction of the additive, corresponding to the maximum yield, can give information regarding the relative reactivity of the additive as compared with the results of the above numerical analysis. It is concluded from the present study that the experiment of the flow system for the autoxidation of toluene containing various additives is necessary to get exact kinetic information concerning these additives by using the present numerical analysis, because the equation is derived on the assumption that the concentration of the additive is constant.
An X-Ray Emission Spectroscopic Investigation of the Chemical Bond of Sulfur. III. The Profile of SKβ Band in Sulfur Compounds
Authors: Takahashi Yoshihito , Yabe Katsumasa 
Published: July 2006

Abstract
The profile of the SKβ band in various sulfur compounds, including many organic compounds, was separated into peaks, and the wavelength values and the intensities of the separated peaks were discussed in relation to the chemical bonding. The band of sulfone and sulfoxide consists of three or four peaks. We named the peaks A, B, C (the strongest), and D, beginning from the longer-wavelength side. The relative intensity of the peak A (generally named Kβ′) increases as the number of valence electrons of the sulfur atom decreases. The peak B may be attributed to the non-polar single bond of sulfur in sulfone and sulfoxide. The clear peak, D, appears only in the band of sulfite and sulfoxide. The band of the compounds of thiourea type consists of two peaks. Using the results of the above study, the chemical structures of aldehyde-bisulfite adducts and 2-mercaptobenzimidazole, etc., were discussed.
Energy Transfer between Benzene and Toluene in the Singlet States at 90°K
Authors: Nakahara Akihiko , Koyanagi Motohiko , Murakami Yoshio , Edamura Takao , Kanda Yoshiya 
Published: July 2006

Abstract
The fluorescence spectrum of toluene in benzene has been photographed at 90°K and analyzed accurately. Systematic studies of concentrations made it possible to estimate the efficiency of energy transfer from the singlet state of the host molecule to that of the guest molecule. The fluorescence spectrum of pure benzene has also been studied at 4.2°K and 90°K for comparison, and the effect of toluene as an impurity in the benzene spectra has been discussed.
A Study of the Properties of Dilute Polymer Solutions by the Archibald Ultracentrifugal Method
Authors: Kotera Akira , Matsuda Hideomi , Miyazawa Yuji , Joko Etsuo 
Published: July 2006

Abstract
A modification of the Archibald method for determining the molecular weight of a polydisperse sample in ideal and non-ideal solutions is developed in this paper. A reliable value of the weight average molecular weight is obtained from the plot of an apparent weight average molecular weight against the centrifugal time rather than against the amount of the solute sedimented from the meniscus. This fact is explained on the assumption of a fractionation effect of the solute caused by the centrifugal potential.
Oscillopolarographic Behaviour of Lanthanide Ions in Potassium Iodide Solutions
Authors: Iwase Akio , Yokoyama Chieko 
Published: July 2006

Abstract
The oscillopolarographic depolarization effect of lanthanide ions in KI solutions was investigated using dropping (DME) and hanging-drop (HME) mercury electrodes. The lanthanide-ion incision depth in the dE⁄dt=f(E) curve, measured in a 1m KI solution (pH 3.65) with a DME, was found to be much deeper than that in a 1m KCl solution. The temperature coefficient was negative for the La and Sm incision depths in the temperature range from 25° to 50°C. The incision depths of the La (pH 4.0) and Sm (pH 4.5) ions in a solution with an ionic strength of 0.7 (KCl added) were found to depend on the I− concentration. These facts seem to show that I− is adsorbed on DME, and that the adsorbed I− (at −1.4 V) promotes the electrode reaction of lanthanide ions.
Imidazoles. II. A General Synthesis for 1-Hydroxyimidazoles
Authors: Akagane Katsuo , Allan F J , Allan G G , Friberg T , Muircheartaigh S Ó , Thomson J B 
Published: July 2006

Abstract
The reaction of α-dione monoximes with aldehydes and ammonia affords a general and facile synthetic route to 1-hydroxyimidazoles. By selection of the starting materials substituents can be readily introduced into the 2,4 and/or 5 positions of the imidazole ring which is formed via the intermediacy of a gem-aminoalcohol. The reactions of the N-hydroxyl function are discussed.
The Polymerizations and Copolymerizations of α-Methoxy-acrylonitrile and Methyl α-Methoxyacrylate
Authors: Otsu Takayuki , Yamada Bunichiro , Yoneno Hiroshi 
Published: July 2006

