bluuebunny/crossref_metadata_2025_split huggingface dataset:
Reactions of Transition-Metal-Olefin Complexes. III. Kinetics of the Oxidation of Substituted Styrenes Catalyzed by Palladium Salts in an Aqueous Tetrahydrofuran Solution
Authors: Okada Hiroyoshi , Noma Takashi , Katsuyama Yoshihisa , Hashimoto Harukichi 
Published: July 2006

Abstract
The kinetics of the oxidation of ring-substituted styrenes catalyzed by palladium(II) salts in a homogeneous aqueous tetrahydrofuran solution containing p-benzoquinone have been investigated at 30°C under a nitrogen atmosphere. The rate equation was found to be identical with the one previously found for styrene, i.e., −d[olefin]⁄dt=(kI+kII[Pd2+][olefin], where kI is the rate constant for ketone-formation and kII is the rate constant for aldehyde-formation. It was found that both the proton and the chloride ion affect the rate inhibition at high concentrations and the rate acceleration at low concentrations. The product ratio of the ketone to the aldehyde decreased monotonously with the increase in proton concentration and with the increase in chloride ion concentration. An increase in the ionic strength from 0.052 to 0.787 increased the rate constants, but the ratio of the products scarcely changed at all. The substituent effects for the sites of nucleophilic attack were specific; i.e., the electron-releasing substituents facilitated the formation of substituted acetophenone and diminished the formation of substituted phenylacetaldehyde. The reverse trend was found for the electron-withdrawing substituents. From these results, there is proposed a mechanism in which two active species, [ArCH=CH2Pd(H2O)-(OH)Cl] and [ArCH=CH2Pd(H2O)(OH)Cl2]−, are involved and in which the rate-determining step is the decomposition of the σ-complexes with the hydride shift to the carbonyl products.
Cleavage Reactions of Alkoxy Radicals Produced by Anodic Oxidation of t-Alcohols
Authors: Maruyama Kazuhiro , Murakami Katsuya 
Published: July 2006

Abstract
The anodic oxidation of t-alcohols in water - dioxane - sodium hydroxide system has been examined. The possibility of production of t-alkoxy radicals by anodic oxidation of t-alcohols in the electrolytic system was found. The relative ease of bond scission of the intermediate t-alkoxy radical was determined by quantitative analysis of the mixture of ketones produced. The relative rates of cleavage decrease in the order: allyl&gt;sec-butyl&gt;isopropyl&gt;ethyl&gt;n-propyl&gt;n-butyl&gt;n-pentyl&gt;isobutyl&gt;methyl. The hyperconjugative effect of β-hydrogen and effect of double bond at β-position to the rate enhancement of cleavage reaction was confirmed.
Studies of Phosphorylation. II. Reaction of 2′, 3′-O-Isopropylideneinosine and -guanosine with Phosphoryl Chloride1
Authors: Kusashio Koji , Yoshikawa Masaharu 
Published: July 2006

Abstract
Several reactions accompanied by the phosphorylation of 2′, 3′-O-isopropylidene nucleosides with phosphoryl chloride in the absence of an organic solvent were investigated. When the reaction temperature exceeded 30°C, 2′, 3′-O-isopropylideneinosine gave 5′-chloro-5′-deoxy 2′, 3′-O-isopropylideneinosine and 5′-deoxy-2′, 3′-O-isopropylidene-3, 5′-cycloinosine. This cycloinosine, was then further subjected to rapid cleavage in a pyrimidine ring to give 5-amino-4-carbamoyl-N5, 5′-cyclo-1-β-d-(5′-deoxy-2′, 3′-O- isopropylideneribofuranosyl)-imidazole, 5-amino-4-cyano-N5, 5′-cyclo-1-β-d-(5′-deoxy-2′, 3′-O-isopropylideneribofuranosyl)-imidazole, and the N5-formyl derivative of the latter. Similar sequences of the chlorination at the 5′-position and the cyclization between 3 and 5′-positions were observed in the case of 2′, 3′-O-isopropylideneguanosine, but the resulting 5′-deoxy-2′, 3′-O-isopropylidene-3, 5′-cycloguanosine was not susceptible to ring cleavage under the conditions used. The factors affecting these reactions were described, and possible mechanisms were proposed.
Infrared Spectra and Stereochemistry of Bis-pyridine Complexes of Tin(IV)
Authors: Tanaka Toshio , Matsumura Yoshio , Okawara Rokuro , Musya Yoshihiko , Kinumaki Susumu 
Published: July 2006

