bluuebunny/crossref_metadata_2025_split huggingface dataset:
Studies of the Solvent Effects on the Chemical Shifts in NMR Spectroscopy. IV. Methoxyl Proton Signals of Methoxybenzenes in the Benzene Solutions
Authors: Matsuo Taku , Yoshida Toshiaki , Higuchi Osamu 
Published: July 2006

Abstract
The chemical shifts of methoxyl protons of a series of methoxybenzenes and the related compounds in cyclohexane, carbon tetrachloride, and benzene solutions have been investigated. The benzene-induced high-field shifts for methoxyl protons are large if the substituent at the benzene ring is a highly electron-withdrawing group. In carbon tetrachloride, the methoxyl proton signals appear at lower field than those in cyclohexane solutions. The low-field shifts also increase with the electronegativities of the substituents. An attempt has been made to interpret the solvent effects by the use of a model where benzene molecules are assumed to cluster around the methoxyl group and the benzene ring of the solute molecule. The attraction between solute and solvent molecules has been suggested to be due to the van der Waals interactions and partly to the charge-transfer interaction.
ESR Study of the Mercury-photosensitized H2+O2 Reaction
Authors: Shimokoshi Kazuo , Mori Yuji , Tanaka Ikuzo 
Published: July 2006

Abstract
The ESR technique has been applied to a study of the mercury-photosensitized reaction of H2+O2 mixtures in the PO2=10–200 μHg and PH2=0.2–4 mmHg regions. For the determination of this reaction, the concentration (ESR signal amplitude) of H atoms was followed with time throughout the reaction. The concentration of H atoms varied with time; its maximum was determined. The time (Tm) at which the H atom concentration reached a maximum depended on oxygen and hydrogen pressures. From the variations in Tm and some kinetic considerations, it was concluded that oxygen played an important role in this reaction in increasing the stationary concentrations of H atoms in the system. In this experiment, I0=2.4×1015 molecules/sec, the rate of the production of H atoms in Reaction (1), was determined from the variations in Tm with the initial oxygen pressure:
(Remark: Graphics omitted.)
The pressure of oxygen at the maximum concentration of H atoms was found to be little dependent on the PH2 used in this experiment; 5 μHg was found to be this pressure.
The Electron Spin Resonance of γ-Irradiated Sodium Polyphosphate. II. Effects of the Degree of Polymerization and the Kind of Cation
Authors: Hasegawa Akinori , Miura Masaji 
Published: July 2006

Abstract
Sodium polyphosphate irradiated with γ-rays was investigated with ESR by varying the degree of polymerization and by replacing sodium ion with other cation. By irradiating at room and liquid nitrogen temperatures and observing ESR at various temperatures, nine kinds of paramagnetic centers were detected. Two of them were attributed to trapped electrons and the others to trapped holes. Four among the latter groups were assigned to radicals on polyphosphate; fragments by bond rupture, –O3PO°· and °·PO3–, radical on end group, –O3PO°·, and radical on chain, –O2P\overset·°OO–.
Active Sites for the Dehydrogenation of Ethyl Alcohol on Lithium Fluoride Single Crystal
Authors: Yamashina Toshiro , Watanabe Kuniaki 
Published: July 2006

Abstract
The dehydrogenation of ethyl alcohol on LiF single crystal surfaces has been investigated to determine the role of surface dislocations and another defects on the catalysis. The catalytic activity of the single crystal of LiF was greatly influenced by the surface treatments such as the manners of cleaving of the crystal and vacuum heating and so on. After radiation quenching subsequent to vacuum anealing at 350°C for 2 hr, the catalytic activity was greatest in the present work, being over seven times greater than that of nontreated crystal. The catalytic activity after the quenching treatment was found to increase in proportion to logarithm of the dislocation density. In observations with the electron microscope, the small spots concentrated in the center of dislocation was found on the highly activated crystal surface. From the results of kinetic and microscopic observations discussion was made on the catalytic sites of the LiF single crystal.
The Reaction of Tris(acetylacetonato)aluminum with Bromine in Dichloromethane
Authors: Nakamura Yukio , Hirata Masaaki , Kawaguchi Shinichi 
Published: July 2006

