bluuebunny/crossref_metadata_2025 huggingface dataset:
An X-Ray Determination of the Structure of Chamaecynenol
Authors: Shimanouchi Hirotaka , Sasada Yoshio
Published: July 2006

Crystals of chamaecynenol 4-bromo-3-nitrobenzoate, C21H22O4NBr, are monoclinic, with two molecules in a unit cell of the dimensions, a=10.47, b=14.08, c=6.75Å, and β=101.8° and with the space group of P21. The intensities were recorded on multiple-film equi-inclination Weissenberg photographs and measured visually with a standard scale. The structure was determined by the heavy atom method. The positional and thermal parameters were refined by the least-squares method. The final R factor for the observed reflections is 0.090. The absolute configuration was also determined using anomalous dispersion effect of the bromine atom. It was thus established that chamaecynenol is 7β-ethynyl-4β-hydroxymethyl-10β-methyl-Δ1-cis-octaline in the steroid conformation.
An ESR Study of Photochemical Intermediates from Rigid Organic Solvents Containing Benzene
Authors: Tanei Tadayoshi , Hatano Hiroyuki
Published: July 2006

The present work was undertaken in order to examine a photochemical intermediate from benzene using rigid organic matrices: EPA (a mixture of E: diethyl ether, P: isopentane, and A: ethyl alcohol, 5:5:2, v/v), diethyl ether, and isopentane. The UV irradiation of EPA, diethyl ether, and ethyl alcohol at 77°K, in wavelength regions from approximately 2200Å to 2600Å, gave ESR spectra which can be ascribed to the ethyl and/or the ethanol radical, even when a solute was not added. On the contrary, the UV irradiation of isopentane under similar conditions did not show any ESR spectrum. However, the UV irradiation of isopentane containing benzene in concentration regions from 10−1 to 10−2  m gave two kinds of ESR spectra, ascribed to phenyl and tert-pentyl radicals. This reaction may be interpreted as a sensitized photodecomposition brought about by an excitation and/or a photolytic degradation of benzene.
Infrared Absorption Spectra of Urea-formaldehyde Initial Condensation Products. II. Dimethylurea
Authors: Mido Yoshiyuki , Murata Hiromu
Published: July 2006

The infrared absorption spectra of symmetric and asymmetric dimethylurea have been observed in the 4000—400 cm−1 region. In order to investigate the amide characteristic bands, the spectra of CH3NHCONHCH3 and CH3NDCONDCH3 have also been measured in the solid and liquid states, and in solutions. The in-plane normal vibrations of these molecules have been calculated. As a result of our measurements and calculations, it has been found that: (1) The contribution of the polar resonance structure of asymmetric dimethylurea is small compared with that of symmetric dimethylurea, and molecular geometry contributes to the formation of hydrogen bonding. (2) From the position of the amide bands, the molecular configuration of symmetric dimethylurea is the “trans” form as well as that of methylurea. (3) The results of normal coordinate analysis show a good agreement with that observed within an average deviation of 2.6%.
Effects of Solvent on the Copolymerization of Ethylene with Tetrafluoroethylene by Cobalt-60 Gamma Radiation
Authors: Hagiwara Miyuki , Miura Takeshi , Kagiya Tsutomu
Published: July 2006

The cobalt-60, γ-radiation induced copolymerization of ethylene with tetrafluoroethylene was carried out in the gas phase and in the liquid phase by using five solvents (liquefied carbon dioxide, carbon tetrachloride, ethylchloride, chloropentafluoroethane, and 1,2-dichloro-tetrafluoroethane) at a dose rate of 25000 rad/hr under a pressure of 300 kg/cm2 at 30°C. A lower rate of the copolymerization and a copolymer of a lower molecular weight were obtained in liquid carbon dioxide and carbon tetrachloride than in the gas phase without a solvent. In ethyl chloride, the rate increased slightly, but the molecular weight decreased. On the other hand, both the rate and the molecular weight increased markedly in the fluorocarbon solvents. As a result of a detailed investigation of the copolymerization in 1,2-dichloro-tetrafluoroethane, a linear increase in the copolymerization rate and the copolymer molecular weight with the amount of solvent was noted, and there was no noticiable influence of the solvent on the copolymer composition. A kinetical discussion indicated that the addition reaction of tetrafluoroethylene to radicals produced by the influence of primary radiation on the reaction mixture is an important step in initiating the copolymerization. Also, the propagation reaction seemes to be strongly promoted by the fluorocarbon solvents.
The Low Temperature n–π* Absorption Spectra of the Cyclohexane-1,4-dione Crystal
Authors: Ozeki Kayoko , Tanaka Jiro
Published: July 2006

Cyclohexane-1,4-dione is an aliphatic ketone with two carbonyl groups. The absorption due to the n–π* transition of the carbonyl group extends from the 30000 cm−1 to the 42000 cm−1region. The transition is symmetrically forbidden and is assigned to the A1-A2 transition in the C2v system. The spectra in the crystal and in a solution of EPA at 77°K show only prominent carbonyl stretching vibrations. The polarized single crystal absorption spectra at 4.2°K are composed of many sharp lines; the vibrational structures are analyzed in detail. The 0–0 transition is observed at 31408 cm−1; the distinct basic frequencies of the excited state are 1096, 790, 557, 375, 247, and 122 cm−1, while the lattice vibrations are 61, 32, and 22 cm−1. The transition is explained by the vibronic coupling mechanism, assuming the C2v symmetry for the carbonyl group. Two different types of progressions are noticed; one is induced by the out-of-plane b2-type vibration, while the other is allowed by the a2-type vibration. The dichroic properties of the crystal spectra allowed the assignment of the vibrational modes. These vibrations are compared with the infrared and Raman spectral data.
A Solvent-extraction and Spectrophotometric Study of Copper(II) Complexes in Organic Solvents Containing Acetylacetone and Thenoyltrifluoroacetone
Authors: Hasegawa Yuko
Published: July 2006

