bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Liquid Phase Oxidation of Acrolein. III. Decompositions of Peracrylic Acid by Catalysts and with Acrolein
Authors: Ohkatsu Yasukazu , Hara Takao , Osa Tetsuo , Misono Akira 
Published: July 2006

Abstract
Peracrylic acid was decomposed by four kinds of catalysts in a benzene solution at 30°C. The order of the catalysts’ effect on the decomposition was: Mn&gt;Co&gt;Fe&gt;Ni; this agreed, except for the reverse order of Co and Mn, with that of the effective catalysts in the oxidation of acrolein (Co&gt;Mn&gt;Fe&gt;Ni). The empirical rate equation,
−d(CH2=CHCOO2H)⁄dt=k(CH2=CHCOO2H)0.58(catalyst)0.56
was obtained from the decomposition by Co(acac)3. On the other hand, from the stationary-state treatment of elementary steps adequate to the reaction and some assumptions, and from the experimental data, the following equation was derived:
−d(CH2=CHCOO2H)⁄dt=1.3×10−1(CH2=CHCOO2H)(Co3+)+9.6×10−3(CH2=CHCOO2H)1⁄2(Co3+)1⁄2
The above two equations have been confirmed as agreeing with each other over the range of reaction conditions used. The interaction of peracrylic acid with acrolein was carried out in the absence of a catalyst under an oxygen or nitrogen atmosphere. In this case, there was formed a complex consisting of both peracrylic acid and acrolein. The complex was mainly decomposed through the ionic mechanism, but in part through the radical mechanism at a higher temperature, namely, through the homolytic cleavage of its peroxy group, followed by the induced decomposition of peracrylic acid. Furthermore, the formation mechanism of acrylic acid in the oxidation of acrolein was discussed in view of the activation energy of the decomposition of peracrylic acid.
Studies on Seven-Membered Heterocyclic Compounds Containing Nitrogen. VIII. Structural Considerations of Pyrazole and Thiazole Compounds Fused with a Hydrazepine Ring
Authors: Yokoo Akira , Morosawa Shiro 
Published: July 2006

Abstract
The alternative structure of III, 2-methyl-4,5,7,8-tetrahydro-6(H)-azepino[5,4-d]thiazole (IV) has been found by a study of the NMR spectrum of the corresponding 6-ethoxycarbonyl derivative (V). The structure of 1-ethoxycarbonyl-3-hydroxymethylene-1-azacycloheptan-one (VIII) has also been ascertained by a study of the NMR spectrum and also by its conversion into the methyl derivative (XI).
The Grignard Reaction of 1,3-Diazaazulene
Authors: Mukai Toshio , Tsuruta Haruki , Momotari Yoshitaka 
Published: July 2006

Abstract
From the point of view of the nucleophilic substitution, the Grignard reaction of 1,3-diazaazulene (I) was investigated using phenyl magnesium bromide and t-butyl magnesium chloride. Substitution occurred at 4- and/or 6-positions of I and 4-phenyl-4H-(II), 4-t-butyl-4H- (VIIIa) and 6-t-butyl-6H-cycloheptaimidazole (VIIIb) were isolated respectively. The NMR and UV spectra of these products were discussed. Of the products, II and VIIIb afforded 4-phenyl-(III) and 6-t-butyl-1, 3-diazaazulene (XI) by dehydrogenation.
Studies of Antibiotics and Related Substances. XXXI. The Synthesis of Kanamycin-6′-phosphate
Authors: Umezawa Sumio , Tatsuta Kuniaki , Tsuchiya Tsutomu , Yamamoto Eiichi 
Published: July 2006

Abstract
The introduction of a phosphate group into the 3-amino-3-deoxy-d-glucose moiety of kanamycin, a useful antibiotic, has been described. Tetra-N-anisylidene kanamycin was treated with diphenyl phosphorochloridate. Hydrolysis of the product followed by hydrogenolysis afforded kanamycin-6′-phosphate in a good yield. An alternative phosphorylation of kanamycin via tetra-N-carbobenzoxykanamycin to hexa-O-acetyl-tetra-N-carbobenzoxy-6′-diphenylphosphoro-kanamycin was described, however, the removal of the all protecting groups except the phosphate group encountered a difficulty.
The Reactions of the Photochemically Produced Electron in Aqueous Hexacyanoferrate(II) Solutions
Authors: Ohno Shin-ichi 
Published: July 2006

