bluuebunny/crossref_metadata_2025_split huggingface dataset:
Thallic Salt as the Catalyst for the Conversion of Acetylenes to Carbonyl Compounds
Authors: Uemura Sakae , Kitoh Ryohzoh , Fujita Koichi , Ichikawa Katsuhiko 
Published: July 2006

Abstract
It has been shown that the conversion of acetylenes to carbonyl compounds proceeds in various solvents containing thallic salts as the catalyst. Acetylene, methylacetylene, phenylacetylene, propargyl alcohol and its ester, and phenylpropiolic acid and its ester reacted to form acetaldehyde, acetone, acetophenone, acetoxyacetone and acetophenone respectively.
The Photochemical Oxidation Reaction of Benzylic Alcohols in Dimethyl Sulfoxide
Authors: Sato Takeo , Inoue Hiroshi , Hata Kazuo 
Published: July 2006

Abstract
A new photochemical oxidation reaction of benzylic alcohols has been developed by using DMSO as a solvent. The oxidation, which has been performed in an oxygen atmosphere, can be carried out under neutral conditions at room temperature. Detailed studies on the role of DMSO as the solvent were carried out by using benzyl alcohol; it has been established that, in the photo-oxidation in DMSO, the uptake of oxygen was much facilitated compared with the reactions using other solvents, and also that, the benzaldehyde formed was well protected from further oxidation by a complex formation. Three secondary benzylic alcohols gave moderate yields of the corresponding ketones. The same experiments on ten substituted benzyl alcohols have revealed that the presence of an electron-releasing group facilitates the oxidation affording benzaldehydes, whereas an electron-attracting group retards it.
Studies on Reactions of Polypropylene. VIII. The Thermal Degradation of Polypropylene Accelerated by Polyglycidyl Methacrylate
Authors: Mizutani Yukio , Yamamoto Keiichi , Matsuoka Seishiro , Hisano Shigeo 
Published: July 2006

Abstract
The thermal degradation of polypropylene was investigated in the presence of polyglycidyl methacrylate (PGMA) by the use of an extruder under a nitrogen atmosphere. PGMA was found to be effective as an accelerator for the thermal degradation of polypropylene. The accelerating effect of PGMA was attributed to the facts that PGMA was degraded thermally by the zipper-scission mechanism and that the active radical thus generated was effective in accelerating the thermal degradation of polypropylene by the random-scission mechanism. The surviving ratio of the epoxy group throughout the thermal degradation was not as large as had been expected.
Electron Spin Resonance of Anion Radicals of N-Alkyl Phthalimides and Aromatic Acid Anhydrides
Authors: Hirayama Masatoshi 
Published: July 2006

Abstract
The ESR spectra of anion radicals of N-methyl, N-ethyl, and N-n-butyl phthalimides, naphthalic acid anhydride, and pyromellitic acid anhydride were measured in acetonitrile. Both the electrolytic and alkali metal reduction methods were used for the radical generation. The spin densities of these anion radicals were then calculated by McLachlan’s method; the calculated results were partly in agreement with the experimental data. Satellite lines due to three kinds of 13C nuclei in the pyromellitic acid anhydride anion radical were observed; one of these splitting constants was assigned to the position 1.
NMR Spectra of Some Metal Acetylacetonates
Authors: Kawasaki Yoshikane , Tanaka Toshio , Okawara Rokuro 
Published: July 2006

