bluuebunny/crossref_metadata_2025 huggingface dataset:
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

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

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

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>C2H5\gtrsimn-C3H7\gtrsimn-C4H9>iso-C3H7>s-C4H9>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

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

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

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

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

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

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

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

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

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

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

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.
Magnetic Susceptibilities of Crystalline Phenothiazine, N-Methylphenothiazine and Thianthrene Radical Salts with Antimony Pentachloride
Authors: Sato Yoichiro , Kinoshita Minoru , Sano Mizuka , Akamatu Hideo
Published: July 2006

Phenothiazine, N-methylphenothiazine and thianthrene are oxidized with antimony pentachloride, and give the corresponding monopositive ion radicals. These aromatic positive ions form crystalline salts with the complex negative ion of antimony pentachloride or tetrachloride. The paramagnetism for these salts is attributed to the aromatic ion radicals, and follows the Curie-Weiss law at higher temperatures, and deviates from it at lower temperatures. This behavior has been interpreted by assuming the linear chain model being applicable, which suggests a remarkable spin exchange interaction in the crystalline salt of phenothiazine·SbCl4, of J/k∼395°K.
Dependence of the Crosslinking Efficiency on the Reaction Conditions in the Peroxide Crosslinking of Unsaturated Polyolefins
Authors: Ashikari Nobuyuki , Kawashima Izumi , Kawashima Takehisa
Published: July 2006

The crosslinking reactions of several unsaturated polyolefins with organic peroxides were carried out in an attempt to establish the dependence of the crosslinking efficiency on the reaction conditions, especially the reaction temperature and the peroxide concentration. Usually, the efficiency gradually increased up to a certain temperature and then decreased abruptly. This efficiency decrease can be considered to be due to (1) a decrease in the hydrogen abstraction, which is one reaction producing crosslinks, and (2) an increase in the termination rate in a chain reaction arising from opening up the double bond, which is another reaction producing crosslinks. Except for cases in which an extremely high temperature was employed or when a very high concentration of peroxide was used, the efficiency decrease by scission reaction upon an elevation of the temperature seems to be comparatively small.
Solvent Effects in the Electron Spin Resonance Spectra of Some Phenoxyl, Nitroxide, and Anilino Radicals
Authors: Mukai Kazuo , Nishiguchi Hiroaki , Ishizu Kazuhiko , Deguchi Yasuo , Takaki Hideo
Published: July 2006

The electron spin resonance spectra of 2,6-di-t-butyl-4-methylphenoxyl (I) and 2,4,6-tri-t butylphenoxyl (II) have been observed under high resolution, and it has been shown experimentally that the para methyl proton hyperfine splitting (aCH3H) in the radical (I) increases, while, inversely, the meta proton hyperfine interaction decreases, as the dipole moment of the solvent (μ) increases. The relationship between these two variables can be written as:

a(μsolv)=a(μsolv=0)+K·μsolv,

where μsolv is the dipole moment of the solvent and where K is the constant of proportionality. Further study of diphenyl nitric oxide (DPNO) (IV) and di-p-anisyl nitric oxide (DPANO) (V) radicals has shown this to be a general form of the solvent effect. However, in the case of various kinds of solvents with OH or NH groups, it has been found that aN deviates from the equation. This phenomenon has been explained qualitatively by the effect of hydrogen bonding. Therefore, the variation in the coupling constants has generally been explained by two effects, that is, the μ dependence described above and the electron delocalization arising from hydrogen bonding. Similar experiments performed with 2,4,6-tri-t-butylphenoxy (II) and 2,4,6-tri-t-butylanilino (III) radicals have shown that the variation in the hyperfine splitting constants is small because of the steric hindrance of tertiary butyl groups in these molecules.
Unusual Behaviors in Electrical Conductivity of Phenanthrene Crystal
Authors: Matsumoto Shoichi
Published: July 2006