Abstract
Assignments are given for the infrared spectra of bis-pyridine complexes of SnX4, (CH3)2SnX2(X=Cl,Br and I), and (C2H5)2SnCl2 in the 80–1610 cm−1 region. These complexes show the Sn–N stretching band near 200 cm−1. Most pyridine vibrations shift to a higher or a lower frequency upon complex formation. Among these, the ν10, in-plane ring deformation vibration is the most sensitive to the substituents on the tin atom as well as to the complex formation. Thus, the frequency may be a qualitative measure of the tin-pyridine coordination bond strength. The infrared spectra suggest a cis-configuration for the tin tetrahalide complexes and a distorted octahedral configuration for the dimethyltin diiodide complex. The remaining complexes may be assumed to have trans-alkyl and cis-halogen configurations.
The Termination Processes of the Autoxidations of Benzene, Toluene and Ethylbenzene in the Aqueous Phase as Studied by Oxygen-18
Authors: Hotta Hiroshi , Suzuki Nobutake 
Published: July 2006

Abstract
The autoxidations of benzene, toluene and ethylbenzene were investigated at 70°C by using the oxygen-18 enriched Fenton’s reagent. The oxygen-18 atom percentage in the products suggests that all the oxygen of benzaldehyde from toluene and of acetophenone from ethylbenzene is donated by molecular oxygen dissolved in the aqueous phase, while the oxygen of the hydroxylation products, namely, phenol from benzene, benzyl alcohol from toluene and methyl phenyl carbinol from ethylbenzene, is donated partly from water and partly from molecular oxygen. From the latter finding, the rate of the carbonium cation formation from the intermediate radicals without their oxidation to the peroxide is in the order of phenyl&gt;α-methyl-benzyl&gt;benzyl.
Heats of Mixing for Binary Mixtures. V
Authors: Murakami Sachio , Koyama Mituo , Fujishiro Ryoichi 
Published: July 2006

Abstract
The heats of mixing were measured at 25.0°C for binary mixtures of chloroform+tetrahydrofuran,+furan, and +2-methyl furan systems and for cyclohexane+chloroform,+tetrahydrofuran,+furan, and +2-methyl furan systems. Using these data and the treatment described in a previous paper [Bull. Chem. Soc. Japan, 37, 1776 (1964)], the intermodular hydrogen bond energies between chloroform and cyclic ethers were estimated to be ΔH=−12 kJ for the chloroform-tetrahydrofuran-cyclohexane system, ΔH=−4 kJ for the chloroform -2-methyl furan-cyclohexane system, and ΔH=−3 kJ for the chloroform-furan-cyclohexane system. From these results, two types of intermolecular hydrogen bonds between chloroform and cyclic ethers are discussed.
Ion-exchange Properties of Anion-exchanger Containing Cobalticinium Cations
Authors: Ito Takuji , Kenjo Tadao 
Published: July 2006