Abstract
The reactions of the photochemically-produced electron, e−aq, in an aqueous solution of hexacyanoferrate(II) were studied when H2PO4−, NO3−, H2O2, CO2, [Fe(CN)6]3− and H3BO3 were used as the solute. The relative reaction rates, obtained by competition kinetics, are compared with those calculated using the published data on the absolute rate constants. The agreements are satisfactory in some cases, but not in other cases (e.g., H2PO4−, H2O2 and CO2), for which a possible explanation is given. This explanation includes the postulation of an electrontransfer reaction between the solutes employed; it is shown that information on the efficiency of this electrontransfer reaction may be obtained by using the relative rates obtained both from competition kinetics and from pulse radiolysis.
The Rheological Study of Aqueous Solutions of Polyethylene Glycol at Ultrasonic Frequencies
Authors: Arakawa Kiyoshi , Takenaka Nobuo 
Published: July 2006

Abstract
Ultrasonic investigations of aqueous solutions of polyethylene glycol solutions have been made by means of an ultrasonic pulse technique. Two samples of the polymer have been used, the molecular weights being 4000 and about 6000. The measurements of the sound velocity and of the absorption have been made on 5–30 wt% solutions of the polymers, together with an ethylene glycol-water mixture for the sake of comparison, over the frequency range of 5–45 Mc/sec. The temperature has been varied over the range of 10–70°C. It has been found that the velocity vs. temperature curve for each solution has a peak, and that the peak has a trend to shift to a lower temperature with the increase in the concentration. From the absorption data obtained, it has been found that a characteristic relaxation frequency appears near 40 Mc/sec at room temperatures. The magnitude of the absorption has been found to increase linearly approximately with the increase in the concentration, and to be independent of the molecular weight of the polymers at least in the range studied. From the temperature dependence of the relaxation frequency, the apparent activation energy of the relaxation process has been estimated to be not larger than 1 kcal/mol. It has been concluded from the results that the source of the relaxation process is not the hydrogen bonding between polymer molecules and water, as recently stated by G. G. Hammes et al. (J. Phys. Chem., 70, 1610 (1966)), but some intramolecular process.
The Chemistry of Protactinium. IV. On the Absorption Spectra of Tetravalent Protactinium in Aqueous Solutions
Authors: Mitsuji Toshikazu 
Published: July 2006

Abstract
The liquid zinc amalgam method was developed as a rapid procedure for the reduction of pentavalent protactinium. Several minutes were sufficient for the complete reduction of 4.2×10−4 m pentavalent protactinium in both hydrochloric and sulfuric acid solutions. The stability of tetravalent protactinium in these media was investigated by spectrophotometry. Re-oxidation occurred gradually, even in the absence of atmospheric oxygen, and amounted to 8% in 15 hr. These results may be understood in terms of the slow rate of the (2Pa4++2H+\ightleftarrows2Pa5++H2) reaction. The formation of sulfato complexes of tetravalent protactinium was inferred by spectrophotometry with relation to the similarity of the electronic structure between Pa4+(5f1) and Ce3+(4f1).
The Electronic Structure of Peptide and the Base Components of Nucleic Acids in the Triplet State
Authors: Imamura Akira , Fujita Hiroko , Nagata Chikayoshi 
Published: July 2006

Abstract
The electronic structures of β-naphthol, the base components of nucleic acids, and peptide have been calculated for the ground, singlet-excited, and triplet-excited states by means of the ASMO SCF CI method. The calculated π electron density of β-naphthol agrees well with the experimental data. The π electron density, the dipole moment, and the bond order for the ground, singlet and triplet excited states have been obtained, and the characteristics of the electronic structures for the ground, singlet-excited, and triplet-excited states have been discussed in connection with the chemical behavior of the molecule.
The Kinetics of Substitution Reactions Involving Metal Complexes. XI. The Reactions between Nickel(II) Ions and Copper(II)- and Cobalt(II)-Nitrilotriacetate Complexes
Authors: Tanaka Nobuyuki , Kimura Masaru 
Published: July 2006