Two kinds of unusual behavior in the temperature dependence of electrical conductivity has been observed. One is the anomaly that the resistance begins to increase remarkably with the rise in the temperature around 64°C; the other is a bending-phenomenon in the linear temperature-dependence of the resistance about 54°C. The observed activation energies for conduction are 3.0–3.3 eV below and 4.5–4.8 eV above the anomaly, the energies of which are almost compatible with the intrinsic band-gap energies for conduction, 3.5 and 4.6 eV, estimated, respectively, from the optical absorption and from the values of the ionization potential and the electron affinity. As for below the bending-phenomenon, the observed activation energy is 1.4–1.6 eV, which is quite small compared with the intrinsic band-gap energies estimated. The anomaly beginning around 64°C is interpreted as due to the crystal-phase transition of a higher-order at 60–70°C; the remarkable increase in resistance may be connected with the changes in the intermolecular interaction in the crystal due to the rearrangement of molecules caused by the phase transition. The bending-phenomenon at about 54°C seems to be attributable to an impurity-effect by oxygen.
Crystal Structure of Dichlorobis(cyclohexanone oxime)palladium
Authors: Tanimura Masamitsu , Mizushima Toshio , Kinoshita Yukio
Published: July 2006

The crystal structure of dichlorobis(cyclohexanone oxime)palladium, PdCl2(C6H10NOH)2, has been determined from three-dimensional X-ray photographic data. The crystals belong to the triclinic space group P\bar1, with these cell parameters: a=8.81 Å, b=9.99 Å, c=4.99 Å; α=91°32′, β=99°41′ and γ=102°02′. The unit cell contains one molecule of the complex. The palladium atoms are spaced at intervals of 4.99 Å along the c-axis and have a square planar coordination, with two chlorine atoms at 2.24 Å and two nitrogen atoms of the oxime group at 2.08 Å. The complexes are hydrogen-bonded with each other in strings of indefinite length along the c-axis, and the hydrogen bond distance between the oxygen atom of the hydroxyimino group and the chlorine atom is 2.93 Å.
Electrolyte-Solvent Interaction: Conductance of Lithium Bromide in Acetone-Water Mixtures at Different Temperatures
Authors: Singh D , Mishra Anirudh
Published: July 2006

The conductance of lithium bromide in acetone-water mixtures has been measured at different temperatures (25–40°C) in the dielectric constant range from 17.80 to 61. The association constants and centre-to-centre cation-anion distances have been calculated by a modified Fuoss-Onsager equation applicable to 2<b<15, where b is the Bjerrum parameter. The increase in ion size and the decrease in association constants with the addition of water have been interpreted in terms of the solvated dipoles which contain both solvent molecules in the sheath of solvation. The variation in Walden products and in association constants with the change in the composition of the solvent and the temperature is well represented on this model.
The Mössbauer Spectra of the Iron - Sodium Metaphosphate Systems
Authors: Kamo Mutsukazu , Takashima Yoshimasa , Ohashi Shigeru
Published: July 2006

The Mössbauer spectra of three iron - sodium metaphosphate systems have been studied. The bonding characteristics of the iron atom with the phosphates have been discussed from the results of the Mössbauer spectra. The data for the fused iron oxide - sodium metaphosphate system suggest that the bonding of the iron atom with the phosphates is considerably ionic and the arrangements of metaphosphates in these systems are at random and in a tangle. Some informations on the structure of the Fe2(OH)(PO3)5 system were described.
The Chemistry of Protactinium. V. The Separation of Pa(IV) and Pa(V) by Co-precipitation with Thorium Fluoride
Authors: Mitsuji Toshikazu
Published: July 2006

The separation of Pa(IV) and Pa(V) was investigated using various co-precipitants which were insoluble in acidic solutions. Among them, thorium fluoride was found to be the most useful co-precipitant. The conditions for the separation of both valency states of protactinium were also investigated in detail. This method was applicable to protactinium solutions in the concentration range down to tracer level. It was difficult to reduce Pa(V) completely on a tracer scale by means of a liquid zinc amalgam. When Cr(III) was added to the system, however, the complete reduction of 233Pa(V) was readily attained. The role of Cr(III) was considered to be that Cr(II) formed by liquid-zinc-amalgam reduction mediates the reduction of Pa(V) and protects Pa(IV) from re-oxidation. By this method tetravalent protactinium in a perchloric acid medium was also confirmed to be very stable.
Reaction of 2-Benzimidazolinethione with Dimethylsulfoxide and Acetyl Chloride
Authors: Anzai Kentaro , Suzuki Saburo
Published: July 2006