Abstract
The reaction between tris(acetylacetonato)aluminum and bromine in dichloromethane was studied. The main product of this reaction was tris(γ-bromoacetylacetonato) aluminum which was soluble in dichloromethane. A small amount of slightly yellow precipitate was also produced as a minor product. The same compound was obtained in the reaction of tris(γ-bromoacetylacetonato) aluminum with hydrogen bromide in dichloromethane containing water, and identified as bromoaquobis(γ-bromoacetylacetonato) aluminum on the bases of the elemental and water analyses, the ion exchange study, and the infrared spectroscopy.
Altenin. V. Pathogenic Activity of Reductones to the Pear
Authors: Sugiyama Noboru , Kashima Choji , Yamamoto Makoto , Takano Tadao , Mohri Ryotaro 
Published: July 2006

Abstract
The three reductones, 3-hydroxy-2, 4-dioxopentane, ethyl 2-hydroxy-1, 3-dioxovalerate and ethyl 2-hydroxy-3-oxobutyrate, were synthesized. These compounds were examined for the pathogenic activities to the pear. The pathogenic activities of reductones have some relations with the endiol contents. The center of pathogenic activity in altenin is shown to be the endiol carbonyl grouping.
The Wolff Rearrangement. I. Kinetic Studies of the Decomposition of α-Diazoacetophenone
Authors: Yukawa Yasuhide , Tsuno Yuho , Ibata Toshikazu 
Published: July 2006

Abstract
Kinetic studies of the Wolff rearrangement of α-diazoacetophenone were performed in t-butyl alcohol, by the volumetric measurement of the evolved nitrogen, using a solution of silver benzoate in triethylamine as a catalyst. A pseudo-first-order rate constant was obtained accompanying the induction period. The effects of the concentrations of silver benzoate and triethylamine on the reaction rate were studied. The concentration of silver ions was determined by the gravimetric measurement of silver chloride in the course of the reaction. The silver ions were found to be consumed only in the initial stage of the reaction. On the basis of these results, a novel reaction mechanism, in which the active entity of the catalyst was thought to be a silver ion-triethylamine complex, was proposed.
The Wolff Rearrangement. II. The Substituent Effects on the Rate of the Catalytic Decomposition of Substituted α-Diazoacetophenones
Authors: Yukawa Yasuhide , Tsuno Yuho , Ibata Toshikazu 
Published: July 2006

Abstract
The substituent effect on the reaction rates of the Wolff rearrangement of meta- and parasubstituted α-diazoacetophenones was studied in t-butyl alcohol, isopropyl alcohol, and t-butyl alcohol-toluene mixed solvents, and also on the decomposition rates in toluene, using a solution of silver benzoate in triethylamine as a catalyst. Similar substituent effects were observed regardless of the solvents used. Strong electron-releasing conjugative substituents at the para position, such as methoxy and ethoxy groups, retard the reaction rate greatly. The other substituents accord roughly with the Hammett relationship, having small negative ρ-values. The decomposition rate constants in toluene were apllicable to the Yukawa-Tsuno equation, which has a negative γ-value:
logk⁄k0=−0.45(σ−2.7ΔσR+)−0.05
proving that the resonance stabilization on the reaction origin are caused by the electron-releasing substituent at the para position. The results of the kinetic isotope effects (no apparent kinetic isotope effect was observed within the range of experimental error) of the Wolff rearrangement of carbonyl-14C, and phenyl-1-14C labeled α-diazoacetophenone under the same reaction conditions favor the two-step mechanism to the concerted one for the elimination of nitrogen and the migration of the alkyl group.
The Preparation of 1-Dimethylamino-1-ethylthioethylene (Ketene-N, S-acetal) and Its Reactions with Some Electrophilic Reagents
Authors: Mukaiyama Teruaki , Aizawa Shin-ichi , Yamaguchi Tatsuaki 
Published: July 2006