The complex-formation equilibria of copper(II) in chloroform, benzene, or methyl isobutyl ketone (MIBK) containing both acetylacetone (AA) and thenoyltrifluoroacetone (TTA) have been determined by means of a liquid-liquid distribution method and a spectrophotometric method. The extraction constants or the extinction coefficients of the pure complexes were first determined in solutions containing only one of the liquids, and then these constants for the mixed complex and the equilibrium constants among the three complexes in these solvents were determined by the analysis of the results obtained from the experiments in mixed-ligand solutions. From these data, the following conclusions were reached. The constants experimentally obtained are almost identical with those statistically expected. The absorption spectrum of the mixed complex isolated from the absorption of the mixed-ligand system by the statistical analysis is more similar to that of the TTA complex than to that of the AA complex. The results obtained by these two methods are somewhat different from each other.
Group Theoretical Treatment of Crystal Vibrations; Application to Orthorhombic Polyethylene
Authors: Kitagawa Teizo , Miyazawa Tatsuo
Published: July 2006

Irreducible representations of k groups of the space group Pnam were derived with Slater’s method. Degeneracies of crystal vibrations due to space symmetry and time reversal symmetry were treated on the basis of Maradudin’s theory. With irreducible representations of k groups, symmetry coordinates of the carbon atoms of orthorhombic polyethylene were constructed from translational-symmetry coordinates with nonintegral index vectors. A general matrix method was worked out for treating crystal vibrations of any phase-difference vector. Useful methods were derived for treating molecular crystals and chain polymer crystals and for approximate treatment of low frequency lattice vibrations.
Decomposition of Ammonia and Reactivity of Nitrogen Absorbed on Molybdenum
Authors: Tsuchiya Susumu , Ozaki Atsumu
Published: July 2006

Adsorption measurements during the course of ammonia decomposition over molybdenum catalyst have been carried out in a closed circulating system. It was found that most of the nitrogen produced was taken up by molybdenum, and the initial rate of the reaction was independent of the ammonia pressure in a certain region. During the decomposition the nitrogen uptake was several times as much as the amount required to saturate the catalyst surface, which indicates the formation of nitride layers. The catalytic activity of molybdenum trioxide for ammonia decomposition was also observed, and the formation of nitride layers was again suggested. The nitrogen sorbed on molybdenum was removed as ammonia by admitting hydrogen and was displaced by oxygen added afterwards.
Reactions of Tungsten Oxy-dichlorodialkoxides with Cyclopentadiene and Sodium Cyclopentadienide
Authors: Anand S P , Multani R K , Jain B D
Published: July 2006

The formation of π-cyclopentadienyl tungsten oxychlorodialkoxides as a result of the interaction between cyclopentadiene or its sodium derivative with tungsten oxy-dichlorodialkoxides, having the general formula C5H5WOCl(OR)2, where R is CH3, C2H5, (Remark: Graphics omitted.), CH3CH2CH2 and CH3CH2CH2CH2 along with the thermal stabilities and infrared spectra of the above products, has been studied and reported.
The Indirect Determination of Mercury in an Aqueous Solution using the Ligand Exchange Reaction
Authors: Kawai Itsuro , Hara Tadashi
Published: July 2006

A new method for the indirect determination of mercury in an aqueous solution has been established on the basis of the fact that the absorption and evolution of propylene in the reaction between mercuric ion and propylene take place reversibly and quantitatively under proper conditions. In the method proposed, the propylene in the 1 : 1 π-complex is displaced with such complexing agents as chloride, bromide, iodide and EDTA, and the quantity of the propylene evolved is measured manometrically. By the present method, up to 70 mg Hg can be estimated within ±0.08 mg in about 15 min. Common cations and anions do not interfere. Though silver(I) and palladium ions interfere, their interferences are removed by suitable procedures. By improving the apparatus, it should be possible to estimate much smaller amounts of mercury than the above value.
Solvolysis of Organic Phosphates. II. Pyridylmethyl Phosphates as Effected by the Presence of Polyvalent Metal Ions
Authors: Murakami Yukito , Takagi Makoto
Published: July 2006

Influence of polyvalent metal ions on the hydrolysis of 2-, 3- and 4-pyridylmethyl phosphate was investigated at μ=0.01 in a lower pH range. The thorium ion accelerated the hydrolysis rate of all the phosphates to a remarkable extent as investigated at 40, 70 and 90°C. The primary participation of the phosphate moiety of each pyridylmethyl phosphate in the interaction with thorium(IV) was considered to be the main cause of this catalysis. Thus, the thorium catalysis was mechanistically distinguished from the copper catalysis which has been clarified previously. In addition, the vanadyl ion also demonstrated positive catalytic effect. On the other hand, iron(III) and aluminum(III) retarded the hydrolysis rate. This was ascribed to the reduced fraction of the active monoionic species as a result of metal-complex formation with the phosphates in the course of hydrolysis.
Oxytocin Analogues Containing No Disulfide Bond. I. Synthesis of the Lactam of l-Tyrosyl-l-isoleucyl-l-glutaminyl-l-asparaginyl-l-α-aminosuberyl-l-prolyl-l-leucylglycine Amide
Authors: Kobayashi Akiko , Hase Satoe , Kiyoi Reiko , Sakakibara Shumpei
Published: July 2006

The synthesis of an analogue of deamino-oxytocin, which has an ethylene linkage in place of the disulfide bond, was studied in order to establish a general route for the synthesis of such cyclic peptides. l-α-Aminosuberic acid (Asu) was converted to the N-benzyloxycarbonyl-ω-t-butyl ester and was used as the starting substance for the synthesis. A protected octapeptide was prepared by the step-by-step elongation method with the respective benzyloxycarbonylamino acid active esters, and finally the cyclization of the ω-carboxyl group of the Asu-residue to the amino group of the tyrosyl-residue was achieved by the trifluoroacetate method. The final product showed obviously higher oxytocin-like activities than those reported previously. The conditions for the syntheses of p-nitrophenyl and 2,4,5-trichlorophenyl trifluoroacetates were improved during the investigation.
Structural Study of the Catalytic Activity of Alkyl Chloride in the Polymerization of N-Phenylethylenimine
Authors: Kagiya Tsutomu , Kondo Tomizo , Obata Keigo
Published: July 2006