Abstract
The kinetics of the substitution reaction of nickel(II) and copper(II)-nitrilotriacetate complexes and that of nickel(II) and cobalt(II)-nitrilotriacetate complexes in acetate buffer solutions have been studied by a similar method in principle to that reported previously. The reactions were treated as to proceed through both hydrated metal ions and monoacetato complexes. The rate constants of eight reaction paths, of which four involve hydrated nickel(II) ions and the others, monoacetatonickel(II) complexes, were determined at ionic strength 0.2 at 0°C. The backward reactions were found to proceed also through eight reaction paths in which the dissociation of Ni(II)-nitrilotriacetate complexes is rate-determining. The values of rate constants obtained for the forward and the backward reactions indicate that all the reactions proceeding through monoacetatonickel(II) complexes are faster than the corresponding reactions through hydrated nickel(II) ions.
Studies of the Behavior of Trivalent Uranium in an Aqueous Solution. I. Its Reduction and Its Stability in Various Acid Solutions
Authors: Satô Akiko 
Published: July 2006

Abstract
Various methods for the reduction of hexavalent uranium to the trivalent state were examined. It was found that the liquid-zinc-amalgam method is simple and rapid, and gives a high yield with a good reproducibility in hydrochloric, sulfuric, and perchloric acid solutions. The percentage of reduction is over 99% in a 0.5 n hydrochloric acid solution. Next, the stability of trivalent uranium in these media was investigated; it was observed that the trivalent uranium ion is fairly stable in any hydrochloric, sulfuric and perchloric acid solutions at a low concentration of the acids in the absence of atmospheric oxygen, but that it becomes unstable as the acid concentration increases. Both the percentage of reduction by the liquid-zinc-amalgam method and the stability of trivalent uranium are highest in a hydrochloric acid solution, next highest in a perchloric acid solution, and lowest in a sulfuric acid solution.
Steric Effects in the Copolymerization of β-Alkylstyrenes with Acrylonitrile
Authors: Yasufuku Katsutoshi , Hirose Sumio , Nozakura Shun’ichi , Murahashi Shunsuke 
Published: July 2006

Abstract
To investigate the steric effect of β-substituents of styrene derivatives on their reactivities in radical copolymerization, fourteen cis- and trans-β-alkylstyrenes were synthesized and copolymerized with acrylonitrile. The reactivities of β-alkylstyrenes toward the acrylonitrile radical decreased in the order: CH3&gt;C2H5\gtrsimn-C3H7\gtrsimn-C4H9&gt;iso-C3H7&gt;s-C4H9&gt;t-C4H9 in both the cis- and trans-series. Linear relationships were found between the relative reactivities and Taft’s or Hancock’s steric parameter. These relationships and the study of the monomer structures led to the following conclusions: 1) The low reactivity of β-alkylstyrenes in radical polymerization is to be attributed to the steric hindrance of β-alkyl substituents. 2) The effect of the hyper conjugation of the β-alkyl groups is not important. 3) The difference in the reactivities among intramolecularly-hindered cis-β-alkylstyrenes is due not to the difference in resonance of the monomer, but to the difference in the steric hindrance of the β-alkyl groups toward the attacking radicals.
The Flow Properties of Polyvinylpyrrolidone Solutions
Authors: Mineshita Takeshi , Watanabe Takehiko , Ono Sôzaburo 
Published: July 2006