Abstract
A study of the polymerizations and copolymerizations of α-methoxyacrylonitrile(MeOAN) and methyl α-methoxyacrylate(MeOA) has been made. These monomers were homopolymerized with a radical initiator at 60°C, but did not give any polymer with such ionic catalysts as BF3O-(C2H5)2 and C6H5MgBr at 0°C. From the radical copolymerizasions of these monomers with styrene at 60°C, their Q, and e values were determined to be as follows:
Q=0.72, e=0.40 for MeOAN
Q=0.47, e=0.04 for MeOA
These monomers were also copolymerized with acrylonitrile, and the copolymerization parameters were determined.
The Reaction of Carboxylic Acids and Hydrocarbons in a Silent Electric Discharge. II. The Reactions of Ethylene with Methyl Acetate and with Acetic Anhydride
Authors: Hiraki Teruo 
Published: July 2006

Abstract
The present study was undertaken in order to ascertain the difference, if any, in the chemical behavior of methyl acetate and acetic anhydride submitted to a silent discharge between that in the presence and that in the absence of ethylene. (1) In the reaction of methyl acetate without ethylene, the main products were methanol, diacetyl, liquid hydrocarbons, formaldehyde, methane, carbon dioxide, carbon monoxide, and hydrogen. Although the methanol yield was almost the same, regardless of the presence or absence of ethylene, the yields of the hydrocarbons, all the carbonyl compounds, and of n-butyl acetate increased in the presence of ethylene. The great quantity of methanol produced might indicate that C–OCH3-bond breaking in the methyl acetate occurs preferably upon the discharge. (2) With acetic anhydride, on the other hand, acetaldehyde, acetone, ethyl acetate, ethyl methyl ketone, diacetyl, hydrocarbons, carbon monoxide, carbon dioxide, and hydrogen were obtained as the main products. The yields of acetone and diacetyl decreased remarkably in the presence of ethylene, while the yields of hydrocarbons, ethyl methyl ketone, n-butyl methyl ketone, and of n-butyl acetate increased. The CH3COO· and CH3CO· radicals are thought to be the main intermediates in this reaction. The formation of n-butyl acetate and of n-butyl methyl ketone in the presence of ethylene can be explained on the basis of the telomerization of ethylene initiated by these radicals.
Intermolecular Hydrogen Bond Involving a π Base as the Proton Acceptor. VI. Hydrogen Bonding of Phenols and Naphthols to Aromatic Hydrocarbons. Entropy Anomaly and the Role of Charge-Transfer
Authors: Yoshida Zen-ichi , Ishibe Nobuyuki 
Published: July 2006

Abstract
Using a series of alkylphenols and naphthols as the proton donors, the hydrogen bond shifts and the association constants of hydrogen-bonded complexes involving methyl benzenes, naphthalene, and phenanthrene as the proton acceptors have been determined from the infrared spectra in carbon tetrachloride. The frequency shifts (Δv) of the hydroxyl stretching vibration and the free energy changes (−ΔF) for complex formation increase with decreasing pKa of the proton donors. Linear correlation between −ΔF and Δv are obtained for each proton donor interacting with methyl benzenes. The entropy anomaly discovered previously was confirmed. Chargetransfer arguments of Basila and co-workers are reconsidered for the hydrogen-bonded systems involving a π base as the proton acceptor.
Intermolecular Hydrogen Bond Involving a π Base as the Proton Acceptor. VII. Substituents and Steric Effects in the Hydrogen Bonding of 2,6-Xylenols to Mesitylene
Authors: Yoshida Zen-ichi , Ishibe Nobuyuki 
Published: July 2006

Abstract
Hydrogen bonding of 4-substituted-2,6-xylenols to mesitylene has been investigated by measurement of the hydroxyl stretching vibration. A linear relationship between the electronic effects of para substituents (Hammett σp constant) and the frequency shifts of the hydroxyl stretching vibration was obtained. A similar correlation was also observed with the free energy change associated with the formation of the hydrogen-bonded complex. The thermodynamic sutdies on the hydrogen bonding of 2,6-xylenol and phenol with both mesitylene and acetonitrile demonstrated the steric effect of 2- and 6-methyl groups on hydrogen bond formation. The free energy change for hydrogen bond formation with 2,6-xylenols as the proton donor was lower than with phenol. This is explained in terms of both entropy and enthalpy factors.
Nitroalkenylferrocene. IV. Preparation of 1-Ferrocenyl-2-iodo-2-nitroethylene and Configurations of Several Nitroalkenylferrocenes
Authors: Kono Hiromichi , Shiga Mikio , Motoyama Izumi , Hata Kazuo 
Published: July 2006