The catalytic activity of various alkyl chlorides in the polymerization of N-phenylethylenimine was studied from the structural point of view. Both the polymerization rate and the molecular weight of the polymer obtained varied with the kind of alkyl chloride. The rate of monomer consumption is expressed by a first-order rate equation with respect to the monomer concentration in the early stage of the polymerization. The efficiency factors of the catalysts differ with the kind of alkyl chloride and increase with an increase in the reaction time. When the chloride of a conjugated alkyl group is used, the polymerization rate decreases with an increase in the ionization potential of the alkyl radical, while it increases when chlorides of a non-conjugated alkyl are used. The structural study of the catalytic activity of the alkyl chloride was made quantitatively from the energetic point of view.
Alkaline Decomposition of Triarylsulfonium Halides with Various Bases
Authors: Oae Shigeru , Khim Yong He
Published: July 2006

Alkaline decomposition of triarylsulfonium bromides with various bases was found to give different products depending on the nature of the bases. The reaction of triarylsulfonium bromide with either piperidide anion or thiophenoxide ion seems to proceed with the initial attack of piperidide anion or thiophenoxide ion of the carbon atom of C-S bond (SN reaction on carbon atom), while the reaction of diarylethoxysulfonium tetrafluoroborate with thiophenoxide ion is presumed to involve the initial attack of thiophenoxide ion on the sulfur atom at low temperature (SN reaction on sulfur atom). When triarylsulfonium bromide was subjected to the reaction with potassium hydroxide in aqueous ethanol, the main path was the alkaline decomposition which proceeds via the nucleophilic attack of the ethoxide ion on the sulfur atom. In the treatment with hydroxide ion in water, the decomposition appears to proceed mainly via two mechanistic routes, i.e., the processes involving the nucleophilic attack of hydroxide ion on both aromatic carbon and the sulfur atoms. A free radical process cannot be excluded, but appears unlikely.
Reaction of Ethyl Diazoacetate with Cupric Chloride
Authors: Saegusa Takeo , Ito Yoshihiko , Shimizu Toyoji , Kobayashi Shiro
Published: July 2006

The reaction of ethyl diazoacetate (1) with CuCl2 was investigated. Ethyl chloroacetate (2), ethyl dichloroacetate (3) and a mixture of ethyl dichloromaleate (4) and ethyl dichlorofumarate (5) were produced. These products were explained by assuming 1-chloro-1-ehtoxycarbonylmethylcopper complexes, (10) and (11). The reactions of 1 with HgCl2 and CoCl2 were examined in detail as reference reactions from the mechanistic view point.
Preparation of Vinyl Ethers by Transetherification in the Presence of Molecular Sieves
Authors: Yuki Heimei , Hatada Koichi , Nagata Kazuhiko , Kajiyama Ken-ichi
Published: July 2006

The interchange reaction: CH3OCH=CH2+ROH \ightleftarrows ROCH=CH2+CH3OH, which is catalyzed by Hg(OAc)2, has been studied. It was found that the equilibrium could be smoothly shifted toward the product by the selective absorption of the produced methanol on molecular sieves of the type 4A (MS-4A) and that the yield of the desired vinyl ether could be increased. According to this method, we prepared various vinyl ethers, including ethyl, isopropyl, isobutyl, t-butyl vinyl ether, and benzyl vinyl ethers. The yields of the alkyl vinyl ethers decrease as their alkyl groups become more electron-donating. The effects of the reaction conditions and the pretreatment of the molecular sieves have been investigated.
Electronic Spectra of O-Alkyl Thiobenzoates and Their Derivatives
Authors: Ohno Atsuyoshi , Koizumi Tamotsu , Ohnishi Yutaka , Tsuchihashi Gen-ichi
Published: July 2006

The absorption spectra of O-methyl and -ethyl thiobenzoates and their p- and m-methoxy, methyl and chloro derivatives have been studied. The substituent effect on the n→π* transition of thiocarbonyl group has been discussed with the use of the Hammett relationship.
Electrical Conduction of TCNQ Ion Radical Salts under High Pressure
Authors: Shirotani Ichimin , Kajiwara Takashi , Inokuchi Hiroo , Akimoto Syun-iti
Published: July 2006

With an increase in the pressure, the electrical resistance of several TCNQ anion radical salts dropped rapidly in the low-pressure region and levelled off at high pressures. The temperature dependence of the resistance of compressed salt was studied over the region from 77°K to 200°K. The values of the activation energy decreased with an increase in the pressure. However, the metallic behaviour was not observed under very high pressures. The conduction mechanism of TCNQ, salts was discussed from the point of view of a band scheme.
Optical and Acoustic Branches and Frequency Distribution of Polyethylene Glycol Chain
Authors: Matsuura Hiroatsu , Miyazawa Tatsuo
Published: July 2006

Optical and acoustic branches of chain vibrations of polyethylene glycol were treated. The nature of these branches was elucidated on the basis of potential-energy distributions and phase relations. From dispersion curves (frequency versus phase difference), the frequency distribution of chain vibrations was calculated, in order to analyze thermal-neutron scattering spectra. Vibrational assignments of scattering peaks in the region 600–200 cm−1 were made with reference to the frequency distribution peaks and potential-energy distributions calculated for the single chain.
Gravimetric Determination of Palladium, Silver, Mercury and Copper with 2-Mercaptomethylbenzimidazole
Authors: Bera Bimal C , Chakrabartty M M
Published: July 2006

New selective methods are described for the gravimetric determination of palladium, silver, copper and mercury with 2-mercaptomethylbenzimidazole. In the presence of EDTA or tartrate, palladium, silver and mercruy are determined at pH of 4–5. Copper is determined as the copper(I) complex in the same pH range using cyanide as a reducing and complexing agent. Thermogravimetric studies reveal adequate thermal stability of the complexes. X-Ray studies confirm the identity of the end products in the thermolysis of the copper(I) and copper(II) complexes.
The Effect of Acetate Ion on the Rate of the Reaction between Cobalt(II) and Manganese(II)-Ethylenediaminetetraacetate Complexes
Authors: Kimura Masaru
Published: July 2006