Dimethyl sulfoxide (DMSO) and acetyl chloride reacted with 2-benzimidazolinethione (I), converting the latter compound to its thiomethoxymethyl and methylenebis derivatives. From the reaction mixture the following compounds were isolated: 1, 3-dithiomethoxymethyl-2-benzimidazolinethione (VII), 1, 1′-methylenebis-3-thiomethoxymethyl-2-benzimidazolinethione (VIII), 1-thiomethoxymethyl-2-benzimidazolinethione (IX), 1, 1′-methylenebis-2-benzimidazolinethione (XIII), and 2-(methylenesulfonium)benzimidazolide (XIV). The mechanism for the formation of these compounds will be discussed. The reaction of 2-benzoxazolinethione (XX) with DMSO and acetyl chloride yielded, besides its thiomethoxymethyl and methylenebis derivatives, 1-hydroxymethylbenzoxazolone (XXIII); the mechanism for the exchange of the sulfur in XX with the oxygen will also be discussed. N-Alkyl derivatives of I could be distinguished from S-alkyl derivatives by their ultraviolet spectra.
The Alkaline Sulfide Reduction of Aromatic Nitro Compounds. XI. The Autocatalytic Reaction of the Monosulfide to the Disulfide in Aqueous Solution
Authors: Hashimoto Shizunobu , Sunamoto Junzo , Sato Katsuhiko
Published: July 2006

The autocatalytic reactions of the aqueous monosulfide to the aqueous disulfide by an ultraviolet light, oxygen, and sodium m-nitrobenzene sulfonate have been investigated. The rate of the disulfide formation by the photo-oxidation of the aqueous monosulfide was given by the following equation: d(S22−)/dt=k0(S2−)2/(S2−)02. Also in the reaction of aromatic nitro compound and aqueous monosulfide, the disulfide formation was observed prior to the amine formation. On the basis of the results obtained, the mechanisms of the alkaline sulfide reduction of aromatic nitro compounds have been discussed.
The Peptide Synthesis. I. Use of the S-Ethylmercapto Group for the Protection of the Thiol Function of Cysteine
Authors: Inukai Noriyoshi , Nakano Kohzi , Murakami Masuo
Published: July 2006

The S-ethylmercapto group was an useful protecting group for the thiol group of cysteine. This group was stable under the conditions of peptide synthesis and was simply split by thiophenol without any side reaction. Glutathione and oxytocin were synthesized using S-ethylmercapto-l-cysteine.
The Reduction of 4-Thiazones and 4-Thiazone-imines, and the Conversion of Triphenyl-4-thiazone to Thiazolium Salts
Authors: Takayanagi Zenichi , Kato Hiroshi , Ohta Masaki
Published: July 2006

The reduction of 4-thiazones and N-acetyl-4-thiazone-imines with sodium borohydride gave thiazolidin-4-ones and 4-acetylaminothiazolidines respectively. Attempts to isomerize 5-alkylidenethiazolidin-4-ones, prepared by the reduction of 5-acyl-4-thiazones, followed by dehydration, to 5-alkyl-4-thiazones were unsuccessful. The ethylation and acetylation of 2, 3, 5-triphenyl-4-thiazone gave the corresponding 4-ethoxy- and 4-acetoxy-thiazolium salts.
Azirines. II. The Reaction of 2-Phenylazirine with Acylating Agents
Authors: Sato Shimao , Kato Hiroshi , Ohta Masaki
Published: July 2006

The reaction of 2-phenylazirine (I) with acid chlorides, anhydrides, an imidoyl chloride, and carboxylic acids were investigated. When I was treated with acid chlorides and anhydrides, the corresponding 2, 5-disubstituted oxazole derivatives were obtained. The reaction of I with phthalic and maleic anhydride, however, gave ring-cleavage products. The reaction of I and N-phenylbenzimidoyl chloride gave 1,2, 5-triphenylimidazole. On the other hand, I and benzoic and thiobenzoic acid gave N-benzoylphenacylamine and N-benzoyl-α-benzoylthio-β-aminostyrene respectively.
Synthetic Studies of Bacitracin. IV. Synthesis of Thiazoline Peptides by Iminoether Coupling Method
Authors: Hirotsu Yoshihiro , Shiba Tetsuo , Kaneko Takeo
Published: July 2006