Abstract
Selectivity coefficients of various anions vs. chloride or nitrate and water uptake at a saturated vapor pressure with polymeric pentamethylene cobalticinium exchanger were calculated from the experimental data and compared with those of anion-exchange resins. The selectivity coefficient sequence was nearly identical with that for quaternary ammonium type anion-exchangers, and the position of hydroxide ion indicated that the cobalticinium type anion-exchanger was a strong base type. Inspection of selectivity coefficients data revealed that strong base anion-exchangers were more selective than weak base anion-exchangers. The cobalticinium type anion-exchanger was found to have a high selectivity coefficient of iodide vs. bromide, even in comparison with strong base anion-exchange resins. Column separation of bromide and iodide using the cobalticinium type anion-exchanger was easily accomplished. The separation factor was three times that of the quaternary ammonium type anion-exchanger. The water uptake at a saturation vapor pressure by the cobalticinium type anion-exchanger in a given form increased with decreasing selectivity coefficient for the same anion. These trends were similar to those for quaternary ammonium type anion-exchanger. The relation between selectivity coefficient sequence of various anions vs. a common anion, and solubilities of the salt whose cation was the ionogenic group and anion adsorbed ion was discussed.
Behavior of Methyl Iodide in the Reaction of Acetic Acid Synthesis from Methanol and Carbon Monoxide
Authors: Mizoroki Tsutomu , Nakayama Mikitake 
Published: July 2006

Abstract
The reaction of methyl iodide with carbon monoxide in the presence of cobalt (II) iodide as the catalyst has been investigated to know the effect of methyl iodide on the acetic acid synthesis from methanol and carbon monoxide catalyzed by the same catalyst. The reaction, CH3I+CO+H2O→CH3COOH+HI, does not take place before the methyl iodide used has been hydrolyzed completely into methanol and sodium iodide by adding enough amount of sodium acetate (CH3I+CH3COONa+H2O→CH3OH+NaI+CH3COOH). Methyl iodide also strongly inhibits the reaction of methanol with carbon monoxide catalyzed by cobalt (II) ion or dicobalt octacarbonyl, although iodide ion promotes the reaction effectively. The promotion effect of iodide ion has been discussed by considering the effect of an additive on carbonylation reactions in terms of a labilizing ligand and a non-labilizing ligand and a possible reaction scheme of methanol with carbon monoxide catalyzed by cobalt(II) iodide has been proposed.
Hot Atom Chemistry of Phosphorus Compounds. II. Chemical Effects of Neutron Irradiation on Phosphoric Esters of Hexoses
Authors: Kiso Yoshiyuki , Kobayashi Mitsue , Kitaoka Yoshinori , Kawamoto Keizo , Takada Jitsuya 
Published: July 2006

Abstract
Phosphoric esters of hexoses were subjected to neutrons and the resulting 32P-labeled recoil products were separated by paper chromatography and paper electrophoresis. The main recoil products were phosphorous and phosphoric acids, independent of the chemical form of the target material and the kind of its salt. A small amount of inorganic acids containing a P–P or P–O–P bond was also found. The yield of the retention product was less than a few percents. The presence of organic diphosphorus compound was supposed by paper electrophoretic analysis. An addition of a small amount of water to the target material before irradiation favored formation of 32P-labeled phosphorus oxyacids in lower oxidation state. The results from irradiation of aqueous solution gave an unexpected chromatographic behavior owing to some unstable complex of recoil 32P atom with water molecule.
Polymerizations by 1,3-Dipolar Cycloaddition Reactions. V. The 1,3-Dipolar Polycycloadditions of Dinitrile N-Oxides with Diolefins
Authors: Iwakura Yoshio , Shiraishi Shinsaku , Akiyama Masayasu , Yuyama Masahiro 
Published: July 2006

Abstract
Terephthalonitrile di-N-oxide and isophthalonitrile di-N-oxide were synthesized from the corresponding hydroxamic chlorides by dehydrochlorination with triethylamine. Their chemical properties and the polycycloadditions with diolefins were examined. The polymers obtained were amorphous and their molecular weights were not so high. The thermal gravimetric analyses of them showed that the polymers were stable up to 300–350°C in air.
Polymerizations by 1,3-Dipolar Cycloaddition Reactions. VI. Syntheses of Polyurethans with Isoxazoline or Isoxazole Linkages
Authors: Iwakura Yoshio , Shiraishi Shinsaku , Asakawa Zin , Akiyama Masayasu , Tanaka Nobuo 
Published: July 2006