The kinetics of the substitution reactions of cobalt(II) ions and manganese(II)-ethylene-diaminetetraacetate complexes have been studied in acetate buffer solutions at 25°C and at ionic strength of 0.2. The reaction was treated as to proceed through both hydrated metal ions and monoacetato complexes. The rate constants for six elementary reaction paths, three of which involve hydrated cobalt(II) ions and the others, monoacetatocobalt(II) complexes, were determined. The values obtained indicate that all the reactions proceeding through monoacetatocobalt(II) complexes are about three times faster than the corresponding reactions proceeding through hydrated cobalt(II) ions.
The Effect of Phthalate Ion and Acetate Ion on the Rate of the Reaction between Nickel(II) and Cobalt(II)-Nitrilotriacetate Complexes
Authors: Kimura Masaru
Published: July 2006

A kinetic study of the substitution reactions of nickel(II) ions and cobalt(II)-nitrilotriacetate complexes in phthalate and in acetate buffer has been carried out using a procedure previously reported. The reaction was made to proceed through both hydrated nickel(II) ions and monophthalatonickel(II) complexes or monoacetatonickel(II) complexes. The rate constants for eight elementary reaction paths, four of which involve the hydrated nickel(II) ions, while the others involve the monophthalatonickel(II) complexes (the monoacetatonickel(II) complexes in the case of the measurements in acetate media), were determined at an ionic strength of 0.2 at 25°C. The values obtained indicate that all the reactions proceeding through the monophthalatonickel(II) complexes are slower than the corresponding reactions proceeding through hydrated nickel(II) ions; however, all the reactions proceeding through monoacetatonickel(II) complexes are faster than the corresponding reactions proceeding through hydrated nickel(II) ions. Thus, the kinetic reactivity is in the order of: NiOAc+>Ni2+>NiPh, where Ph2− indicates a bivalent phthalate anion.
Stability Constants of Some Uranyl Complexes. II
Authors: Ramamoorthy S , Santappa M
Published: July 2006

Stability constants of complexes of uranyl ion with various carboxylic acids were determined by the pH titration method at 31°C and μ=0.1 (NaClO4) in the pH range 2.5–3.5. The 1 : 1 and 1 : 2 complexes were formed with crotonic, pyruvic, malonic, and diglycolic acids and only the 1 : 1 complex with formic, propionic, succinic, adipic, maleic, fumaric acids. The effect of ring size and presence of oxygen atom as keto or ether oxygen or that of double bonds in the ligand acids on the stabilities of the corresponding complexes are discussed.
Chemical Effects Associated with β-Decay Process. III. The Chemical Behavior of 144Pr Decayed from 144Ce(III)-EDTA Complexes in the Solid Phase
Authors: Shiokawa Takanobu , Kudo Hiroshi , Omori Takashi
Published: July 2006

The chemical behavior of 144Pr formed by the β−–decay of 144Ce in crystals of 144Ce(III)-EDTA complexes has been investigated by means of ion-exchange techniques. The initial yield of 144Pr3+ ion, which reflects the distribution of the 144Pr atoms in the crystal, is independent of the dissolving condition, but is affected by the amount of hydration in the crystal. Abnormal behavior of 144Pr atom has not been found in the ammonium salt. These results suggest that in the solid phase 144Pr3+ or its precursor may be produced as a result of multiple charging of the daughter following electron shake-off and internal conversion of γ-rays.
Long-term Integration of Polarographic Currents and Its Analytical Application
Authors: Matsuda Kiyoshi , Tamamushi Reita
Published: July 2006

The integral readout technique was applied to the accurate determination of average polarographic currents. The long-term integration of polarographic currents provides a useful method of compensating residual currents and thus of increasing the sensitivity and accuracy of the d. c. polarographic analysis. The analytical utility of the proposed method was tested with cadmium, lead, and zinc ions in chloride solutions; these ions were found to be determined with reasonable accuracy even at concentrations as low as 10−6  m. Depolarizers at concentrations of the order of 10−4  m can be determined accurately in air-saturated solutions. The present method has the considerable merit that its sensitivity is not affected by the degree of reversibility of the electrode reaction. The integral technique was also applied successfully to the compensation of residual currents by the twin-cell system, in which a pair of dropping mercury electrodes is not necessarily synchronized.
The Reaction of Alcohols and Hydrocarbons in a Silent Electric Discharge. I. The Decomposition of 2-Propanol by the Discharge
Authors: Hiraki Teruo
Published: July 2006

The reaction of 2-propanol under a silent electric discharge was studied using two kinds of discharge tubes. One was Siemen’s tube, which was used for investigating a silent discharge decomposition of 2-propanol. The other was a special tube that had one side of the walls made of copper or its salts; it was used for studying the effects of the wall on the decomposition. The main liquid products were acetaldehyde, acetone, dl-2-butanol, 2-methyl-2-propanol, 2-methyl-2-butanol, and hydrocarbons. The gaseous products were methane, C2–C4-hydrocarbons, carbon monoxide, carbon dioxide, and hydrogen. These components were obtained in every run, regardless of the type of tube used. However, the distribution of the products varied with the sort of tube. The formation of 2-methyl-2-butanol can be explained by the addition of a 1-hydroxyisopropyl radical with the ethylene produced; the only product formed by adding this radical to ethylene was the one-to-one adduct. By replacing one side of the glassy walls with a wall of a glass-filter-packed copper or its salts, the yield of 2-methyl-2-propanol was increased relatively, and those of 2-methyl-2-butanol and dl-2-pentanol were decreased.
The Synthesis of Poly-l-arginine Hydrobromide and Copolymers of l-Arginine and Other Amino Acids
Authors: Hayakawa Tadao , Kondo Yoshiyuki , Yamamoto Hiroyuki , Murakami Yukiko
Published: July 2006