For the purpose of a total synthesis of bacitracin A, a synthetic method of the thiazoline peptide was investigated. A benzyloxycarbonylaminoalkylimino ethyl ether derived from glycine, l-alanine, l-valine, l-leucine or l-isoleucine was coupled with ethyl l-cysteinate hydrochloride to afford the corresponding thiazoline peptide, that is, a dehydrated form of cysteine peptide. While l-cystine was obtained from acid hydrolyzates of those thiazoline peptides, hydrolysis of them after treatment with alkali or ammonia gave Dl-cystine. Furthermore, alkaline treatment caused a racemization of the amino acid residue adjacent to the thiazoline ring too.
Aminocyclitols. XVI. A Synthesis and Configurational Study of Dibromo-dideoxyinosamine
Authors: Suami Tetsuo , Ogawa Seiichiro , Nakashima Yasuo , Sano Hiroshi
Published: July 2006

Bromination of epi-inosamine-2 in a mixture of acetyl bromide and acetic anhydride afforded 1, 5-dibromo-1, 5-dideoxy-rac-inosamine-6. From this compound, two hitherto unknown inosadiamines: myo-inosadiamine-2, 4 and muco-inosadiamine-2, 3, were obtained by displacement of the bromo groups by azide ions, followed by hydrogenation. The configurations of the new compounds obtained were established by the nuclear magnetic resonance spectra.
Study on Nickel Oxide-Silica-Alumina Catalysts for Ethylene Polymerization. IV. The Structure of the Catalysts Studied by the Oxidation of Carbon Monoxide and by Magnetic Measurements
Authors: Imai Hisao , Uchida Hiroshi
Published: July 2006

The oxidation of carbon monoxide and magnetic susceptibility measurements have been carried out with a series of nickel oxide-silica-alumina catalysts, all of which are the same in aluminum content but which are different in nickel content. The kinetic data of the oxidation followed an Elovich rate equation, and the initial activity per unit of surface area of the catalyst increased as the nickel content increased from 0 to 8.0 atom%. The apparent activation energy was found to be 8±2 kcal/mol. The magnetic susceptibility vs. temperature curves followed the Curie-Weiss relationship in the temperature range between 240 and 723°K, and the effective Bohr magneton number increased to an approximately constant value of 3.7 Bohr magnetons as the nickel content decreased. The structure of the nickel oxide-silica-alumina catalysts has been discussed on the basis of the results obtained, and the Thomas model of the nickel acid site previously proposed for the active site of the ethylene polymerization (H. Uchida and H. Imai, Bull. Chem. Soc. Japan, 35, 995 (1962)) has been confirmed.
The Thermal Decomposition of Metal Oxalato Complexes
Authors: Tanaka Nobuyuki , Nanjo Michio
Published: July 2006

The thermal decomposition of trioxalato complexes of cobalt(III), iron(III) and chromium-(III) has been investigated by the thermogravimetric, the polarographic and the infrared spectroscopic method. The results indicate that, in the case of the iron(III) and the cobalt(III) complexes, the decomposition reaction is initiated by the electron transfer from the coordinated oxalate ion to the central metal ion. In the case of oxalatoamminecobalt(III) complexes, the oxalate ion is considered to be an electron donor; the more oxalate ions are coordinated, the complexes are thermally less stable.
Nucleophilic Reactions of Diethyl N-Phenyliminocarbonate
Authors: Fujisawa Tamotsu , Mukaiyama Teruaki
Published: July 2006