Abstract
Polyurethans with isoxazoline or isoxazole linkages in the polymer main chains were prepared by polyadditions of diols with isoxazoline or isoxazole rings and diisocyanates. The diols were prepared by 1,3-dipolar cycloaddition reactions of tere- and iso-phthalonitrile di-N-oxides with allyl or propargyl alcohol. Polyurethans of the same structures were also prepared by 1,3-dipolar polycycloadditions of the nitrile oxides with bisallyl or bispropargyl carbamates.
Dehydrocyclization of 3-Methyl Heptatriene-1, 4, 6
Authors: Komatsu Youji 
Published: July 2006

Abstract
Xylenes, mainly consisting of ρ-xylene and o-xylene, were selectively synthesized by the dehydrocyclization of 3-methyl heptatriene-1, 4, 6 (MHT) using a chromia-alumina catalyst. MHT was easily converted to xylenes in a good yield; this reaction proceeded even under mild conditions, as at 200°C. The effects of the catalyst composition, and the influence of the reaction temperature on the conversion of MHT, the xylene yield, the by-products, etc., were studied.
3d-Orbital Resonance in Divalent Sulfides. XIV. Free Radical Copolymerization of Ketene Diethylmercaptal with Styrene
Authors: Tagaki Waichiro , Tada Tsutomu , Nomura Ryuichi , Oae Shigeru 
Published: July 2006

Abstract
Free radical copolymerization reactions of ketene diethylmercaptal (I) and p-methyl-mercaptostyrene (III) with styrene have been carried out. The Q-values for I and III are found to be 2.7 and 3.3 respectively, and these and other related observations are discussed in terms of electron-sharing conjugation involving 3d-orbital of sulfur atom.
Studies of Photosensitive Resins. III. The Thermal Hardening of Polyvinyl Cinnamate
Authors: Nakamura Kenichiro , Sakata Toshifumi , Kikuchi Shinichi 
Published: July 2006

Abstract
The thermal hardening of polyvinyl cinnamate was investigated. The IR spectrum of the thermally-hardened polyvinyl cinnamate was measured, and the change of its structure by heat was studied. The results showed that the structure of the resin hardened by heat was the same as that of the illuminated resin. The kinetics of the crosslinking by heat was also evaluated; the activation energy for the crosslinking was estimated to be 25.4 kcal/mol. The critical hardening value of polyvinyl cinnamate was also measured and estimated to be about 1.3 crosslinking per polymer molecule.
Nuclear Quadrupole Resonance Study of Antimony Pentachloride and Its Phase Transition
Authors: Chihara Hideaki , Nakamura Nobuo , Okuma Hideo , Seki Syûuzô 
Published: July 2006

Abstract
A phase transition was found in solid antimony pentachloride at 212°K by the nuclear quadrupole resonance and the differential thermal analysis. In the high temperature solid phase, five resonance lines were observed that were all assigned to antimony resonances and that were dependent on temperature only slightly. The quadrupole coupling constant of 121Sb was 84.54±0.01 MHz (asymmetry η=1.0±0.3%). Chlorine resonances were not detected above the transition point. In the low temperature phase, many resonance lines were observed due both to chlorine and antimony; the latter gave the coupling constant for 121Sb 186.43±0.03 MHz (η=79.54±0.02%) and 172.8±0.3 MHz (η=79.2±0.3%). There are two nonequivalent sites for antimony. The structure in the two solid phases was suggested as being trigonal bipyramidal above 212°K and a dimerized Sb2Cl10 bridged by two chlorine atoms with hexa-coordinated antimony atoms below 212°K.
The Cobalt Carbonyl-catalyzed Intramolecular Hydroesterification of Allyl Alcohol with Carbon Monoxide
Authors: Matsuda Akio 
Published: July 2006