Pure crystalline Nω,ω′-dicarbobenzyloxy-l-arginine N-carboxyanhydride hydrochloride was obtained from Nα,ω,ω′-tricarbobenzyloxy-l-arginine and thionyl chloride. It was polymerized to poly-Nω,ω′-dicarbobenzyloxy-l-arginine. This polymer was converted to poly-Nω-carbobenzyloxy-l-arginine by treating it with alcoholic potassium hydroxide; also, both carbobenzyloxy groups of the protected polymer were completely removed into poly-l-arginine by treating them with hydrogen bromide in glacial acetic acid. Several copolymers containing l-arginine residue were also prepared by the copolymerization of the above NCA and the NCAs of other amino acids, such as γ-benzyl-l-glutamate, l-alanine, and Nε-carbobenzyloxy-l-lysine.
Intramolecular Hydrogen Bonds. XIII. The Preferable Conformation of α-Hydroxy-carboxylic and o-Hydroxybenzoic Acids
Authors: Mori Nobuo , Asano Yuzuru , Irie Toshiko , Tsuzuki Yojiro
Published: July 2006

The infrared hydroxyl and carbonyl stretching absorption spectra of salicylic, mandelic, and α-hydroxyisobutyric acids have been measured in dilute carbon tetrachloride solutions. The spectral data indicate that the first two acids exist exclusively in an internally-bonded conformation, one where the phenolic and the alcoholic hydroxyl groups form a hydrogen bond with the carbonyl oxygen atom of the cis-carboxyl structure, while the last acid takes, apart from such a conformation, another internally-bonded conformation, one where the hydroxyl group of the trans-carboxyl structure interacts with the alcoholic oxygen atom.
Ethylidenation of l-Sorbose
Authors: Maeda Takashi , Kiyokawa Masumi , Tokuyama Kanji
Published: July 2006

The ethylidenation of l-sorbose (I) with acetaldehyde dimethylacetal in the presence of an acid was studied. When the reaction was interrupted at the initial stage, an equilibrium mixture of the two possible cyclic acetals, 1,2-O-(III) and 1,3-O-ethylidene-α-l-sorbopyranose (V), was obtained. When the reaction was allowed to proceed for longer periods of time, 1,3:4,6-di-O-ethylidene-β-l-sorbofuranose (IX) was mainly isolated; the transformation of this to two diastereoisomeric 2,3:4,6-di-O-ethylidene-α-l-sorbofuranoses (XV and XVIII) required the use of highly acidic conditions. A pathway of I→(III\ightleftarrowsV)→IX→(XV+XVIII) was tentatively proposed for the ethylidenation of I.
Ultrasonic Relaxation of Water-Dioxane System
Authors: Arakawa Kiyoshi , Takenaka Nobuo
Published: July 2006

Ultrasonic investigations of the water-dioxane system were made by means of an ultrasonic pulse technique. The ultrasonic velocity and absorption of the solutions were measured in the frequency range from 5 to 45 Mc/sec. The temperature was varied from 20 to 60°C. It was observed in the velocity vs. concentration curves obtained at various temperatures that all curves converged at 0.03–0.04 mol fraction of dioxane. The ultrasonic absorption of pure dioxane was found to increase with the rise of temperature, which might be ascribed to the vibrational relaxation. From the ultrasonic absorption data obtained for the solutions of the water-dioxane system in various compositions and temperatures it was observed that at 0.3–0.4 mol fraction of dioxane an absorption peak was present in the absorption vs. concentration curve, and also that there was no shift of the concentration at the peak with the variation of temperature. Some discussion on the structure of the water-dioxane system was given from the ultrasonic data obtained.
Syntheses and Reactions of Functional Polymers. XL. Enhanced Reactivity of Poly(vinyl chloride) by Neighboring-Group Participation of the N,N-Disubstituted Dithiocarbamate Function
Authors: Nakai Takeshi , Kawaoka Hideo , Okawara Makoto
Published: July 2006

In order to demonstrate that neighboring-group participation of the N,N-disubstituted dithiocarbamate function is involved in the substitution reaction of poly (vinyl chloride) (PVC) with the dithiocarbamate anion, the rates of reactions of PVC and the copolymer (vinyl chloride-S-vinyl N,N-diethyldithiocarbamate) with −SCS-NEt2 were compared under the same conditions. These polymer reactions were undertaken in dimethylformamide or tetrahydrofuran at 45°C. The rate enhancements with the copolymer were observed in both solvents. From these observations, it was concluded that the chloromethylene groups in PVC neighboring the dithiocarbamate function were activated .toward the nucleophile via neighboring-group participation. This is the first time that neighboring-group participation involving the polymer main chain might be observed in the polymer reaction. The difference in reaction mechanism between the polymer reaction and the model reaction was discussed.
The Synthesis of Regular Copolymers of Glycine and Alanine
Authors: Takahashi Sho
Published: July 2006

The synthesis of polypeptides with a repeating sequence of glycines and l-alanines, i. e., poly-(l-Ala-Gly-Gly), poly-(l-Ala-l-Ala-Gly), and poly-(l-Ala-l-Ala-l-Ala-Gly), are reported. Polymerization was achieved by a self-condensation of p-nitrophenyl esters of the corresponding tri- or tetrapeptides.
Studies of Aminosugars. XXIII. The Total Synthesis of Kanamycin B
Authors: Umezawa Sumio , Koto Shinkiti , Tatsuta Kuniaki , Hineno Hirokuni , Nishimura Yoshio , Tsumura Takayuki
Published: July 2006