The reactions of diethyl N-phenyliminocarbonate with alkyl halide, acid chloride, lactone, and acid anhydride were studied in order to examine the nucleophilicity of the imino group. These reactions gave the corresponding carbamates at elevated temperatures, much as in the previously reported reactions of iminocarbonates with acids. On the other hand, from the reaction of the iminocarbonate with ethylene carbonate or ethylene sulfite, 3-phenyloxazolidone-2 was obtained along with the evolution of carbon dioxide or sulfur dioxide, respectively.
The Rearrangement of Tropones to Dihydrobenzene Derivatives
Authors: Kikuchi Katsuo
Published: July 2006

The positions of the double bonds in 1-phenylcyclohexadiene-1,2-dicarboxylic acid, which had been obtained previously by the alkaline rearrangement of 2-phenyltropone-7-carboxylic acid, were elucidated from the spectral data. A similar rearrangement of tropone derivatives to dihydrobenzene derivatives was also observed. Tropone-2-carboxylic acid gave 2,5-cyclohexadiene-1,2-dicarboxylic acid, while 2-phenyltropone-5-carboxylic acid afforded 1-phenyl-2,4-cyclohexadiene-1,4-dicarboxylic acid. 2-Phenyltropone was also rearranged by alkali to 2-phenyl-2,5-cyclohexadiene-1-carboxylic acid.
The Solvent Effect on the Rate Ratio of Esterifications of Enantiomeric Menthols with l-Menthoxyacetyl Chloride
Authors: Akiyama Fuminori , Sugino Keiichi , Tokura Niichiro
Published: July 2006

Esterifications of l- and d, l-menthols were undertaked in various solvents, such as chloroform, benzene, n-hexane, acetonitrile, methyl ethyl ketone, and liquid sulfur dioxide, in order to obtain some information on the solvent effect of the resolution of epimers by a kinetical method. The rate ratios, kdl/kll (generally larger than unity except in the case of sulfur dioxide), are in the following order: chloroform, benzene, n-hexane, acetonitrile, methyl ethyl ketone, and liquid sulfur dioxide, indicating higher kdl/kll ratios, in the less specific solvating solvents. The possibility of kinetical resolution in a non-specific solvating solvent is suggested, and the reason for it is discussed.
The Crystal Structure of 1, 6-Dimethoxy Phenazine
Authors: Yaji Hiroshi , Higuchi Taiichi , Shimada Akira , Namba Yoshiyuki , Oda Tsutomu
Published: July 2006

The crystal structure of 1, 6-dimethoxy phenazine was solved by the method of the molecular Fourier transform, and a refinement based on the two-dimensional data was achieved by the Fourier method and also by the least-squares method. The space group is P21/n with two molecules in the unit cell. The lattice constants are a=8.60 Å, b=12.59 Å, c=5.17 Å, and β=93.5°. The molecule has an exact center of symmetry and lies approximately on a plane, with the exception of the methyl groups, which are 0.21 Å outside the plane of the molecule. As for the phenazine ring, almost all the bond distances and angles exhibit normal values. The bond distances around the oxygen atom seem to indicate that the lone-pair electrons in this atom flow into the π-electron system of a phenazine ring. The planar molecules are stacked parallel to each other along the c axis, with an inter-planar spacing of 3.41 Å.
Effect of Molecular Vibrations on Gas Electron Diffraction. II. Probability Distribution Function and Phase Parameter for Polyatomic Molecules
Authors: Kuchitsu Kozo
Published: July 2006

A method has been presented for calculating the first, second, and third moments of the displacement of an internuclear distance in a polyatomic molecule, 〈Δr〉, 〈Δr2〉, and 〈Δr3〉. The moments, which depend on the frequencies of normal vibrations, the cubic potential constants, and the temperature of the system, have been related to the extent of distortion of the probability distribution function of the internuclear distance from a Gaussian function caused by the anharmonicity in the potential function. An approximate expression has been obtained for the phase parameter κ in the molecular intensity of gas electron diffraction in terms of the moments. Numerical results are given for CO2, CS2, SO2, H2O, D2O, CH4, and CD4 by the use of experimental or estimated cubic potential constants. The phase parameters for bonded distances agree with simple estimates based on “diatomic approximation” to the accuracy of current experimental studies, while the phase parameters for nonbonded distances are similar in magnitude to those for bonded distances in spite of their larger mean-square amplitudes of vibration.
Semi-empirical Self-consistent Field Molecular Orbital Calculation of the Electronic Structure of the Base Pairs of Deoxyribonucleic Acid
Authors: Imamura Akira , Fujita Hiroko , Nagata Chikayoshi
Published: July 2006