Abstract
The NMR spectra of a series of complexes, XX′Sn(acac)2 (X, X′ =alkyl, aryl and halogen), (CH3)2Pb(acac)2, Cl2Ti(acac)2, Cl2Ge(acac)2, Cl4Sb(acac) and (C6H5)Cl3Sb(acac), have been studied in chloroform. A linear relationship has been found between the chemical shifts of the γ proton and those of the methyl protons of acetylacetone for various type of complexes. In XX′Sn-(acac)2, both τ values decrease with an increase in the electron-attracting power of the substituents, X and X′, and the chemical shifts of these protons are found to be correlated with the Sn–O and C=O stretching frequencies. This behavior can be explained in terms of the inductive effect of the substituents on the tin atom.
Solvent Effect on the Proton Magnetic Resonance Spectra of Dimethyltin Dichloride, Trimethyltin Chloride and Trimethyllead Chloride
Authors: Matsubayashi Gen-etsu , Kawasaki Yoshikane , Tanaka Toshio , Okawara Rokuro 
Published: July 2006

Abstract
The chemical shifts of methyl protons (τ(M–CH3) values) and the coupling constants between the methyl protons and the metal atom JM–CH3 values for dimethyltin dichloride, trimethyltin chloride, and trimethyllead chloride have been measured in thirty-two organic solvents. From the relation between the τ(M–CH3) and the JM–CH3 values, the solvents used here have been classified into four groups. Carbon tetrachloride is representative of the first groups. The second group consists of usual polar organic solvents which can coordinate to the metal atom. The third consists of nitrobenzene, benzonitrile, pyridine, and its derivatives among the solvents studied here. The fourth consists of alkyl- or halogen-substituted aromatic solvents. The configurations of trimethyltin chloride in these solvents have been discussed on the basis of the J119Sn−CH3 values and the intensity of the Sn–C symmetric stretching band relative to that of the asymmetric one. The effects of the temperature and the concentration of the solute on the τ(Sn–CH3) and the J119Sn−CH3 values of trimethyltin chloride have been examined in several solvents.
The Dipole Moments and Polarizabilities in the Excited States of Four Benzene Derivatives from Spectral Solvent Shifts
Authors: Abe Takehiro 
Published: July 2006

Abstract
According to Abe’s expressions for the spectral solvent shifts (Bull. Chem. Soc. Japan, 39, 936 (1966)), the dipole moments, polarizabilities, and solvation energies in the excited states of nitrobenzene, anisole, acetophenone, and p-chloroacetophenone have been estimated. The large dipole moments of 6.78 and 4.23 D for the excited states of nitrobenzene and acetophenone respectively have supported Nagakura and Tanaka’s theory of the intramolecular charge-transfer band.
Heat Measurement by Differential Thermal Analysis
Authors: Ozawa Takeo , Momota Michihiko , Isozaki Hiroshi 
Published: July 2006

Abstract
A new method of measuring the heat of transformation is described; the apparatus used in quantitative differential thermal analysis is calibrated by using an electrical heater inserted in the sample cell. The heats of transformation obtained by using the proportionality coefficient thus calibrated are then compared with the reported values. Good agreements are obtained between them.
The Isomerization Polymerization of 2-Butene
Authors: Iwamoto Masao , Yuguchi Sadao 
Published: July 2006

Abstract
The crystalline polymer has been obtained by polymerizing 2-butene using a Ziegler-type catalyst containing titanium trichloride. 2-Butene was transformed into an equilibrium mixture of 1-butene and cis- and trans-2-butene by the catalytic action of titanium trichloride. When alkylaluminum was present in the system, isotactic poly-1-butene was obtained. These results can be explained by the concept of isomerization polymerization.
The Electronic Spectra of Nitrile N-Oxides and the Solvent Effect on Them
Authors: Yamakawa Masumi , Kubota Tanekazu , Akazawa Hideko 
Published: July 2006