4-O-(3,4-Di-O-benzyl-2,6-dicarbobenzoxyamino-2,6-dideoxy-α-d-glucopyranosyl)-N,N′-dicar-bobenzoxy-2-deoxystreptamine has been prepared from neamine and condensed with 3-acetamido-2,4,6-tri-O-benzyl-3-deoxy-α-d-glucopyranosyl chloride by a modified Koenigs-Knorr reaction to give an α,α-diglycoside. The identity of the product with a substance of the same structure derived from natural kanamycin B was shown. Removal of the masking groups from the product gave the synthetic kanamycin B, which was identical with natural kanamycin B.
Measurement of Negative Ions Formed by Electron Impact. I. Negative Ion Mass Spectra of Nitroalkanes
Authors: Tsuda Satoru , Yokohata Akira , Kawai Michihiro
Published: July 2006

The negative ion mass spectra of nitroalkanes (nitromethane, nitroethane, 1-nitropropane and 2-nitropropane) have been mesaured with a mass spectrometer under electron energies of 80 eV, 40 eV, 9.5 eV and 4.5 eV in the range of pressure used for usual analysis. The spectral intensities of negative ions were compared with those of positive ions. In 80 or 40 eV electron impact experiments, m/e 16 (O−), 46 (NO2−), 26 (probably, CN−) and 42 (probably, CNO− or C2H4N−) ions were commonly found. Their yields showed good linearity against pressure under the present experimental conditions. The peaks of m/e 61 (parent ion; CH3NO2−) in nitromethane, of m/e 25 (C2H−) in nitroethane, 1-nitropropane and 2-nitropropane, and a relatively strong peak of m/e 60 (CH2NO2−) in 1-nitropropane were characteristic. For lower electron energies, the strong dependency of the yield of negative ions on the electron energy was confirmed. The yield of negative ions as compared with positive ions for 80 eV and 40 eV of electron energy was lower by a factor of ∼104. On the other hand, the comparison of the yield of positive ions for 15 eV electrons with that of negative ions for 9.5 eV electrons gave the value of ∼0.2. In addition, of the role these negative ions in radiolysis has been briefly discussed.
Mechanism of a Stereospecific, Photosensitized, Cyclization Reaction of 3-Methylene-1,5-heptadiene
Authors: Kita Sin-ichiro , Fukui Ken-ichi
Published: July 2006

In order to understand the mechanism of the photosensitized, stereospecific cyclization of 3-methylene-1,5-heptadiene, we calculated the electronic state of two intermediates (13 imaginary conformations) by the extended Hückel molecular orbital method and discussed its rotation angle dependency. We obtained the following conclusions. 1) In the two intermediates, the second model (we suppose this to be more like a real intermediate) has lower energy than the first model (we suppose this to be an initial intermediate) both in the ground state and the excited state. 2) If it is necessary for this cyclization that an overlap stabilization exists between two carbon atoms to be bonded and the intermediate has lower energy in that state, the intermediate seems to cyclize after the transition to the ground state singlet. 3) The overlap stabilization between two carbon atoms mentioned above is mainly defined by the interaction between 2p electrons in the highest occupied orbital. This fact coincides with the consequence of the frontier electron theory. 4) The existence of the overlap stabilization between 2p electrons mentioend above corresponds to the fact that the special valence atomic orbital of that two carbon atoms has the same symmetry. This fact is in line with the Woodward-Hoffmann rule on “electrocyclic reactions.”
Solubility of Ag2O in Na2O-B2O3 Melts
Authors: Maekawa Takashi , Yokokawa Toshio , Niwa Kichizo
Published: July 2006

The solubility of silver oxide in Na2O-B2O3 melts was determined as a function of the Na2O contents, the temperature (825°C–935°C), and the oxygen partial pressures. The results show that the silver oxide dissolves in a borate as a network modifier, just like alkali metal oxides, which destroy the B–O–B bonds to produce four coordinated boron as well as three. In the Ag2O-B2O3 binary system, the solubility of silver oxide increases with an increase in the oxygen partial pressures. In the Ag2O-Na2O-B2O3 ternary system, the solubility of Ag2O decreases with an increase in the Na2O contents. This shows that the silver oxide is a weaker base than sodium oxide. The activity of the oxygen ion, ao=, was determined from the iso-activity lines of silver oxide. In a constant basic oxide content, ao= increases with an increase in the Na2O content. By extrapolating the Ag2O contents to zero, the oxygen-ion activity in the Na2O-B2O3 melt was determined.
A Spectrophotometric Study of the Uranyl Chelate of 2-(1,8-Dihydroxy-3,6-disulfo-2-naphthylazo)-phenoxyacetic Acid
Authors: Shimoishi Yasuaki
Published: July 2006

2-(1,8-Dihydroxy-3,6-disulfo-2-naphthylazo)-phenoxyacetic acid reacts with the uranyl ion in an acidic medium to form a violet chelate. The composition of the chelate is 1 : 1 in the molar ratio. The apparent stability constants over the pH range from 3.4 to 5.2 and the formation constant of the chelate, are estimated spectrophotometrically at 25°C and an ionic strength of 0.1 by the use of KNO3. The value of the formation constant was calculated as 1.25×1010 from the apparent stability constants.
Electronic Structure of Tris(1,10-phenanthroline)iron(II) Complex
Authors: Ito Tasuku , Tanaka Nobuyuki , Hanazaki Ichiro , Nagakura Saburo
Published: July 2006

The SGF MO’s for the π-electron system of 1,10-phenanthroline have been determined by following the Pariser-Parr-Pople’s treatment. For the description of the lower excited states, the configuration interaction among nineteen singly-excited configurations with lower energy has been taken into account. The electronic spectrum of 1,10-phenanthroline has been interpreted on the basis of the results of the theoretical calculation. The SCF MO’s for the π-electron system of a coordinated 1,10-phenanthroline in the tris-iron(II) complex have been determined to be self-consistent under the electrostatic potential field of the central metal ion and the other ligand molecules. On the basis of the results for coordinated ligand, the π-electronic structure of tris-(1,10-phenanthroline)iron(II) ion has been investigated from the theoretical point of view. It has been shown that two kinds of the charge-transfer transitions are responsible for an intense absorption band in the visible region, namely electron transfers from the 3dπ orbital of iron to the lowest and the second lowest vacant π MO’s of the ligand 1,10-phenanthroline. The discussions have been given on the change of the π–π* states of 1,10-phenanthroline by the coordination.
Polarographic Study of Thallium(I) Chelates of 2,2′-Ethylenedioxybis[ethyliminodi(acetic acid)] and Cyclohexane-1,2-diamine-N,N,N′,N′-tetraacetic Acid
Authors: Kodama Mutsuo , Tominaga Yayoe
Published: July 2006

