Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 45 , Issue 9
Showing 1-50 articles out of 82 articles from the selected issue
  • Nobuko Enomoto, Michio Kondo
    1972 Volume 45 Issue 9 Pages 2665-2668
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The NMR spectra of 2-formylaminopyridine and 2-formylamino-γ-picoline have been recorded under various conditions. At low temperatures, these compounds were found to exist in two forms. In these two forms, the chemical shifts of the ring proton-3 differ much from each other because of the difference in the orientation of the formylamino group, which has a large magnetic anisotropy. The difference in the chemical shifts of the formyl protons in the two forms are too large to be explained by the anisotropic shielding effect of the pyridine-ring currents. At higher temperatures, the signal coalescence of these protons in two forms have been observed. The molecular structures of these compounds have been concluded to be planar.
  • Takayuki Sano, Nobuhide Tatsumoto, Toshio Niwa, Tatsuya Yasunaga
    1972 Volume 45 Issue 9 Pages 2669-2673
    Published: 1972
    Released: March 27, 2006
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    The ultrasonic absorptions in n-butyric, isobutyric, n-valeric, isovaleric, and n-caproic acids have been measured in the frequency range from 2.5 to 95 MHz in order to study the relationship between the ultrasonic absorption and the chemical structure of the alkyl group in carboxylic acids. The relaxation absorptions were observed for all the acids with relaxation frequencies in the range of 1.6–8.7 MHz. The kinetic parameters have been calculated on the basis of an assumption that the absorptions are associated with the breakage of one of the two hydrogen bonds in the dimer, as in the case of propionic acid. The values of the heat of reaction, ΔH, were calculated to be 4.7–6.4 kcal per mole of dimer. By an application of the results to Taft’s equation, logK*σ*+sEs, it is deduced that the change in the ΔH in a series of monocarboxylic acids is due to variations in the inductive effect of each alkyl group. However, the change in the heat of activation, ΔH, can not be explained in terms of the inductive effect.
  • Takayuki Sano, Nobuhide Tatsumoto, Yukio Mende, Tatsuya Yasunaga
    1972 Volume 45 Issue 9 Pages 2673-2677
    Published: 1972
    Released: March 27, 2006
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    The ultrasonic absorptions in several halogeno carboxylic acids, such as monochloroacetic, dichloroacetic, trichloroacetic, trifluoroacetic, α-chloropropionic, and β-chloropropionic acids, have been measured in the frequency range from 2.5 to 95 MHz. Excess absorptions were observed in all the acids. The kinetic and the thermodynamic parameters based on the equilibrium between the open dimer and the cyclic dimer were calculated. An application of Taft’s equation, logK*σ*+sEs, to the results suggests that neither the equilibrium constant nor the rate constant depends on the polarity effect of the alkyl group, but depends mainly on the steric effect, and that the reaction is controlled not only by the enthalpy change, but also by the entropy change.
  • Yoshihiro Sensui
    1972 Volume 45 Issue 9 Pages 2677-2683
    Published: 1972
    Released: March 27, 2006
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    The self-diffusion of chloride ions in the bulk of nickel dichloride crystallites was studied in the temperature range of 180–340°C in a carefully-evacuated vacuum system; the isotopic exchange reaction between gaseous chlorine and the crystallites was also studied. The activation energy for the migration of chloride ions was determined to be 1.01 eV (=23.3 kcal/mol). The exchange reaction proceeded with activation energies of 3.6 and 9 kcal/mol for the active and the less-active part of the surface first layer, 13 and 16 kcal/mol for the active and the less-active one of the second layer, and 21 kcal/mol for the third layer. (These activation energies converge to the value of the self-diffusion in the bulk.) The Θ-rule nearly holds good in the present case.
  • Yasuhiko Shirota, Kiyoshi Kawai, Naoto Yamamoto, Kazuhiro Tada, Tadama ...
    1972 Volume 45 Issue 9 Pages 2683-2687
    Published: 1972
    Released: March 27, 2006
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    Photochemical formation of transient N-vinylcarbazole cation and chloranil anion-radicals has been demonstrated by means of flash spectroscopy for the N-vinylcarbazole–chloranil–solvent systems. Identification and decay of the species formed by flash illumination are described.