Abstract
The electronic spectra of several substituted benzonitrile N-oxides and 9-anthronitrile N-oxide were recorded in various solvents and compared with those of the corresponding nitriles. The following results were thus obtained. (1) Substituted benzonitrile N-oxides showed a characteristic strong π–π* band at wavelengths much longer than those of the 1La band of the corresponding nitriles. (2) The π–π* band showed a blue shift with an increase in the polarity of the solvents. Quantitative analyses of the solvent effect led to the result of the decreasing dipole moment at π–π* state. (3) The hydrogen-bonding ability of the nitrile N-oxides was found to be weak from experiments on three-component systems and from analyses of the above solvent effect. (4) The electronic structures of the nitrile N-oxides were discussed on the basis of the above-mentioned findings and the measurements of the infrared spectra. It was suggested that the interaction of oxygen 2pπ electrons with the rest of the π electron system should be taken into consideration.
Kinetic Study of Pyrolysis of Toluene-d5
Authors: Takenaka Jumpei , Endo Harumi , Mikuni Hitoshi , Takahasi Makoto 
Published: July 2006

Abstract
Reaction mechanism of pyrolysis of toluene was studied with toluene-d5 of high isotopic purity. The rate constant of pyrolysis of toluene-d5 in gas phase was determined to be k=1011.5±0.3×exp(−70±1 kcal/mol) (sec−1) and compared with that of toluene. Hydrogen isotope mixtures produced in the pyrolysis of toluene-d5 were collected and analyzed by mass spectrometer. Formation of some amount of D2 is confirmed, and it is concluded that the fission of ring C–D bond is involved to some extent in the pyrolytic reaction of toluene-d5 at high reaction temperatures. The ratio of rate constants of abstraction type (kD–H⁄kH–H) is also determined, and the difference of the activation energies between kD–H and kH–H is found to be approximately 14 kcal/mol.
The Polarographic Behavior of the Condensation Products of o-Phenylenediamine with Biacetyl and with Methylglyoxal, and Its Application to the Determination of Biacetyl and Methylglyoxal
Authors: Wasa Tamotsu , Musha Sôichirô 
Published: July 2006

Abstract
Both the condensation product of o-phenylenediamine (OPD) with methylglyoxal and that with biacetyl produce two diffusion-controlled reduction waves, each corresponding to a one-electron transfer, at pH values below 3 (E1⁄2:−0.220 V and −0.332 V vs. SCE for the methylglyoxal product, and −0.270 V and −0.447 V for the biacetyl product respectively, at pH=1.5), or a single well-defined reduction wave corresponding to a two-electron transfer at pH values above 3 (E1⁄2:−0.831 V and −0.902 V respectively, at pH=9.0). At pH values below 8, it has also been observed that the reduction product with the two-electron wave shows an ill-defined reduction wave (E1⁄2:−1.15 V and −1.07 V respectively, at pH=5.0) at a little more positive potential than that of the hydrogen ion discharge. During the course of the controlled-potential electrolysis at −1.0 V vs. SCE at a pH value of about 9, it has been observed that the anodic wave of the reduction product with the same half-wave potential as the above reduction wave grows at the expense of the reduction wave (probably because of the quinoxaline formed by the condensation), while, though the reduction wave decreases with the electrolysis at −0.7 V, no anodic wave due to the oxidation of the electrolytic reduction product is obtained at pH values lower than 6. A linear relationship between the limiting current of the condensation product and the concentration (0.5–20×10−4m) of methylglyoxal or biacetyl has been obtained under the following conditions, which are recommended for the practical determination: 3–10 for pH, (1–2)×10−2m for the concentration of OPD, 25°C for the temperature, and 20–60 min for the condensation time. The method was also used to determine the purity of a methylglyoxal prepared in the laboratory and that of a commercial biacetyl.
The Polarographic Behavior of the Condensation Products of o-Phenylenediamine with Glycolaldehyde and with Glyceraldehyde, and Its Application to the Determination of Glycolaldehyde and Glyceraldehyde
Authors: Wasa Tamotsu , Musha Sôichirô 
Published: July 2006