Abstract
The intramolecular hydroesterification of allyl alcohol with carbon monoxide to give γ-butyrolactone occurred in the presence of cobalt carbonyl under the pressure of carbon monoxide containing a small amount of hydrogen; propionaldehyde and isobutyraldehyde were produced as by-products. The selectivity toward γ-butyrolactone increased with the use of acetonitrile or its derivatives as the solvent. The addition of pyridine, in the absence of these solvents, was effective only in increasing the reaction rate, not in increasing the selectivity toward γ-butyrolactone. On the other hand, in the presence of acetonitrile as a solvent, the selectivity toward γ-butyrolactone increased together with the reaction rate when a catalytic amount of an organic base such as pyridine was added. The higher the reaction temperature, the higher the pressure necessary to attain a maximum selectivity toward γ-butyrolactone; the best yield of γ-butyrolactone was ca. 60%. The effect of the partial pressures of hydrogen and carbon monoxide on the initial rate of the formation of each product was made clear. The experimental results were explained by a mechanism involving two different paths for the formation of an alkylcobalt carbonyl-intermediate. The order of effectiveness of acetonitrile and its derivatives as solvents has been interpreted in terms of the HSAB principle by Pearson et al.
Electrochemical Fluorination of Glycols and Esters of Dicarboxylic Acids
Authors: Nagase Shunji , Abe Takashi , Baba Hajime 
Published: July 2006

Abstract
The electrochemical fluorination of glycols (1,3-propanediol and 1,4-butanediol), and dimethyl or diethyl esters of dicarboxylic acids (malonic, succinic, and maleic acids) was carried out. Difluoromalonic acid from esters of malonic acid, and perfluorosuccinic acid from esters of succinic acid or maleic acid, were obtained in reasonable yields, while 1,3-propanediol and 1,4-butanediol were cleaved or underwent ring formation and yielded only small amounts of perfluoro-dicarboxylic acids. Perfluoromonocarboxylic acids and fluorocarbons were among the by-products of these esters and glycols.
Hydrogen Abstraction Reaction of α-Heteroatom Substituted Compounds by t-Butoxy Radical
Authors: Uneyama Kenji , Namba Hiroshi , Oae Shigeru 
Published: July 2006

Abstract
Hydrogen abstraction reactions of various α-substituted compounds were examined in chlorobenzene using di-t-butyl peroxide. The reactivities are not satisfactorily correlated with σ* values of the substituents. The relative rates of substituted anisoles, N,N-dimethylanilines and phenyl methyl sulfones give good correlations with Hammett σ values with ρ values of −0.39, −0.42 and −0.2 respectively, but those of thioanisoles requires an additional term due to conjugative effect as described in logk⁄k0=−0.11(σ+0.75ΔσR+) in order to get a good Hammett correlation. These results were discussed in terms of a combination of an inductive effect, an electron-releasing and an electron-sharing conjugation.
Anionic Polymerization of trans-β-Methylstyrene
Authors: Okamoto Yoshio , Yuki Heimei , Murahashi Shunsuke 
Published: July 2006

Abstract
The anionic polymerization of trans-β-methylstyrene by n-butyllithium was carried out in hydrocarbon solvents and in tetrahydrofuran. In hydrocarbon solvents the monomer was consumed by n-butyllithium, but gave no polymer insoluble in methanol. In tetrahydrofuran the polymerization proceeded rapidly, giving a polymer insoluble in methanol. This polymer was produced by the normal addition polymerization of a C=C double bond. The relatively lower degree of polymerization of poly-β-methylstyrene indicated a chain transfer in the reaction. The chain transfer reaction due to the active hydrogen of a methyl group in this monomer was also observed by means of the electronic spectra of the reaction mixtures. The polymer anion was converted to inactive anions at high temperatures.
Studies of Photosensitive Resins. IV. Photosensitization Mechanism of Polyvinyl Cinnamate
Authors: Nakamura Kenichiro , Kikuchi Shinichi 
Published: July 2006