Abstract
The preparation of 1-dimethylamino-1-ethylthioethylene (ketene-N, S-acetal) from N, N-dimethylamino-S-ethylthioacetamidium iodide and the reactions of the ketene-N, S-acetal with some electrophilic reagents were investigated. One equivalent of phenyl isocyanate and two equivalents of diphenylketene reacted with the ketene-N, S-acetal to produce substituted acrylanilide and 2, 3-dihydro-α-pyrone derivative, respectively. On the other hand, the reactions of the ketene-N, S-acetal with carbon disulfide in the presence of elemental sulfur and with electrophilic oleflns, such as acrylonitrile and methyl acrylate, gave 5-dimethylaminotrithione and substituted cyclobutenes, respectively, by eliminating ethyl mercaptan. Further, it was found that α, β-unsaturated carbonyl compounds, such as acrolein and methyl vinyl ketone, afforded bicyclic compounds, 2, 10-dioxabicyclo[4. 4. 0]decadiene-3, 8 derivatives.
Anionic Copolymerization of Styrene and 1, 1-Diphenylethylene
Authors: Yuki Heimei , Hotta Junichi , Okamoto Yoshio , Murahashi Shunsuke 
Published: July 2006

Abstract
The anionic copolymerization of styrene (M1) and 1, 1-diphenylethylene (M2) was investigated. 1, 1-Diphenylethylene, which can not homopolymerize by itself, was copolymerized with styrene by means of an anionic initiator. The copolymerization reaction seemed to proceed without termination or chain transfer, and gave a high molecular alternating copolymer under appropriate reaction conditions. The monomer reactivity ratio, r1, was obtained from the copolymer composition at the complete consumption of M1, assuming the rate constant k22=0. The monomer reactivity ratio was affected by the solvent (n-hexane, benzene, toluene, or THF), but not by the catalyst (n-BuLi, Na-dispersion, Na-naphthalene, or K-dispersion) or the reaction temperature. It was 0.4 in toluene at 30°C.
Polymerization Initiated with a Potassium Complex of Aromatic Ketone and Its Use in the Preparation of a Multi-Chain Copolymer
Authors: Nobutoki Koji , Sumitomo Hiroshi 
Published: July 2006

Abstract
Four kinds of complexes were prepared by the reactions of benzil with a potassium or potassium-sodium alloy in tetrahydrofuran. The polymerizations of styrene (St), isoprene (Ip), methyl methacrylate (MMA), and ε-caprolactone (CL) initiated with these complexes were attempted. St and Ip were found to be polymerized by the dipotassium or tetrapotassium adducts of benzil, but not by the monopotassium ketyl. All these complexes were effective in polymerizing MMA and CL. A new class of multi-chain copolymers with different kinds of branches was also prepared by the polymerizations of MMA and CL with the potassium adducts of polystyrene ketones synthesized by the coupling reactions of one-ended living polystyrene with 2, 4′-dichlorobenzophenone or terephthaloyl chloride.
Solution Properties of the Methyl Methacrylate-Acrylonitrile Copolymer
Authors: Shimura Yuko 
Published: July 2006

Abstract
Short-range interactions between chain units of random copolymers in solution may be influenced by the characters of the pendant side groupes or, more precisely, by the dipole moment of the substituent. In those experiments the steric factor was derived for a random copolymer composed of methyl methacrylate and acrylonitrile from the relation between the limiting viscosity number and the molecular weight. Mark-Houwink relations were obtained in N,N′-dimethylformamide (DMF) and in methyl ethyl ketone (MEK) at 30°C for the copolymer containing 0.48 mol fraction of acrylonitrile, and for polymethyl methacrylate (PMMA) for the sake of comparison:
[η]=4.61×10−4M0.65 for the copolymer in DMF
[η]=1.70×10−4M0.65 for PMMA in DMF
[η]=1.26×10−3M0.52 for the copolymer in MEK
With the Stockmayer-Fixman expression, these correlations become, respectively:
[η]=213×10−5M1⁄2+12.4×10−7M
[η]=78.2×10−5M1⁄2+5.05×10−7M
[η]=163×10−5M1⁄2+1.05×10−7M
The unperturbed mean square end-to-end distance, 〈L2〉0, determined from the first term of the latter expressions, together with the 〈L2〉0f value calculated by assuming the completely free rotation, gives the steric factor of σ=(〈L2〉0⁄〈L2〉0f)1⁄2 2.59±0.01 from the DMF solution; this factor is larger than that for polymethyl methacrylate (2.11±0.08),, and that for polyacrylonitrile (2.20+0.05). The steric parameter derived from the MEK solution is 2.37±0.05 for this co-polymer; this value does not agree with the value obtained from the DMF solution. In both cases, it may be concluded that the dimensions of the copolymer between acrylonitrile and methyl methacrylate are influenced by the electrostatic interactions between nitrile groups of acrylonitrile units and methoxy-carbonile and/or methyl groups of methyl methacrylate units. The second virial coefficient in MEK obtained from the light scattering measurements also has a larger value for this copolymer than for polymethyl methacrylate. This tendency of copolymers to show a larger second virial coefficient seems to be an essential characteristic of some copolymers.
Some Applications of the Regular Solution Theory to Solvent Extraction. IV. Oxine-Inert Solvent System
Authors: Wakabayashi Toshiki 
Published: July 2006