Abstract
Glycolaldehyde and glyceraldehyde condense with o-phenylenediamine (OPD) in a buffered solution (pH 2–10) containing an excess of the latter to produce the corresponding condensation products. Both condensation products give a single diffusion-controlled oxidation wave E1⁄2:−0.08 V vs. SCE for both aldehydes at pH 6.0) at the dropping mercury electrode, and their electrode reactions are irreversible over all the pH range studied (pH 2—10). The limiting currents of both waves show their maximum values at pH values of about 6 and decrease either with an increase or a decrease in the pH from about 6. From the results of the present polarographic investigations, it has been deduced that the condensation products of OPD with glycolaldehyde and with glyceraldehyde are probably benzimidazoline derivatives. The equilibrium constants for the condensation reaction of glycolaldehyde and glyceraldehyde with OPD were calculated to be 551 and 294 l/mol respectively at 25°C. A linear relationship between the limiting current of the condensation product and the concentration [(0.5–30)×10−4m] of glycolaldehyde or glyceraldehyde was obtained under the following conditions, which are recommended for the practical determination: 5.5–6.5 for pH, 2×10−2m for the concentration of OPD, 25°C for the temperature, and 5–60 min for the condensation time. The present method was applied to the determination of the glycolaldehyde present as an impurity in a commercially-available ethylene glycol.
Cholestanol Esters of Amino Acids
Authors: Matsumoto Yoshio , Shirai Michiko , Minagawa Michio 
Published: July 2006

Abstract
The cholestanol (5α-cholestan-3β-ol) esters of amino acids were synthesized with an interest for their possible biochemical activities. The cholestanol esters of glycine, l-alanine, β-alanine, l-leucine and l-aspartic acid were synthesized by a direct fusion of the two components under the passing of hydrogen chloride through the reactants. That of glutamic acid was prepared by using quinoline hydrochloride as a solvent. From the condensation product of aspartic acid and cholestanol, mono- and di-ester were isolated. The monocholestanol ester of aspartic acid was also synthesized by the Gabriel process.
Studies on Hydrogenation Reactions with Metal Sulfide Catalysts. III. Hydrogenation and Isomerization of Cyclohexene
Authors: Hai Chang King 
Published: July 2006

Abstract
The catalytic liquid phase hydrogenation and/or isomerization of cyclohexene are investigated at 160–350°C under 50–90 kg/cm2 of hydrogen or atmospheric nitrogen using molybdenum trisulfide and various other metal sulfides or oxides, with or without additives, as catalysts. The activity of catalysts is found to be in the order of MoS3≥MoS2&gt;WS3&gt;CoS3&gt;NiS2. The hydrogenation product is almost entirely cyclohexane, except when molybdenum trisulfide is used as a catalyst, in which case the reaction at 310°C accompanies isomerization to a considerable extent, yielding up to 24% of methylcyclopentane. The molybdenum disulfide catalyst with the addition of sulfur or hydrogen sulfide is similar to the molybdenum trisulfide in its selectivity for the course of reaction. The reason for these results is discussed. The main isomerization reaction path is found to be cyclohexene → methylcyclopentene-(1) → methylcyclopentane.
γ-Ray Induced Telomerization Reactions between Allylic Compounds and Carbon Tetrachloride. IV. Reactions of Acetates of Methyl-substituted Allylic Alcohols
Authors: Okubo Masao 
Published: July 2006

Abstract
The γ-ray induced telomerization of allyl, α-methallyl, α,α-dimethylallyl, and β-methallyl acetates with carbon tetrachloride was carried out in order to compare the effects of methyl substituents. In the cases of the former three acetates, the effect of successive methyl substitution on the allylic α-position was found to show exactly the same regularity as to the effects on the velocities of C=C consumption, the telomer production ratios, and their change with the initial concentration of esters. In contrast with the case of α-substitution, while the β-methyl substituent retards the velocity of the C=C consumption to the utmost extent, it retards the telomer production ratio only a little; moreover, it depresses the effect of the ester concentration upon the former to some extent, but it minimizes that upon the latter. Together with these observations, the amounts of hydrogen chloride generated during irradiation was discussed in relation to the degradative chain transfer mechanism.
Studies of Peptide Antibiotics. IX. Synthesis of cyclo-(l-Valyl-l-ornithyl-l-leucyl-d-phenylalanyl-glycyl)
Authors: Aoyagi Haruhiko , Kondo Michio , Kato Tetsuo , Makisumi Satoru , Izumiya Nobuo 
Published: July 2006