Abstract
The photosensitization mechanism of polyvinyl cinnamate was investigated by measuring the phosphorescence spectra of cinnamic acid and sensitizers. The peak of phosphorescence for trans-cinnamic acid was found to be 20100 cm−1, and the triplet energies of the effective sensitizers were found to be situated near or higher than that of cinnamic acid. It was established that the phosphorescences of sensitizers were exceedingly quenched when cinnamic acid was introduced into their solutions. This finding can be understood if it is assumed that the excitation energy is transferred from the triplet state of the sensitizer to that of cinnamic acid. The critical separation of donor and acceptor and the configuration of the triplet state for cinnamic acid are also discussed.
An MO-theoretical Interpretation of the Nature of Chemical Reactions. I. Partitioning Analysis of the Interaction Energy
Authors: Fukui Kenichi , Fujimoto Hiroshi 
Published: July 2006

Abstract
The molecular interaction energy, without considering the nuclear configuration change, is discussed by partitioning it into the Coulomb, exchange, delocalization, and polarization terms. A succinct approximate expression for each term is derived, and its magnitude is discussed. The expressions obtained as the second-order perturbation terms for the delocalization and the polarization energies are in accord with those of the well-established reactivity indices, the delocalizability, and the self-atom polarizability respectively. The chemical reactivity can thus be measured by the combined sum of these four terms. In usual ionic reactions the Coulomb and the delocalization terms are more important than the exchange and the polarization terms respectively.
The Crystal Structure of the Copper(II) Chelate of N,N′-Ethylene-bis(l-ephedrine)
Authors: Motohashi Michio , Amano Yoshiharu , Uno Toyozo 
Published: July 2006

Abstract
The crystal structure of the copper(II) chelate of N,N′-ethylenebis(l-ephedrine), where two molecules of l-ephedrine are connected through an ethylene group, has been determined by three dimensional X-ray analysis. The dimensions of the orthorhombic unit cell with the space group P212121-D24 are a=8.431, b=15.92, c=16.70 Å,Z=4 and ρ0=1.34g/cm3. The intensity data were collected by multiple film technique, and the structure was determined by the heavy atom method. The positions of the copper atom simulated the symmetry of a higher space group than that of P212121 and the phases calculated from them gave two pseudo mirrors in the Fourier map based on the copper atom only. The structural determination was made with the use of the methods of successive approximations and diagonal and block diagonal least-squares. The problems concerning the pseudo mirrors were solved mainly from the behaviors of the thermal parameters. The final results were obtained by correcting some unsuitable positional and thermal parameters found by the block diagonal least-squares refinement. The final R-factor is 13.0%. The structure shows that two crystalline water molecules do not coordinate to the copper atom and that the N–C–C–N bridge causes distortion of the square planar coordination around the copper atom.
The Reactivities of Nuclear-Substituted Phenyl Methacrylates in Radical Copolymerization with Styrene
Authors: Otsu Takayuki , Ito Toshio , Fujii Yoshihiro , Imoto Minoru 
Published: July 2006

Abstract
In order to clarify the effects of the alkyl substituents on the reactivities of methacrylate monomers toward the attack of a radical, the copolymerizations of a series of nuclear-substituted phenyl methacrylates with styrene were investigated. From the results, the monomer reactivity ratios and the Alfrey-Price Q, and e values were determined. It was found that the relative reactivities toward the polystyryl radical were not correlated with the ordinary Hammett equation, but a linear relationship was obtained with a modified Hammett equation which contained a term of the resonance contribution by the substituents. Accordingly, it was considered that the reactivities of substituted phenyl methacrylates depend on both polar and resonance effects caused by the substituents.