Abstract
The distribution coefficients of oxine between aqueous solutions with the ionic strength of 0.1 and 12 inert solvents were determined photometrically at 25°C. By a previously-proposed equation, the distribution coefficients were then correlated quantitatively with the solubility parameters of the solvents. The solubility parameter for oxine was evaluated as 10.9, and that for an aqueous solution, as 16.95, while the molar volume of oxine was estimated to be 124 cc/mol. The distribution of the two methyl derivatives of oxine was also discussed.
Studies of Phosphorylation. I. Phosphorylation of 2′, 3′-O-Isopropylidene Nucleoside by Phosphoryl Chloride
Authors: Yoshikawa Masaharu , Kato Tetsuya 
Published: July 2006

Abstract
5′-Nucleotides could be conveniently prepared in high yields by the phosphorylation of 2′, 3′-O-isopropylidene nucleosides with phosphoryl chloride in the absence of any organic solvent. The rate of phosphorylation in a large excess of phosphoryl chloride was markedly promoted by the partial hydrolysis of phosphoryl chloride with a small amount of water. The undesirable cleavage of the glycosidic linkage in nucleoside, which was observed particularly in a strongly acidic medium caused by the addition of excessive water, could be suppressed by the addition of ethers or amines in a phosphoryl chloride solution. 2′, 3′-O-Isopropylidene derivatives of adenosine, inosine, and guanosine gave the corresponding 5′-nucleotides in good yields, whereas that of xanthosine reacted very slowly, unlike the above nucleosides. All attempts at the phosphorylation of 2′, 3′-O-isopropylidene-2-mercaptoinosine were unsuccessful. The influence of substituents at the 2-position in purine bases on phosphorylation was investigated by comparing the reactivity between the above-mentioned nucleosides and their methylated derivatives, such as 2-dimethylaminoinosine, 2-methoxyinosine, and 2-methylthioinosine; it was found that these methylated nucleosides were readily phosphorylated to give the corresponding 5′-nucleotides in nearly quantitative yields.
Effects of Ligands in the Cobalt Salt-catalyzed Decomposition of t-Butyl Hydroperoxide
Authors: Onuma Kazuhiko , Wada Keisuke , Yamashita Junzo , Hashimoto Harukichi 
Published: July 2006

Abstract
A kinetic study has been made of the cobalt acetate-catalyzed decomposition of t-butyl hydroperoxide in acetic acid at 40.4°C, and the effects of added lithium salts on the decomposition rate have been studied. The observed rate law for the cobalt acetate-catalyzed decomposition is: v=k2[Co(II)][t-C4H9OOH]+k3[Co(II)]2[t-C4H9OOH]. When lithium halides (chloride and bromide) are added to this system, the cobalt acetate is changed to cobaltous halide and the rate of decomposition is markedly decreased. In the case of lithium bromide the hydroperoxide decomposition is accompanied by the generation of molecular bromine. The mechanisms for the bromine formation will be discussed. The role of these cobalt salts in the course of autoxidation in relation to the hydroperoxide decomposition will also be discussed.
Studies of Peptide Antibiotics. XII. Syntheses of [2,2′-α,γ-Diaminobutyric acid]- and [2,2′-Lysine]-gramicidin S
Authors: Waki Michinori , Abe Okitoshi , Okawa Reiko , Kato Tetsuo , Makisumi Satoru , Izumiya Nobuo 
Published: July 2006