  • Hitoshi Kanno
    1972 Volume 45 Issue 9 Pages 2687-2692
    Published: 1972
    Released: March 27, 2006
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    As an improvement of the significant structure theory, a new partition function of monatomic liquid was derived:
    Zl(T, Vl)=\left{\overset3Nv\underseti=1Π\left[2sinh\left(\frachνi2kT\ ight)\ ight]−1\ ight}\left{\left(\frac2πmkTh2\ ight)3⁄2\fraceVfNt\ ight}Ntexp\left{\fracΦl(Vl)kT\ ight}
    where 3Nv and 3Nt, (Nv+Nt=N; Avogadro number), are the numbers of freedom in vibrational and translational motions, respectively, vi the i-th normal vibration in the vibrational motion, m the mass of molecule, Vf the free volume of liquid, and Φl(Vl) the configurational potential energy of liquid. Melting of argon at high pressures is successfully interpreted by means of the partition function.
  • Hitoshi Kanno
    1972 Volume 45 Issue 9 Pages 2692-2694
    Published: 1972
    Released: March 27, 2006
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    A partition function of liquid recently proposed by the present author has been applied to the change of the electrical conductivity of metal at melting point. The relation between σs⁄σl and θD⁄θl is more successfully interpreted by this partition function than that used by Mott.
  • Seizo Misumi, Toshiyuki Isobe, Shinkichi Kimoto
    1972 Volume 45 Issue 9 Pages 2695-2697
    Published: 1972
    Released: March 27, 2006
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    Copper(II) complexes with some natural amino acids were prepared, and their powder ESR spectra were measured. The pattern types of the ESR spectra of these Cu(II) complexes with amino acids were classified into four types, and by the pattern type, the cis- or trans-isomer was estimated.
  • Yoshikiyo Moroi, Kinshi Motomura, Ryohei Matuura
    1972 Volume 45 Issue 9 Pages 2697-2702
    Published: 1972
    Released: March 27, 2006
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    Molecular interaction between dodecyl alcohol and dodecyl sulfate of divalent metal cations such as Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Co2+, Ni2+, and Cu2+ was studied by measurement of heat of complex formation, differential thermal analysis and infrared spectroscopy. It was found that magnesium, manganese, cobalt, nickel, and copper dodecyl sulfates formed two or three kinds of complexes with dodecyl alcohol, differing in composition depending on temperature. On the other hand, no evidence of complex formation could be found by these experimental techniques for calcium, strontium and barium dodecyl sulfates, all of which are very small in solubility into water. For the former class of metal dodecyl sulfates the composition of complex was 3.5–4.0 in molar ratio of alcohol to sulfate at temperature below the melting point of alcohol, while it was 5.0–6.0 at temperature above it. The heat of complex formation above the melting point of alcohol was −40–−44 kcal/mol-sulfate. Two or three characteristic absorption bands could be found over the range 3200–3500 cm−1, suggesting that the complex formation is due to hydrogen bonding between two components.
  • Hiroshi Yamamura, Ryôiti Kiriyama
    1972 Volume 45 Issue 9 Pages 2702-2708
    Published: 1972
    Released: March 27, 2006
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    The Mössbauer effect was studied for the solid-solution Sr1−xLaFeO2.5+x⁄2 system, prepared by firing in a vacuum. The intensity of the characteristic six absorption lines of the tetrahedral-iron site in the brownmilleritetype phase (0.0≤x≤0.02) was weakened with an increase in the La content because of an increasing incorporation of oxygen, while the Mössbauer parameters remained constant. SrFeO2.5 with a brownmillerite-type structure, completely changed into a cubic perovskite-type structure at the composition with x=0.30; however, the original absorption peaks for the tetrahedral-iron site still exist even if the intensity is considerably decreased. Moreover, new peaks came out, with Mössbauer parameters different from those for the octahedral- or the tetrahedraliron sites. On the basis of the values of their Mössbauer parameters, the origin of the new peak can be assigned to the presence of a five-coordinated iron site surrounded by a trigonal bipyramidal polyhedron of oxygen rather than a square pyramidal one. The three kinds of iron site lead to a single octahedral one when most of Sr is replaced with La (x≥0.50). The oxygen-deficient, perovskite-type phase with a cubic symmetry may be stabilized by the presence of the mixed-coordination scheme of Fe3+, i.e., the octahedral, trigonal bipyramidal, and tetrahedral sites.