Abstract
It was previously observed that the cyclization reaction of l-valyl-δ-benzyloxycarbonyl-l-ornithyl-l-leucyl-d-phenylalanyl-glycine p-nitrophenyl ester in pyridine yields a large amount of the pyridine-insoluble product (IV), besides a small amount of the protected cyclic decapeptide by the dimerization. By the molecular weight determination of IV with a osmometer, it was proved that the product IV is the protected cyclic pentapeptide. Hydrogenolysis of IV in a mixture of acetic acid and dimethylformamide gave cyclo-(valyl-ornithyl-leucyl-d-phenylalanyl-glycyl) acetate which showed no antibacterial activity in relation to any of the microorganisms tested.
(Remark: Graphics omitted.)
The Spectra of the Chemiluminescence, Fluorescence and Absorption of Lucigenin and Its Electron Spin Resonance
Authors: Maeda Koko , Hayashi Taro 
Published: July 2006

Abstract
In order to study the mechanism of the chemiluminescence of lucigenin which was emitted with hydrogen peroxide in an alkaline solution, the color and the spectrum of the chemiluminescence and fluorescence, the spectrum of absorption, and the electron spin resonance were investigated. The color of the chemiluminescence was found to vary from green to blue with a decrease in the concentration of lucigenin. The spectrum of the blue chemiluminescence spread over only a visible region of 420—650 m/μ, with a peak at 485 mμ. With an increase in the concentration of lucigenin, the peak shifted to 510 m/μ or longer, corresponding to the green color of the chemiluminescence. This shift is due to self-absorption by lucigenin. The fluorescence spectrum of lucigenin in aqueous sodium hydroxide showed a peak at 508 mμ. The peak gradually disappeared, and the spectrum eventually showed new peaks at 435 and 450 m/μ which almost agreed with the peaks of the fluorescence spectrum of 10-methylacridone. Lucigenin exhibited an electron spin resonance of a single peak (g-value 2.004) in a solid state. These results show that the chemiluminescence of lucigenin is neither of the fluorescence of lucigenin nor that of 10-methylacridone yielded in the chemiluminescent solution of lucigenin and that the mechanism of the chemiluminescence is likely to involve a free radical intermediate.
Some 4(1H)-Pyridylidene Compounds. Synthesis and Structure
Authors: Omote Yoshimori , Kuo Kung-Tu , Sugiyama Noboru 
Published: July 2006

Abstract
The reaction of methyl 4-chloro-pyridine-2,6-dicarboxylate with a sodium compound of t-butyl cyanoacetate, ethyl cyanoacetate, or malononitrile, followed by acidification, gives the corresponding 4(1H)-pyridylidene compound, t-butyl cyano-4(1H)-(2,6-bismethoxy-carbonyl-pyridylidene)-acetate (IVa), ethyl cyano-4(1H)-2,6-bismethoxycarbonyl-pyridylidene) acetate (Va), or 4(1H)-(2,6-bismethoxy-carbonyl-pyridylidene)malononitrile (Via). The structures assigned to these compounds are based on the UV, IR and NMR spectra. In an alkaline solution, IVa, Va and Via change into the anion forms. The elimination reaction of IVa and Va is also examined.
Studies on Amino-hexoses. XIII. The Synthesis of Methyl 4′,6′-O-Ethylidene-β-pseudocellobiouronoside Methyl Ester, and Its Degradation with Hydrazine
Authors: Fujinaga Mamoru , Matsushima Yoshio 
Published: July 2006