Abstract
The viscosities of solutions of polyvinylpyrrolidone (\barMv=9×105) are determined at 35°C in pure water, in a 0.25 m MgCl2 aqueous solution, in n-propanol, and in a water -n-propanol mixture at several concentrations (0.5–1.5 g/100 ml). Measurements are carried out with a Maron-Belner type low-shear capillary viscometer with various capillary radii (0.0190–0.0761 cm) within the shear stress range of 0.2–20 dyn/cm2 at the capillary wall. The viscosities of the solution show a non-Newtonian flow behavior and a capillary bore-size dependence. The viscosity decreases with the decrease in the capillary bore size within the range of shear stress studied. The results were represented by Ree-Eyring’s generalized flow formula for a flow system containing one Newtonian flow unit and one non-Newtonian one. The contribution of the Newtonian term of the formula to the solution viscosity lowers in viscosity with the decrease in the capillary bore size, whereas the non-Newtonian term makes a contrary contribution. The change in the viscosity of the polymer solution with the size of the capillary tube may be attributed to the changes in the relaxation time of the solvent molecules and in the shear volume of the polymer molecules in the neighborhood of the capillary wall.
Heats of Sublimation of Polycyclic Aromatic Hydrocarbons and Their Molecular Packings
Authors: Wakayama Nobuko , Inokuchi Hiroo 
Published: July 2006

Abstract
The vapour pressure of some polycyclic aromatic hydrocarbons was measured by means of the effusion method. From the temperature dependence of the pressure, the heat of sublimation (ΔH kcal/mol) and the entropy (ΔS° cal/mol·deg) were calculated for the following hydrocarbons: 1,2-benzanthracene (ΔH=22.8; ΔS°=44.8), tetracene (29.8; 43.3), chrysene (28.1; 43.0), triphenylene (25.6; 33.9), 3,4-benzophenanthrene (25.4; –) p-terphenyl (28.3; 47.9), 1,12-benzperylene (30.0; 40.7), 3,4-benztetraphene (32.6; 45.9), 1,2,5,6-dibenzanthracene (33.9; 49.3), pentacene (37.7; 48.9), picene (33.5; 45.9), coronene (30.7; 36.9), 1,2,4,5-dibenzpyrene (32.9; 48.3), 1,2,6,7-dibenzpyrene (35.1; 45.6), 1,3,5-triphenylbenzene (34.0; 55.6), tetrabenzonaphthalene (33.9; 47.4), isoviolanthrene A (52.2; 54.6), violanthrene A (46.8; 48.1), violanthrene B (36.7; 38.0) and tetrabenzoperylene (28.2; 44.7). The small values of ΔH for violanthrene B, tetrabenzoperylene and tetrabenzonaphthalene may reflect the existence of the non-coplanar structure of their molecules. Further, the large values of ΔS° for triphenylbenzene and terphenyl suggested the possibility of the rotation about their single bonds.
Helix-with-Loops Structure of Polynucleotide. I. Poly(C+IC) and Poly(C+GU)
Authors: Ichikawa Tadayoshi , Fujita Hitoshi , Matsuo Kimiko , Tsuboi Masamichi 
Published: July 2006

Abstract
A copolymer of 57% riboinosinic acid plus 43% ribocytidylic acid has been prepared. The ultraviolet absorbances of aqueous solutions of mixtures of this copolymer and polyribocytidylic acid of various mole ratios were measured. The results indicate that, in these aqueous solutions, a “helix-with-loops” structure is formed; this structure has the hypoxantine-cytosine base pair and the unpaired cytidylic acid residues in the loops. A copolymer of 58% riboguanylic acid plus 42% ribouridylic acid has also been prepared. A similar ultraviolet examination was made of a mixture of this copolymer and polyribocytidylic acid; again the formation of a “helix-with-loops” structure was indicated. This structure is considered to have the guanine-cytosine base pair and the uridylic acid residues in the loops.
Structure and Reactivity of Small Ring Compounds. III. Solvolyses of 4-Methyl Spiro[2,4]hept-4-yl and 4-Methyl Spiro[2,5]oct-4-yl p-Chlorobenzoates
Authors: Tsuji Takashi , Moritani Ichiro , Nishida Shinya , Tadokoro Goro 
Published: July 2006