The electronic structures of adenine-thymine and guanine-cytosine pairs of DNA were calculated using the semi-empirical self-consistent field molecular orbital method. The calculations were carried out for two models, that is, one including hydrogen 2pπ orbitals and the other not. The obtained π electron densities and the π bond orders were then discussed in comparison with those of the corresponding bases. Further, the π electronic stabilization energies due to the hydrogen bond formations were calculated; the π stabilization energy of the G-C pair was found to be larger than that of A-T pair, in agreement with the experimental data. The π electronic structures in the excited states were discussed in connection with the biological behavior of DNA, that is, the misduplication of DNA leading to mutation by irradiation.
The Structures of the Products from the Reaction of 3-Bromotropolone and 7-Bromohinokitiol with Caustic Alkali
Authors: Toda Takashi
Published: July 2006

The main products from the reaction of 3-bromotropolone and 7-bromohinokitiol with caustic alkali are proved not to be 3-hydroxytropolone and 7-hydroxyhinokitiol, but 4-hydroxy-tropolone and 6-hydroxyhinokitiol. The mechanism of this abnormal substitution reaction is then discussed.
Synthesis and Properties of 3-Formyl-1-azaazulan-2-one
Authors: Toda Takashi
Published: July 2006

3-Formyl-1-azaazulan-2-one was synthesized in a good yield from 1-azaazulan-2-one by means of a Vilsmeire reaction and its chemical properties were investigated. The synthesis of the tryptophan analogue from the formyl compound was also attempted.
Proton Magnetic Resonance Spectra of Methyliodothiophenes
Authors: Takahashi Kensuke , Ito Ichi , Matsuki Yasuo
Published: July 2006

PMR data on seventeen compounds, including all of the iodosubstituted derivatives of 2-, 3-methyl and 2, 3-dimethylthiophenes, were given. The signals of β-hydrogens appear at a rather higher applied magnetic field than those of α-hydrogens, while the β-methyl signals appear at a higher field than do the α-methyl signals. The coupling constants between two ring hydrogens, between ring and methyl hydrogens, and between two methyl hydrogens were described.
The Structure of the Free Radical Produced from Carcinogenic 4-Hydroxyaminoquinoline 1-Oxide
Authors: Kataoka Nobuko , Imamura Akira , Kawazoe Yutaka , Chihara Goro , Nagata Chikayoshi
Published: July 2006

A potent carcinogen, 4-hydroxyaminoquinoline 1-oxide, was found to produce a stable free radical oxidatively. The structure of the free radical produced in dioxane was studied by analyizng the hyperfine structure of isotope-substituted 4-hydroxyaminoquinoline 1-oxides, and by comparing the values of the spin densities obtained from the coupling constants with those calculated by the unrestricted SCF MO method. It was concluded that the free radical has the same molecular skeleton as the parent compound, but that it loses a hydrogen atom on the nitrogen atom of the NHOH group.
The Crystal and Molecular Structure of Perchloro-(3, 4, 7, 8-tetramethylene-tricyclo[4.2.0.02,5]octane), C12Cl12
Authors: Furusaki Akio
Published: July 2006

The stereochemistry of perchloro-(3, 4, 7, 8-tetramethylene-tricyclo[4.2.0.02,5]octane) has been studied by three-dimensional X-ray crystal analysis. The crystal of this compound is triclinic, with one molecule in a unit cell with the dimensions; a=9.35, b=7.45, c=8.44 Å, α=111.8°, β=117.6°, and γ=96.0°. The space group is P1 or P\bar1, the latter being assumed throughout the present study. The crystal structure was elucidated by the minimum function method. The atomic parameters thus obtained were refined by the least-squares method, using the diagonal-matrix approximation. Each conjugated system in a molecule is nearly planar in spite of very close contact between the two adjacent dichloromethylene groups of the same system, the nearest approach occurring between the chlorine atoms with a distance of 3.28 Å. The whole molecule has a rather simple chair-like form, with an approximate symmetry of C2h.
Proton Magnetic Resonance of Solid 1,1,1,2-Tetrachloro-2-methylpropane
Authors: Koide Tsutomu , Oda Tsutomu
Published: July 2006