D.c. polarographic behavior of thallium(I) ion in 2,2′-ethylenedioxybis[ethyliminodi(acetate)] (GEDTA) and cyclohexane-1,2-diamine-N,N,N′,N′-tetraacetate (CyDTA) solutions was studied systematically. Compositions and stability constants of thallium(I)-GEDTA and CyDTA chelates were determined from the shift of the half-wave potential. In both GEDTA and CyDTA systems, thallium(I) ion gave a single well-defined wave corresponding to the following reversible one electron reduction.

(Remark: Graphics omitted.)

In contrast to the finding of Anderegg and Bottari, thallium(I) ion was found to form not only a normal chelate but also a protonated chelate with CyDTA.
Polarographic Studies of Copper(II) Chelates of Ethylenediamine-N,N,N′,N′-tetrapropionic Acid and Diethylenetriaminepentaacetic Acid
Authors: Kodama Mutsuo , Tominaga Yayoe
Published: July 2006

D. c. polarographic behavior of copper(II) in ethylenediamine-N,N,N′,N′-tetrapropionate (EDTP) and diethylenetriaminepentaacetate (DTPA) solutions was studied systematically. In EDTP solution, copper(II) ion invariably gave a single well-defined wave corresponding to the following reduction.

CuX2−+nH++Hg+2e−=Cu(Hg)+HnXn−4

In the DTPA solution, copper(II) ion gave a single wave reversible in nature at pH below 5.0, corresponding to the following electrode reaction.

(Remark: Graphics omitted.)

At higher pH, however, two waves could be observed. The second step was irreversible and its wave-height increased with increasing pH at the expense of the height of the first step.
Reaction of Methylsulfinyl Carbanion with Substituted Phthalic Esters
Authors: Otsuji Yoshio , Yabune Hideo , Imoto Eiji
Published: July 2006

The treatment of dimethyl 3-nitrophthalate (I) with a mixture of dimethyl sulfoxide and sodium methoxide, followed by the acidification of the resulting mixture with hydrochloric acid, gave azoxybenzene-2,2′,3,3′-tetracarboxylic acid (II) and 3-nitrophthalic acid (III). The similar treatment of dimethyl 4-nitrophthalate (IV) afforded 5-methoxy-2-nitroso-1,3-indanedione (V) and 4-methoxyphthalic acid (VI). The similar treatment of dimethyl 4-methoxyphthalate (XV) and dimethyl phthalate gave 2-chloro-2-methylthio-5-methoxy-1,3-indanedione (XVII) and 2-chloro-2-methylthio-1,3-indanedione (XIX) respectively. The general features of these reactions are described.
Eine Dienon-Phenol-Umlagerung von 5-Oxo-2-methyl-4,4-dibenzyl-3-äthoxycarbonyl-4,5-dihydro-indol
Authors: Suehiro Tadashi , Eimura Koji
Published: July 2006

Bei der Einwirkung von Acetanhydrid-Schwefelsäure auf 5-Oxo-2-methyl-4,4-dibenzyl-3-äthoxycarbonyl-4,5-dihydro-indol (I) bei 0°C, findet eine Dienon-Phenol-Umlagerung von I zu 4-Acetoxy-2-methyl-5,6-dibenzyl-3-äthoxycarbonyl-indol (III) statt, dessen Struktur aus der leichten Verseifbarkeit der 3-Äthoxycarbonyl-Gruppe von III und aus den spektroskopischen Befunden der von III abgeleiteten Verbindungen folgte.
Deoxygenation of Styrene Oxide by Zinc Metal and Lewis Acid
Authors: Miyano Sotaro , Hida Mitsuhiko , Hashimoto Harukichi
Published: July 2006

Styrene oxide was deoxygenated to styrene in 83% yield by zinc metal and zinc chloride in aqueous ether. Under the same reaction conditions phenyl glycidyl ether gave only 2.8% of phenyl allyl ether, and propylene oxide did not give propylene. Effects of the reaction variables on the deoxygenation of styrene oxide were investigated. The yield of styrene was varied with metal halide in anhydrous THF in the following order; ZnI2>ZnCl2∼ZnBr2>AlCl3>SnCl4>FeCl3>NaI>>MgBr2. Styrene was formed from styrene oxide by zinc metal and zinc chloride in ca. 50% yield in THF, acetone, acetic acid, and aqueous ethanol, but not in anhydrous benzene. The yield of styrene increased almost proportionally with the increase of the molar ratio of zinc chloride to styrene oxide up to 1:1. 2-Phenyl-2-chloroethanol gave styrene when treated with zinc metal in the presence or absence of zinc chloride, but 1-phenyl-2-chloroethanol did not. Possible reaction paths of the deoxygenation of styrene oxide by zinc metal and metal halide were discussed.
Photo-Aryl Coupling and Related Reactions. II. The Formation of Triphenylenes from Halogeno-o-terphenyls
Authors: Sato Takeo , Shimada Shigeru , Hata Kazuo
Published: July 2006