Abstract
To investigate the contribution for the antibacterial activity of the ornithine residues in gramicidin S, two analogs of gramicidin S, [2, 2′-l-α,γ-diaminobutyric acid]- and [2, 2′-lysine]-gramicidin S, were synthesized by the cyclization reaction of linear pentapeptide active esters with pyridine. It was indicated that the crude product of the cyclization of each of the linear active esters was composed of two components. The protected cyclic decapeptide, a less soluble material, was easily isolated by fractional crystallization, and the hydrogenolysis of this product in the presence of hydrogen chloride afforded the crystalline hydrochloride of [2, 2′-diaminobutyric acid]-or [2, 2′-lysine]-gramicidin S. These cyclic decapeptides were as active as natural gramicidin S; the results indicated that the side chains of the ornithines in gramicidin S could be replaced by other chains without a loss of activity.
Über die Reduktion von 5-Oxo-2-methyl-4, 4-dibenzyl-3-äthoxycarbonyl-4, 5-dihydroindol und die Umsetzungen des Reduktionsproduktes mit Säuren
Authors: Suehiro Tadashi , Nakagawa Akihiro 
Published: July 2006

Abstract
5-Oxo-2-methyl-4, 4-dibenzyl-3-äthoxycarbonyl-4, 5-dihydroindol (I) ist ziemlich beständig gegen allgemeine Reduktionsmittel, wird aber reduziert mit Aluminium-Amalgam oder mit Natriumborhydrid. Bei der ersten Reduktion entsteht ein dimerer Alkohol. Bei der letzteren wird 5-Hydroxy-2-methyl-4, 4-dibenzyl-3-äthoxycarbonyl-4, 5, 6, 7-tetrahydroindol (III) gebildet. Die Hydroxy-Gruppe von III wird leicht bei der Behandlung mit Eisessig-Salzsäure oder -Schwefelsäure mit der Chlor- oder Acetyloxy-Gruppe unter Deäthoxycarbonylierung ausgetauscht. Dehydratisierung von III gelingt bei der Einwirkung von syrup. Phosphorsäure unter gleichzeitiger Deäthoxycarbonylierung and Umlagerung einer Benzyl-Gruppe in 2-Methyl-4, 5-dibenzyl-6, 7-dihydroindol (VII). VII lässt sich über Palladium-Kohle in 2-Methyl 4, 5-dibenzylindol (IX) dehydrieren, dessen Struktur synthetisch festgestellt wurde.
An X-Ray Emission Spectroscopic Investigation of the Chemical Bond of Sulfur. I. The Peak Shift of Kα and the Number of Valence Electrons of the Sulfur Atom in Compounds
Authors: Sato Toshio , Takahashi Yoshihito , Yabe Katsumasa 
Published: July 2006

Abstract
The energy shifts of the SKα doublet have been measured in fifty sulfur compounds in solid or liquid states, using rhombic sulfur as a standard. The values were the same as those obtained by Faessler and Goehring, although a slight discrepancy was observed on sulfites and sulfates. The mean number of the valence electrons, N, associated with the sulfur atom in compounds has then been calculated from the shifts according to a theoretical correlation presented by Coulson and Zauli. The values of N have been found to be 6.7, 6.3, 5.2, 4.7, 4.7, and 4.3 for inorganic sulfides, organic sulfides, sulfoxides, sulfites, sulfones and sulfates respectively, assuming that N=6.0 for rhombic sulfur. The dipole moments evaluated from the values of N and structural data were 4.9, 4.8 and 5.2D, for dimethyl sulfoxide, dimethyl sulfone and diphenyl sulfone, respectively; these values were almost compatible with the experimental values of 3.9, 4.41 and 5.14D. respectively.
A Molecular Orbital Investigation of the Electronic Structures of Alkyl Peroxides. II Peracids and Peresters
Authors: Yonezawa Teijiro , Kato Hiroshi , Yamamoto Osamu 
Published: July 2006