The molecular motion in the crystal lattice of 1, 1, 1, 2-tetrachloro-2-methylpropane was studied, by proton magnetic resonance absorption measurements, over the temperature range between 30°C and −190°C. The absorption-line witdhs changed at −62°C. The second moments remain almost constant, about 5 gauss2, between from −63°C to about −150°C, whereas above −62°C the values fall suddenly to 0.5 gauss2. From the analysis of the proton second moment, it was found that, in the high-temperature phase, the molecules rotate almost freely in the crystal lattice, while in the low-temperature phase, the major molecular motion is the rotation of the methyl groups about the C–CH3 bonds in the molecule.
The Spectrophotometric Determination of Perchlorate Ions by Solvent Extraction with Crystal Violet
Authors: Uchikawa Sumio
Published: July 2006

A micro quantity of perchlorate ions is extracted into chlorobenzene with crystal violet. The absorbance maximum of the extract in the organic layer is found to be at 595 mμ. The maximum and the constant extraction was obtained in the pH range of 2–7. In order to ascertain the optimum conditions for the determination of perchlorate ions, various factors have been studied: the effects of the concentration of the dyestuff, the pH of the solution, the standing time of the solution, the times of the extraction, and the presence of diverse ions. The recommended procedure for the calibration curve is as follows: Two milliliters of a crystal violet solution (1×10−3  m), 5 ml of a potassium phosphate buffer solution (1 m, pH 5.8), and various volumes (0–10 ml) of a standard perchlorate solution (2×10−5 mol/l) are mixed. The mixed solution is diluted to 25 ml with water. An aliquot (10 ml) of the solution is then poured into a separatory funnel and is shaken for 5 min with 10 ml of chlorobenzene. The absorbance of the organic layer is measured at 595 mμ against the reagent blank solution. Beer’s law is obeyed in the perchlorate range of 10−7–8×106 mol/l in the aqueous layer before the extraction. Considerable amounts of chloride, iodate, and sulfate ions do not interfere.
Solvent Extraction and Spectrophotometric Determination of the Pertechnetate Ion with Methyl Violet
Authors: Fujinaga Taitiro , Koyama Mutsuo , Kanchiku Yoshihiko , Tsurubo Shigeo
Published: July 2006

A spectrophotometric method of determination of TcO4− subesquent to solvent extraction with methyl violet was investigated. Methyl violet which has a molar extinction coefficient of about 2×105 at 585 mμ in a neutral aqueous solution was found to be extractable with TcO4− into monochlorobenzene. The absorption maximum of the dye in the organic layer after extraction shifts to 595 mμ, at which point the absorbance is proportional to the amount of TcO4− added to the aqueous solution. The effect of the pH on the absorbance of organic layer was very small as long as the absorbance was measured against the reagent blank as a reference. Over the wide range of pH values from 2 to 10, an approximately constant absorbance was obtained for a fixed amount of TcO4−. Effects of diverse ions were also examined. Alkali salts of phosphate, borate, citrate, and tartrate have little effect on the absorbance of the organic layer, whereas perchlorate and perrhenate seriously interfere. When the extraction efficiencies of TcO4− were measured using 95mTc and 97mTc as tracers, they were found to be quantitative, even at a concentration as low as 10−12m.
Separation of the Stereoisomers of Di-s-butyl Ether
Authors: Taniguchi Hiroaki , Iriuchijima Makoto , Komatsu Youji
Published: July 2006

d-Di-s-butyl ether was prepared by the reaction of d-s-butyl-alcoholate and optically inactive di-s-butyl sulfate, followed by displacement chromatography. With the same chromato-graphic technique, meso- and rac-di-s-butyl ether were separated from the commercial di-s-butyl ether.
Untersuchung der freien Fettsäuren, der freien Sterine, der Sterinester und der Glyzeride im Regenwurm (Lumbricus Spencer)
Authors: Naya Yoko , Kotake Munio
Published: July 2006