Abstract
The solvolyses of 4-methyl spiro[2,4]hept-4-yl, 4-methyl spiro[2,5]oct-4-yl, 1,2,2-trimethylcyclopentyl, 1,2,2-trimethylcyclohexyl, spiro[2,4]hept-4-yl, and spiro[2,5]oct-4-yl p-chlorobenzoates have been examined in an aqueous solution of dioxane. The rate of the solvolysis of 4-methyl spiro[2,4]hept-4-yl p-chlorobenzoate was 26000 times greater than that of the corresponding secondary derivatives and 18000 times greater than that of the 1,2,2-trimethylcyclopentyl derivative. Similarly, in the cyclohexyl series, 4-methyl spiro[2,5]-oct-4-yl p-chlorobenzoate solvolyzed 7700 times faster than the sprio[2,5]oct-4-yl ester and 23000 times faster than the 1,2,2-trimethylcyclohexyl ester. All the solvolysis products of tertiary spiro derivatives kept the skeletons of the starting materials entirely. Thus, the 4-methyl spiro[2,4]hept-4-yl ester gave a mixture of 4-methyl spiro[2,4]hept-4-ol (60%), 4-methyl spiro[2,4]hept-4-ene (27%), and 4-methylene spiro[2,4]heptane (13%). The 4-methyl spiro [2,5]oct-4-yl ester gave the original alcohol (58%) and 4-methyl spiro [2,5]oct-4-ene (38%), along with a small amount of an unidentified product. The implications of these results are discussed.
Kinetic Studies of Bimolecular Nucleophilic Substitution. VIII. The Effect of Hydroxylic Solvents on the Nucleophilicity of Aliphatic Amines in the Menschutkin Reaction
Authors: Okamoto Kunio , Fukui Suguru , Nitta Issei , Shingu Haruo 
Published: July 2006

Abstract
The rate of the reactions of methyl iodide with various aliphatic amines, e.g., methyl-, ethyl-, n-butyl-, ethanol- and benzyl-amines, have been measured in methanol solvent and compared with the previous results obtained in benzene solvent. Ethylamine, diethylamine, and triethylamine react slower in methanol than in benzene. In a similar fashion, butylamine, dibutylamine, tributylamine, methylamine and dimethylamine are less reactive in methanol than in benzene. These unusual results, e.g., the lower SN2 reactivity of amines in the more ionizing protic solvent, are attributed to the retardation by the higher activation energy in methanol solvent at the expense of the acceleration by higher values of the entropy of activation. The increase of the activation energy is ascribed to specific solvation, e.g., hydrogen bonding of methanol toward amines. Benzylamines and ethanolamines, which are comparatively less solvated by methanol exhibit the usual reactivity sequence toward methyl iodide, e.g., the higher SN2 reactivity in the more polar solvent.
Reactions of Diazoketones in the Presence of Metal Chelates. I. Reactions in Alcohols
Authors: Takebayashi Matsuji , Ibata Toshikazu , Kohara Hideki , Kim Bu Hong 
Published: July 2006

Abstract
The reaction of diazoacetophenone with alcohols has been studied in the presence of metal chelates. Metal chelates, such as bis(acetylacetonato)copper(II), bis(acetylacetonato)nickel(II), and bis(acetylacetonato)lead(II), were found to be active catalysts for this reaction; they modified the reaction to give alkoxyacetophenones instead of alkyl phenylacetates. When tertiary amines, such as triethylamine, pyridine, and quinoline, were added to the reaction mixture, the formation of alkoxyacetophenones was suppressed and that of alkyl phenylacetates was promoted in proportion to the increase in the amount of amines added. The mechanism of the reaction can reasonably be explained by assuming the intermediacy of a ketocarbene-metal chelate complex.
Azetidines. III. The Tosylation and Acylation of 1-Substituted 3-Azetidinols. The Preparation of 1-t-Butylazetidine-3-carboxylic Acid
Authors: Chen Teng-yueh , Sanjiki Tetutaro , Kato Hiroshi , Ohta Masaki 
Published: July 2006

Abstract
The tosylation of 1-t-butyl-3-azetidinol in pyridine gave 1-t-butylazetidinyl-3 tosylate, but 1-cyclohexyl-3-azetidinol gave mainly N-tosyl-1-cyclohexylamino-3-chloro-2-propanol. The reaction of both the azetidinols with p-nitrobenzoyl chloride in pyridine gave the 3-nitrobenzoates, while in acetone 1-cyclohexyl-3-azetidinol gave a ring cleavage product. The preparation of 1-t-butylazetidine-3-carboxylic acid is described.
The Polarography of Nitrones and the Effect of Substituents on Them
Authors: Kubota Tanekazu , Miyazaki Hiroshi , Mori Yutaka 
Published: July 2006