  • F. Leh, K. M. Chan
    1972 Volume 45 Issue 9 Pages 2709-2711
    Published: 1972
    Released: March 27, 2006
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    The study of the ESR spectra parameters of bis(trifluoroacetylacetonato)copper(II)-phosphorus complexes in chloroform solution at room temperature and 77°C shows that the g and hyperfine tensors change with the formation of 1 : 1 adduct. Such effect is more clearly exhibited by the parameters A|| and g||. A correlation is obtained between the spectral data and the basicity of the tertiary phosphine ligands.
  • Arabinda Ray, D. N. Sathyanarayana
    1972 Volume 45 Issue 9 Pages 2712-2715
    Published: 1972
    Released: March 27, 2006
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    Infrared spectrum of N,N-dimethylthioacetamide (DMTA) has been recorded in the region 250–4000 cm−1. Normal vibration analysis has been carried out employing Urey-Bradley force field and assignments are made and supported by comparison with related molecules. The complexes of DMTA with cobalt (II), copper (I), and mercury(II) chlorides have been prepared and their infrared spectra recorded. The frequency shifts in metal complexes are in accord with the assignments of C=S and C–N frequencies.
  • Fumio Hirata, Kiyoshi Arakawa
    1972 Volume 45 Issue 9 Pages 2715-2719
    Published: 1972
    Released: March 27, 2006
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    Ultrasonic velocity of aqueous solutions of tetraalkylammonium chlorides was measured over wide ranges of concentration and temperature in order to study the nature of solute-solvent interactions. Adiabatic compressibility was obtained from the data of sound velocity and density. The results were discussed in terms of the influence of solutes upon the structure of liquid water. It has been shown that Me4N+ is a structure breaker, while n-Bu4N+ forms a structure or “icebergs” around the cations evidently, and that the ability of iceberg formation begins at n-Pr4N+. It was concluded that the icebergs have a more rigid structure than the ice-like structure in bulk water.
  • Tomoyasu Nakamura, Yasumasa J. I’Haya
    1972 Volume 45 Issue 9 Pages 2720-2723
    Published: 1972
    Released: March 27, 2006
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    The absorption, circular dichroism (CD) and optical rotatory dispersion spectra of DNA–toluidine blue O complexes were observed over the visible absorption spectral region. Effect of temperature on CD was examined at the temperatures 6–86°C. For the complex of a low DNA phosphate to dye ratio, the Krönig-Kramers transform was carried out and one positive and four successive negative CD bands were resolved. It is concluded that the shorter wavelength CD bands, one positive and one negative, are due to an exciton splitting of the dye dimers and that the rest may be induced by an asymmetric environment of the DNA deoxyribose residue.
  • Takuzo Funabiki, Mitsuo Matsumoto, Kimio Tarama
    1972 Volume 45 Issue 9 Pages 2723-2730
    Published: 1972
    Released: March 27, 2006
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    Hydrogenations of 1,3-Butadiene and isoprene catalyzed by pentacyanocobaltate(II) have been studied by the measurements of infrared and nuclear magnetic resonance spectra on the reaction solutions and by following the time-courses of the reactions. Infrared spectroscopy has revealed: (1) The aging reaction is promoted by CN- ion and it hardly occurs at a low CN/Co ratio. (2) In the hydrogenation of butadiene the formation of a σ-but-2-enyl complex at a high CN/Co ratio is very rapid, but that of a syn-π-(1-methylallyl) complex at a low CN/Co ratio is generally slow. The rate of the formation of these complexes is affected by the relative concentration of butadiene to Co(CN)5H3−. (3) In the hydrogenation of isoprene a σ-3-methylbut-2-enyl complex is formed regardless of the CN/Co ratio. Nuclear magnetic resonance spectroscopy has confirmed the structures of these complexes and it also showed that the σ-but-2-enyl complex consists of simliar amounts of the cis- and trans-isomers. The reactions are explained by the mechanisms, in which intermediate complexes in the formation of alk-1-enes and alk-2-enes are the cis- and trans σ-but-2-enyl and the syn-π- (1-methylallyl) complexes in the case of butadiene, and the σ-2- and -3-methylbut-2-enyl and the π-(1,2-dimethylallyl) complexes in the case of isoprene. It is described that the reactivity and the selectivity in the hydrogenation of conjugated dienes are strongly controlled by the steric factor in the transition state.