Aus den beiden Ätherextrakten von getrocknetem und frischem japanischen, gewöhnlichen Regenwurm (Lumbricus Spencer) wurden die freien, niedrigen und höhern Fettsäuren isoliert, und darin wurden neben gewöhnlichen, geradzahlig-gesättigten und ungesättigten Fettsäuren, auch ungeradzahlig-gesättigte und isomere Verbindungen gefunden. Mit Hilfe der Gaschromatographie wurde das Fettsäuremethylestergemisch in seine Komponenten zerlegt und die Strukturzusammensetzungen jener Komponenten wurden mittels Mass- und NMR-Spektren identifiziert. In den freien Sterinen, die wir isoliert haben, wurden neben Cholesterin, auch Brassicasterin gefunden. Provitamin D oder Δ5,7-Sterin wurde durch UV Absorption in rohen Sterinen nicht aus frischem Regenwurm, sondern aus getrocknetem Wurm (etwa 1.7%) entdeckt. Beim Lumbricus Spencer wurde Ergosterin, das beim Lumbricus terrestris (F. Bock und F. Wetter, Z. Physiol. Chem., 256, 55 (1938)) entdeckt wurde, nicht gefunden. Aus je getrocknetem und frischem Regenwurm wurden die Sterinester isoliert. Das Fettsäuregemisch, das man beim Verseifen der Sterinester gewinnt, besteht aus n-C16, n-C17 und n-C18 Fettsäuren. Die Sterine aus den Sterinestern setzen sich aus Cholesterin und Brassicasterin zusammen. Die Glyzeride wurden aus je getrocknetem und frischem Regenwurm isoliert. Die Fettsäuren aus den Glyzeriden waren die gleichen Komponenten wie die freien Fettsäuren.
The Radiation-induced Addition Reactions of Ethers and Alcohols to Perfluoropropene
Authors: Muramatsu Hiroshige , Inukai Kan , Ueda Teruo
Published: July 2006

The radiation-induced addition reactions of ethers and alcohols to perfluoropropene were studied. Mainly the 1:1 adducts were obtained in excellent yields, but in the addition of di-ethyl ether and dioxane the 1:2 adduct with a symmetrical structure was produced along with the 1:1 adduct. The ethers containing the perfluoropropenyl group were prepared by the dehydrofluorination of the corresponding 1:1 adduct. From the proton and fluorine NMR spectra, the attacks of the α-ethereal and α-hydroxyalkyl radicals were found to occur exclusively on the difluoromethylene carbon. The relative reactivities of ethers and alcohols were determined by competitive reaction.
The Conjugative Effects of Thia, Sulfinyl and Sulfonyl Groups on the Dissociation of p-Substituted Phenols
Authors: Oae Shigeru , Yoshihara Masakuni , Tagaki Waichiro
Published: July 2006

Several di- or tetramethyl substituted derivatives of bis-(4-hydroxyphenyl)sulfides, sulfoxides and sulfones were newly prepared and their acid dissociations, UV and IR spectra were reinvestigated. Essentially no steric inhibition was observed in the 3-d orbital resonance with the sulfinyl and the sulfonyl groups in both the acid dissociations and the UV spectra of the substituted phenols. However, a small but noticeable steric inhibition by ortho methyl groups was observed with the mercaptophenol.
Thermo-Analytical Investigation of Phase Equilibria in the Al2O3-SiO2 System
Authors: Horibe Toshiyasu , Kuwabara Senzo
Published: July 2006

The phase equilibrium relation of the Al2O3-SiO2 system was thermo-analytically investigated using a molybdenum resistance furnace with an argon atmosphere and a tungsten-tungsten 26% rhenium thermocouple (supplementary experiments were also made), and the phase diargam for the high aluminous region was presented. The composition of mullite with the highest melting point is 2Al2O3·SiO2 or very close to that value, and the mullite of the composition melts in-congruently at 1890±5°C, giving a liquid with a composition slightly less in Al2O3 content than that of the mullite. Other investigators’ results were interpreted on the basis of the results of the present investigation. In the present experiment an “unstable” growth of corundum was frequently observed.