Abstract
A derivative of pseudocellobiouronic acid, methyl 4′,6′-O-ethylidene-β-pseudocellobiouronoside methyl ester was prepared and subjected to the treatment with hydrated or anhydrous hydrazine. Both of hydrated and anhydrous hydrazine have been found to cause the glycosidic cleavage, the extent of which has been estimated by measuring the amount of 4′,6′-O-ethylidene-d-glucose formed by a gas-liquid partition chromatography. The results obtained suggest that the polysaccharides which contain 1→4 glycosidic bonds to the uronic acids are degraded by the hydrazine treatment, conceivably due to β-elimination reaction.
Verification of Bhattacharya’s Equation for Slow Coagulation by Spectrophotometric Measurements in Copper Ferrocyanide and Zinc Ferrocyanide Sols
Authors: Chaturvedi D N , Bansal O P 
Published: July 2006

Abstract
The copper ferrocyanide and zinc ferrocyanide sols have been prepared, and their precipitation values have been studied by using KCl, BaCl2 and AlCl3 and by employing the spectrophotometric method in the light of the equation:
C=a+\fracm·1⁄tn+1⁄t
It has been found that the values of a and m remain the same at all stages of coagulation, while the value of n depends to a great extent on the coagulation stage.
The Photochemistry of Aqueous Hexacyanoferrate(II) Solutions. II. Photo-oxidation Reaction at 2537Å
Authors: Ohno Shin-ichi 
Published: July 2006

Abstract
The effects of 2537 Å radiation upon solutions of hexacyanoferrate(II) were investigated at 25°C, using specific scavengers for hydrated electrons (N2O, H3O + , and NO3−) and for hydrogen atoms (CH3OH and C2H5OH). In the presence of N2O or NO3−, a photo-oxidation reaction giving hexacyanoferrate(III) was found to take place, the primary process being:
[Fe(CN)6]4−\xrightarrowhν[Fe(CN)6]3−+e−aq
The quantum yield of this photochemical process was determined to be 0.35 at 25°C. The e−aq thus formed reacted with N2O, NO3−, and H3O+ , just like the hydrated electron produced in water irradiated with fast electrons or γ-rays.
The Photochemistry of Aqueous Hexacyanoferrate(II) Solutions. III. The Effect of Acetone on the Photo-oxidation Reaction at 2537 Å
Authors: Ohno Shin-ichi 
Published: July 2006

Abstract
The photochemistry of the hexacyanoferrate(II) ion was investigated at 2537Å in the presence of acetone and of N2O or NO3−. Acetone was found to act as a scavenger for the photo-chemically-produced electron, thus giving an acetone radical which can reduce the hexacyanoferrate(III) ion to the -(II) ion. The relative reaction rates of the electron, k(e−aq+acetone)/ k(e−aq+N2O) and k(e−aq+ acetone)/k(e−aq+NO3−), were found to be 1.5 and 0.45 respectively. These rate ratios were found to vary with the ionic strength value in a way which indicates that e−eq has a unit negative charge and survives long enough for the establishment of its ionic atmosphere.
The Photochemistry of Aqueous Hexacyanoferrate(II) Solutions. IV. A Study of the Mechanism of the Photoelectron Detachment
Authors: Ohno Shin-ichi 
Published: July 2006

Abstract
The effects of environmental changes, such as temperature changes, the addition of salts, and the use of D2O as a solvent, upon the absorption spectrum of the hexacyanoferrate(II) ion, as well as upon the photochemical yield of hydrated electrons, have been investigated. The results observed have then been tentatively interpreted in terms of a proposed mechanism: (1) the absorption of light quanta results in an “internal” metal-(d)→ CN-(π*) excited state; (2) the rate of the detachment of an electron from this excited state to the solvent is dependent on the size of the cavity occupied by the complex ion surrounded by the hydration layers of the water, and (3) environmental changes affect the size of the cavity, thus influencing the magnitude of the quantum yields of e−ap.