Electronic effects on the photochemical conversion of o-terphenyl to triphenylene were examined by comparing the ultraviolet irraiation reaction, carried out in a benzene solution using iodine as an oxidant, of three classes of o-terphenyl derivatives, 4- (3) and 4′-substituted (4) and 4,4″-disubstituted derivatives (5). While a strong electron-withdrawing group such as nitro group, hindered the cyclization reaction to occur, methoxy, fluoro, chloro and bromo compounds afforded the corresponding triphenylene derivatives. With bromo and iodo compounds, however, a complex mixture of the products resulted due to photochemical cleavage of a carbon-halogen bonding, which led to the formation of phenylation products and hence phenyltriphenylenes together with reduction products. Further, with iodo compounds, it was found that no oxidant was necessary to effect the cyclodehydrogenation reaction since iodine was liberated during the photolysis. Possible pathways for the formation of the photolysis products from bromo and iodo compounds were discussed in relation to the relative rates of carbon-halogen cleavage and cyclization reactions. Comparison among three classes of halogeno compounds indicated that, with the exception of iodides, the cyclization reaction occurred more readily with type 4 compound than type 3 compounds, while type 5 compounds reacted only with difficulty.
Organic Syntheses by Means of Noble Metal Compounds. XXXVIII. Cyclohexanone Oxime Complexes of Palladium
Authors: Imamura Sinzo , Kajimoto Tsunesuke , Kitano Yukishige , Tsuji Jiro
Published: July 2006

Ligand exchange reactions of palladium complexes having π-allyl and acetylacetonate as ligands with cyclohexanone oxime were carried out and the formation of several new oxime complexes was reported.
The Structure and the Stereochemistry of Solidagonic Acid
Authors: Kusumoto Shoichi , Okazaki Tomomi , Ohsuka Akio , Kotake Munio
Published: July 2006

A new bitter principle, solidagonic acid C22H34O4, was isolated from the root of Solidago altissima L. It is a bicyclic diterpene carboxylic acid, having an acetoxyl group and two double bonds, and was formulated as II on the basis of chemical and spectroscopic studies. The other constituents of the root, kolavenic acid (XXIV) and kolavenol (XXVIII) were also isolated, and they were chemically correlated to II. The absolute configurations of II, XXIV and XXVIII were established by application of the octant rule on the ORD curves for some ketonic compounds derived from them.
Chemiluminescent Reaction between Polyphenols and Ozone in Acetic Acid
Authors: Iwaki Ryôjirô , Kamiya Isao
Published: July 2006

The chemiluminescence of polyphenols with ozone in acetic acid was investigated in the presence and in the absence of rhodamine B. The emission intensity in the presence of rhodamine B (IM) was about 100–500 times as large as that in the absence of the dye (IP). From the measurement of the emission intensity vs. the reaction time, it was found that the time required to attain the peak intensity of IM is almost equal to that required to attain the peak of IP at equal concentration of polyphenol. A similarity was found in the spectral distributions of IM and the fluorescence emission of rhodamine B determined under comparable conditions. Rhodamine B was scarcely decomposed for the production of the enhanced emission; this lent support to the conclusion that the enhancement effect of rhodamine B is due to an energy-transfer from an excited species produced by the oxidation of polyphenols to the dye. Determining the changes in the absorption spectra during the luminescent reaction, we also found that the emission results not from the decomposition of polyphenols but from the decomposition of an intermediate compound. On the basis of these results, a reaction scheme was proposed. If the increment of the total light emitted by the enhancement effect, (Δ), is defined as:

Δ = (Total light emitted in the polyphenol+rhodamine B system)−(Total light emitted in polyphenol alone)−(Total light emitted in rhodamine B alone),

the scheme gave the following equation:

Δ=A[R]0ln(1+[P]0⁄A[R]0) (1)

where [R]0 and [P]0 are the initial concentrations of rhodamine B and polyphenols respectively. A is the parameter, depending upon the experimental conditions. The values of Δ calculated from Eq. (1) were in fairly good agreement with the measured values.
Extraction of Hydrochloric Acid by Tri-n-octylamine in Benzene
Authors: Kojima Takashi , Fukutomi Hiroshi , Kakihana Hidetake
Published: July 2006

The equilibria involved in the extraction of HCl by tri-n-octylamine (TOA) in benzene have been investigated as a function of the HC1 and TOA concentrations. Two distinctly different extractions were observed for two different acidity ranges. From the extraction in the low acidity range (<0.001 m HCl), it has been found that two complexes of TOA·HCl and (TOA·HCl)2are formed in the organic phase and that the equilibrium constants for the two reactions,

TOA(org)+H+(aq)+Cl−(aq)=TOA·HCl(org)

and

2TOA(org)+2H+(aq)+2Cl−(aq)=(TOA·HCl)2(org),

are K11=(1.51±0.02)×104 and K22=(2.92±0.07)×109 respectively. For higher concentrations of HCl>3 m, it seems probable that two major complexes of (TOA·HCl)2HCl and (TOA·HCl)3-(HCl)2 besides the monomer and the dimer, and three minor complexes of (TOA·HCl)2(HCl)2, (TOA·HCl)3HCl, and (TOA·HCl)3(HCl)3 are formed in the organic phase.
Infrared Spectra of Partially Deuterated Acetamide
Authors: Uno Toyozo , Machida Katsunosuke , Saito Yutaka
Published: July 2006

The infrared spectra of orthorhombic crystals of CH3CONH2, CD3CONH2, and their N-deuterated and partially N-deuterated samples have been recorded in the region between 4000 and 400 cm−1. The bands due to the trans- and cis-NHD species have been assigned by comparing the spectra of various samples containing the NH2, ND2 and NHD species in different proportions. In the spectra of the 50% N-deuterated samples, the absorption bands near 1530 and 1360 cm−1have been assigned to the amide II and III modes, respectively, of the trans-NHD species characteristic of the trans conformation of the -CONH- group, and those near 1480 and 1400 cm−1to the NH in-plane deformation and the CN stretching modes, respectively, of the cis-NHD species. These assignments were confirmed by the normal coordinates analysis of eight isotopic species of acetamide based on the Urey-Bradley force field.
Some Experiments on the Triplet State Mechanism of the Spectral Sensitization of Poly(vinyl cinnamate) and Its Application for Searching New Sensitizers
Authors: Tsuda Minoru
Published: July 2006

The spectral sensitization of poly (vinyl cinnamate) is considered to occur by the triplet energy transfer from sensitizer to the cinnamoyl group of the polymer. The triplet state mechanism is useful for finding new sensitizers. Some new sensitizer were found on the basis of the theory, and the results may verify the mechanism.