  • Mikio Hoshino, Masao Koizumi
    1972 Volume 45 Issue 9 Pages 2731-2736
    Published: 1972
    Released: March 27, 2006
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    The change in the absorption spectrum of p-hydroxybenzophenone (HOBP) and relative quantum yields Φrel for the photoreduction of HOBP have been studied in mixed solvents consisting of cyclohexane and four kinds of alcohol. The change in absorption spectrum occurs in two steps with methanol, ethanol, and 2-propanol, suggesting the following equilibria, HOBP+S\leftrightharpoonsA, and A+S\leftrightharpoonsB (S, alcohol molecule). Φrel changes in two steps with methanol and ethanol and in one step with 2-propanol and amyl alcohol roughly in line with the spectral change. The changes in Φrel have been interpreted to be due to the deprotonation of HOBP. Φrel=1⁄(1+K[S]n) holds for them with n=5.5 for 2-propanol and n=1 for other alcohols. A linear relation holds between 1⁄(n−1)logK and Hammett’s constant of alkyl group of alcohols, suggesting that the deprotonation tendency depends upon the specific interaction between alcohol molecules. The reactivity of A-species is considered to depend largely on the dielectric nature of the solvent.
  • Susumu Kohda, Kimio Ohno, Hiroshi Taketa
    1972 Volume 45 Issue 9 Pages 2737-2738
    Published: 1972
    Released: March 27, 2006
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    The first singlet and triplet excited states of Li2 are studied by the MO and VB methods. As basis, only 1s and 2s AO’s are used. In the MO description, the antibonding MO is more diffuse than the bonding MO and the difference is bigger in 1Σu+ than 3Σu+ In the VB description, splitting of the 2s orbital in the purely ionic (1Σu+) and covalent (3Σu+) wave functions does not lead to any energy lowering. An interpretation of this result is suggested. The calculated singlet-triplet separation is compared with previous calculations.
  • Il-Hyun Park
    1972 Volume 45 Issue 9 Pages 2739-2744
    Published: 1972
    Released: March 27, 2006
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    The decomposition of ammonium paramolybdate (APM) has been investigated by using a quartz spring balance in various ambient pressures. APM is decomposed in four or five stages, including a dehydration procedure, depending on the ambient pressures. However, these results do not agree with those of previous reports. This discrepancy may be attributed to the use of a sensitive quartz spring balance, a small amount of a sample, the application of a slow heating rate, or the utilization of DTG curves in the present study. The control of the ambient pressure was effective in investigating the thermogravimetric change in detail, especially in confirming the dehydration reaction. It is also concluded clearly that, in the course of the decomposition process, there is a final decomposition stage which has never been reported. The kinetics of the thermal decomposition was studied. The activation energies of the decomposition of APM under 760 Torr are 38.6, 194.8, 81.9, and 151.2 kcal·mol−1 respectively for the first to the fourth stages.
  • Il-Hyun Park
    1972 Volume 45 Issue 9 Pages 2745-2748
    Published: 1972
    Released: March 27, 2006
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    Gases evolved by the decomposition of ammonium paramolybdate tetrahydrate have been analyzed by means of an omegatron mass spectrometer. Only water molecules of the hydration were eliminated during the first stage of decomposition, and the final stage was not the elimination reaction of ammonia but the oxidation reaction of ammonia by Mo(VI) oxide. Between 150 and 250°C, ammonia and water were evolved in a mole ratio of roughly 2:1, corresponding to the elimination of (NH4)2O. However, the range is not clear because of the overlap of the elimination of water at the lower limit and that of nitrogen at the upper limit. At higher temperatures, a small amount of NO was observed.