Abstract
A new method of synthesizing 1-ferrocenyl-2-iodo-2-nitroethylene (6) was presented, whereas 1-ferrocenyl-2-halo-2-nitroethylene could not be prepared by the usual method, involving the direct halogenation of the nitroolefin. The iodonitroethylene (6) was prepared by the reaction of the sodium salt of 1-ferrocenyl-2-nitroethylene with iodine or with potassium iodide. This procedure proved to be useful for introducing various groups on the α-carbon of the nitroethylene. The stereochemistry of nitroalkenylferrocenes, including some previously reported ones, was discussed on the basis of their spectral data.
Phenolytic Rearrangement and Isomerization of cis- and trans-4-t-Butylcyclohexyl p-Toluenesulfonates in a Phenol-Benzene Solvent
Authors: Okamoto Kunio , Saitô Seiki , Shingu Haruo 
Published: July 2006

Abstract
As the first examples of solvolytic cis-trans isomerization and 1,2-rearrangement for the 4-t-butylcyclohexyl system, phenolytic cis-trans (or trans-cis) isomerization and 1,2-rearrangement have been found for cis- and trans-4-t-butylcyclohexyl p-toluenesulfonates in the phenol-benzene (1 : 1 by wt) solvent at 75.0°C. The tosylate, recovered after a 75% completion of the SN1 phenolysis of the cis-4-tosylate, was composed of small amounts of the trans-4-tosylate (1%) and the cis-3-tosylate (11%), besides 88% of the starting cis-4-tosylate, clearly indicating occurrence of both the cis-trans isomerization and the 1,2-rearrangement of the starting cis-4-tosylate. In a similar fashion, starting from the trans-4-tosylate, small amounts of the cis-4-tosylate (0.7%) and the trans-3-tosylate (2.6%) were recovered from the tosylate after the SN1 phenolysis was 75% complete. On the basis of the results of an examination into the influence of the added tosylate anion on the extent of isomerization and of rearrangement, it has been suggested that the cis-trans or trans-cis isomerization results largely from the external SN2-like attack of the tosylate anion on the SN1 ion-pair intermediate and partly as a consequence of the rotation of the t-butylcyclohexyl cation within the ion-pair intermediate, whereas the 1,2-rearrangement proceeds through an intramolecular 1,2-shift of hydrogen within the 4-t-butylcyclohexyl cation.
Kinetics of Isotopic Exchange between Acetylacetone-14C and Bisacetylacetonatopalladium(II) in Organic Solvents
Authors: Saito Kazuo , Takahashi Michihiko 
Published: July 2006

Abstract
Bisacetylacetonatopalladium(II) [Pd acac2] was precipitated crystalline free from excessive acetylacetone (Hacac) by adding the reaction mixture in anisole, benzene or 1,2-dichloroethane to chilled petroleum ether. Its specific counting rate was measured by liquid scintillation technique. The isotopic exchange rate is measurable at 40 to 80°C and the kinetics is expressed by the ordinary two term formula, Rate=[Pd acac2](k1+k2[Hacac]). The second term corresponds to the reagent path, in which acetylacetone molecule rather than acetylacetonate anion acts as nucleophilic reagent. The first term seems to express a dissociation mechanism rather than the solvent path; the break of Pd–O bond without the aid of nucleophilic attack by the solvent molecule is responsible for determining the exchange rate. The exchange reaction is accelerated by acids, and the acid-catalyzed reaction path operates independent of the reagent path to give the following kinetic formula:
Rate=[complex](k1+k2[Hacac]+k3[acid])
The Oxygenation-deoxygenation of Cobalt(II) Complexes on Polymers
Authors: Misono Akira , Koda Seiichiro , Uchida Yasuzo 
Published: July 2006

Abstract
Three cobalt(II) complexes, bis-(salicylaldehyde)-ethylenediimine-cobalt(II), bis-(salicylaldimino) cobalt(II), and di-(salicylal)-3,3′-diimino-di-n-propylamine-cobalt(II), were mixed with poly-4-vinylpyridine. These mixtures showed ESR signals which reversively appeared under oxygen. We tried to identify these signals on the basis of the electonic structure, cobalt(III)-O2−1. The oxygenation-deoxygenation rates were also observed and found to obey the Elovich rate equation.
Heat of Mixing for Binary Mixtures: Pyridine Derivatives + Benzene, and +Cyclohexane Systems
Authors: Murakami Takeshi , Murakami Sachio , Fujishiro Ryoichi 
Published: July 2006