Abstract
Polarograms and half-wave potentials (E1⁄2’s) of sixteen substituted benzylidenementhylamine N-oxides were extensively measured in various pH solutions. The half-wave potential, E1⁄2, was expressed in the form: E1⁄2=a·pH+b. It was always observed that the four-electron wave due to the reduction of the C=N→O group decreases in wave height in an alkaline medium, and at the same time another wave appears in a more negative potential. The former behavior was similar to that found for pyridine N-oxide and its derivatives. The plot of the Hammett σ values of the substituents against the E1⁄2 values of nitrones satisfied a linear relation very well, ρ being positive but smaller than that obtained previously for the system of substituted pyridine N-oxides. Controlled-potential electrolysis was carried out in order to compare the results with the polarographic results.
Molecular Orbital Consideration of the Reaction of the Zinc-Methylene Complex with Double Bonds
Authors: Hida Mitsuhiko 
Published: July 2006

Abstract
It has been reported that a zinc-methylene complex prepared from methylene iodide and a zinc-copper couple reacts with olefins to give cyclopropanes, and with aldehydes to give olefins. The former reaction was suggested to be electrophilic, and the latter, nucleophilic. In this report this duality of the zinc-methylene complex and the reactivities of double bonds will be discussed in terms of the interaction between the reagent orbitals and the substrate orbitals. The reactivity of the carbonyl group will mainly be determined by the nucleophilic superdelocalizability of carbonyl carbon, while that of the olefinic double bond will mainly be determined by the electrophilic total delocalizability (SsE+StE+2PstE). The theoretical predictions of these reactivities are consistent qualitatively with the experimental results.
Silent Discharge Reactions in Aqueous Solutions. VII. Alkaline Aqueous Solution of Potassium Ferricyanide in Atmospheres of Helium and Argon
Authors: Yokohata Akira , Tsuda Satoru 
Published: July 2006

Abstract
The silent discharge reactions of aqueous solution have been extended to an alkaline region. Potassium ferricyanide was selected as reaction system. The results show the reduction of ferricyanide ions. The situation is very similar to that in the case of radiation chemistry. The G value of the disappearance of ferricyanide ions was almost the same as that of cerous ions formed from the acidified eerie solution by silent discharge reaction under the same experimental condition. Moreover, the yield of hydrogen peroxide produced in the alkaline solution was almost the same as those of acidic and neutral solutions. Those findings suggest that the radical yields will be also almost equal, irrespective of pH in the range studied. This work gives a further evidence that most of silent discharge reactions of the aqueous solutions in inert gases can be well interpreted in terms of the radiolysis by slow electrons generated in the gas phase.
An Equation for Selectivity Coefficient of Ion Exchange in Mixed Solvent System
Authors: Ohtaki Hitoshi , Kakihana Hidetake 
Published: July 2006

Abstract
Based on thermodynamic considerations an equation was derived for ion exchange equilibria in mixed solvent systems. In mixtures of water, W, and non-aqueous solvent, S, a selectivity coefficient of ion exchange of A and B ions, KAB, was expressed in terms of partial molal volumes of ions, \barvA and \barvB, partial molal volumes of solvents, \barvW and \barvS, and distribution coefficient of the solvents, D, between the external and the resin phases, thus
lnKAB=[(\barvA–\barvB)+(\barhWA–\barhWB)\barvWA]lnD⁄(\barvS–\barvW)
where \barhWA and \barhWB represent hydration numbers of A and B ions and \barvWA is partial molal volume of hydrated water. Symbols with bar denote quantities in the resin phase. Using the above equation and values from literatures, selectivity coefficients for sodium-potassium ion exchange in water-ethanol mixtures were calculated and compared with those experimentally obtained for examination of the validity of the equation.