Abstract
The electronic structures of several alkyl peroxides including the carbonyl group, i. e., performic acid, peracetic acid and their methyl esters, are investigated by the extended Hiickel method proposed by Hoffmann. The structure of the bond between peroxy oxygens, the intramolecular hydrogen bonding in peracid, the pyrolysis of peracid which is caused by the fact that the bond strength between peroxy oxygen atoms is weakened by an intramolecular hydrogen bonding, and the reaction mechanism of both the epoxidation of olefin by peracid and the ionic decomposition of peresters by basic catalysts can be successfully explained on the basis of the calculated results.
The Extraction of Gallium and the Direct Spectrophotometric Determination in the Organic Phase with 4-(2-Pyridylazo)-resorcinol
Authors: Bansho Kenji , Umezaki Yoshimi 
Published: July 2006

Abstract
A rapid method for the spectrophotometric determination of microgram amount of gallium with 4-(2-pyridylazo)-resorcinol (PAR) in the organic phase after the extraction of gallium from a hydrochloric acid solution with isopropyl ether and butyl acetate will be described. A red color is formed in an aliquot of the organic extract by the addition of PAR, pyridine, and sodium acetate in methanol. The complex formed in the organic phase has a maximum absorbance at 510 mμ. The color reaction conforms to Beer’s law, and the molar absorptivity of the complex is estimated to be approximately 100000. The coefficient of the variation of the absorbance measurements on a standard gallium solution at 510 mμ was about 0.8%. A study of the effect of diverse ions showed the method to be highly selective.
The Synthesis and the Electronic Spectra of 1, 1′-Dianthrylpoly-ynes
Authors: Akiyama Shuzo , Nakagawa Masazumi 
Published: July 2006

Abstract
The synthesis of 1, 1′-dianthryldi- and tetra-acetylenes has been reported previously by the present authors. Now, 1, 1′-dianthryltri-, penta- and hexa-acetylenes have been synthesized in order to complete the series of 1, 1′-dianthrylpoly-ynes. It is well known that the square of the wavelength of the longest absorption maxima, λmax in the electronic spectra of some series of poly-enes and poly-ynes varies linearly with the number of the multiple bonds, n(λmax2∞n). It was anticipated that the dianthrylpoly-ynes would exhibit analogous spectral behavior. Unexpectedly, however, it was observed that the λmax of the dianthrylpolyacetylenes varied linearly with the square of the number of the triple bonds, n(λmax∞n2).
The Synthesis of the Cyclohexenone Palladium Complex and Related Compounds
Authors: Kasahara Akira , Tanaka Keiko , Asamiya Kazunori 
Published: July 2006

Abstract
The chloro-bridged π-allylic palladium complex has been prepared from cyclohexenone and sodium chloropalladite. 6-Oxo-4, 4-dimethylcyclohex-2-enyl, 1,2-(4-oxo-2, 2-dimethylbutano)-π-allyl and 1, 2-(1-oxo-butano)-3-phenyl-π-allyl palladium complexes have also been prepared from the corresponding cyclic α, β-unsaturated ketones. The structures of all these compounds have been confirmed by a study of their absorption spectra and of the NMR spectra.
The Synthesis of Friedelan-3-on-24-al
Authors: Hoshino Tokiko , Tsuyuki Takahiko , Takahashi Takeyoshi 
Published: July 2006

Abstract
24-Oximinofriedelan-3β-ol (V) was converted via either lactone (VI) or hemiacetal (VIII) into diol (VII). Monoacetylation of the diol gave 24-acetoxyfriedelan-3β-ol (X), which was oxidized to keto acetate (XI). Hydrolysis of XI afforded the corresponding keto alcohol, followed by Jones’ oxidation giving rise to friedelan-3-on-24-al (I), mp 248—249°C, [α]578 +66°. The physical constants of I are not identical with those of friedelan-3-on-y-al, isolated by Courtney et al. from Siphonodon australe Bent. This furnishes a further evidence that friedelan-3-on-y-al is not friedelan-3-on-24-al (I), but friedelan-3-on-25-al, confirming the recent Courtney’s proposal.