Abstract
The heat of mixing was measured for binary mixtures of pyridine derivatives (α-picoline, β-picoline, γ-picoline, and 2,6-lutidine) with benzene or cyclohexane at 25.0±0.01°C, and for a binary mixture of pyridine with benzene, or cyclohexane, at 30.0±0.01°C. The small values of the heat of mixing for pyridine derivatives-a benzene system were interpreted as an indication of strong specific interactions between pyridine derivatives and benzene. By treating the results in the manner described in a previous paper (Bull. Chem. Soc. Japan, 39, 720 (1966)), the specific interaction energies of pyridine derivatives with benzene were estimated. The strengths of the molecular interaction energy were in the order: γ-picoline&gt;pyridine&gt;β-picoline&gt;α-picoline&gt;2,6-lutidine; the order was discussed in terms of the molecular complexes.
The N→O Acetyl Migration of 5-Substituted-2-pyrrolidinemethanols
Authors: Sakurai Hisayuki , Ishimaru Toshiyasu 
Published: July 2006

Abstract
In order to obtain information about the stereochemistry of a fused-ring system, cis and trans isomers of 5-methyl- and 5-phenyl-2-pyrrolidinemethanols were synthesized and rate constants for their N→O acetyl migrations were measured. Each product was a mixture of cis and trans isomers. For both 5-methyl and 5-phenyl derivatives, it was observed that trans isomers migrated faster than cis isomers. The results were discussed in relation to stereochemistry.
Magnetic Moments and d–d Bands of Copper(II) Halide Complexes with Substituted Pyridine N-Oxides and Some Related Ligands
Authors: Muto Yoneichiro , Kato Michinobu , Jonassen Hans B , Cusachs Louis Chopin 
Published: July 2006

Abstract
In order to test the substituent effect or the effect of variations in chemical structures on the demagnetization and d–d band shift in dimeric copper(II) halide complexes with pyridine N-oxides and some related ligands, a variety of electron-donating or electron-withdrawing substituents attached in 2-, 3- and 4-positions in the pyridine ring of the ligand were extensively studied. In these dimeric complexes, no correlation was observed between the Hammett’s σ constants and the observed d–d band positions or magnetic moments. However, irrespective of the nature of the substituents, a linear relation was observed to exist between the d–d band positions and the magnetic moments, indicative of a magnetochemical support for the interpretation of the spectrochemical series through the idea of symmetry-restricted covalency. For the monomeric complexes with the same ligands, a linear relation exists between Hammett’s constants and the d–d band positions for each series of the electron-donating and electron-withdrawing substituents. Experimental results indicate that the most important factor determining the non-applicability of Hammett’s Rule in these dimeric complexes is the steric condition of the metal ions which shields them from the influence of other molecules or ions. The larger demagnetization effect of the bromide ion compared to the chloride ion has been interpreted as due to its larger nephelauxetic effect. On the basis of the established structure of the parent compound, two pathways for superexchange interaction have been proposed. The importance of a σ type orbital overlap compared to the π type is discussed.
The Spectrophotometric Determination of Thorium(IV) with Bromopyrogallol Red
Authors: Tonosaki Kôichi , Sakai Takayoshi 
Published: July 2006

Abstract
Bromopyrogallol red reacts with thorium(IV) to form a stable complex with an absorption maximum at 645 mμ against a reagent blank. The maximum absorbance is obtained in the pH range of 5.6 to 5.9 when the solution is heated in a boiling water bath for 20 min. The color system obeys Beer’s law in the range 6 to 106 μg of thorium in 25 ml. The molar absorptivity of the complex is calculated to be 5.0×104 at 645 mμ. The sensitivity of the reaction is 0.004 μg thorium per cm2. The complex has the composition 1 to 2 in metal to ligand. The effect of diverse ions on the determination is also examined.
Effects of the Addition of Chlorohydrocarbons on the Oxidation of Propylene; A Consideration of the Negative Temperature Coefficient
Authors: Masai Mitsuo , Echigoya Etsuro , Morikawa Kiyoshi 
Published: July 2006

Abstract
A small amount of allyl chloride, 1,1-dichloroethane, or chloroform was added to the reactant in the oxidation of propylene in an inert fluidized-bed reactor. A negative temperature coefficient is observed in the conversion of propylene and in the formation of various products, but not propylene oxide, in the experiments with allyl chloride or 1,1-dichloroethane added. The results of the chloroform-adding experiments show a positive temperature coefficient in the conversion of propylene and in the formation of gaseous products. The results of the work described here are discussed on the basis of the probable reaction scheme. The results of the chloroform-adding experiments support the proposed catalytic effect of the chlorocarbene on the decomposition of acetaldehyde. It is concluded that the negative temperature coefficient is attributable to the apparent inactivity of acetaldehyde (the branching agent) in the high-temperature region in this reaction atmosphere.