  • Il-Hyun Park
    1972 Volume 45 Issue 9 Pages 2749-2752
    Published: 1972
    Released: March 27, 2006
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    Thermal decomposition of ammonium chromate (AC) and ammonium dichromate (ADC) has been studied by means of TG, DTA, and DTG. It showed four steps in thermal decomposition of AC and three steps in that of ADC. Decomposition product in each step of the thermal decomposition was examined by X-ray diffraction method. From the results of both thermogravimetric analysis and X-ray study, it was concluded that the first decomposition product of AC was ADC, the second was CrO3 and the final product was Cr2O3. The third product gave the X-ray patterns of the mixture of Cr2O3 and CrO3, and the mole ratio of O/Cr in the temperature range for the existence of the product (300–390°C) was 2.1–2.0. The kinetics in the second decomposition step for AC and in the first decomposition step for ADC were studied, giving the values of the energy of activation of 24.2 and 22.4 kcal/mol, respectively.
  • Il-Hyun Park
    1972 Volume 45 Issue 9 Pages 2753-2756
    Published: 1972
    Released: March 27, 2006
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    Constituents of gases evolved in thermal decomposition of ammonium chromate and ammonium dichromate have been studied by an omegatron mass spectrometer. From the data of gas analysis, the following conclusions have been obtained. The decomposition of the first step started with proton transfer mechanism and the ratio of NH3 to H2O was not 2 : 1 at the beginning. The second step corresponded to the formation of N2, N2O, and H2O through oxidation of NH3 by the chromate anion. The decomposition in the third step was accompanied by the evolution of oxygen molecules. The production of CrO3 was confirmed by comparing the dissociation pressure of CrO3 produced in AC decomposition with that of pure CrO3. The decomposition in the last step corresponded to the process from CrO2 to Cr2O3, with the evolution of O2, CO2, and CO.
  • Mutsuo Kodama, Takami Sato, Sadatsugu Karasawa
    1972 Volume 45 Issue 9 Pages 2757-2760
    Published: 1972
    Released: March 27, 2006
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    The substitution reactions of calmagite with nickel(II)-glutamate, -aspartate, -iminodiacetate, -nitrilotriacetate, and -diethylenetriamine complexes, and that with the cobalt(II)-nitrilotriacetate complex, were studied by employing the stopped-flow technique. In the calmagite reactions with the nickel(II)-glutamate, -aspartate, and -iminodiacetate complexes, the reaction products were found to be mixed-ligand complexes involving calmagite and glutamate, aspartate, or iminodiacetate anions. In these reactions, the 1 : 2 ratio complex dissociates rapidly into the 1 : 1 ratio complex first; then, the 1 : 1 ratio complex reacts slowly with the calmagite anion to form a mixedligand complex. From a comparison of the observed rate constant with that estimated on the basis of the proposed reaction intermediate, it was concluded that the latter step proceeds through the outer-sphere complex between the calmagite anion and a 1 : 1 ratio complex, and that the water-loss from the 1 : 1 ratio complex is the slowest step. In the cases of the reactions of calmagite with nickel (II)-nitrilotraicetate and -diethylenetriamine complexes, and that with the cobalt (II)-nitrilotriacetate complex, all the reaction invariably gave a metal (II)calmagite complex with a 1 : 1 composition, MD-. These reactions were found to proceed through the completely-deprotonated and divalent calmagite anions.
  • Mutsuo Kodama, Michinori Hashimoto, Toshiyuki Watanabe
    1972 Volume 45 Issue 9 Pages 2761-2764
    Published: 1972
    Released: March 27, 2006
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    The kinetics of the substitution reactions of EDTA and EDTA-OH with nickel(II)-EDMA and -Dien complexes were studied using the polarographic technique. The substitution reactions of EDTA and EDTA-OH with the nickel(II)-EDMA complex were found to have a common reaction mechanism. They were first-order with respect to EDTA or EDTA-OH, and also first-order with respect to the nickel (II)-EDMA complex with a 1: 1 composition; their reaction mechanism could be formulated as:
    (Remark: Graphics omitted.)
    The substitution reactions of EDTA and EDTA-OH with the nickel(II)-Dien complex were also studied under experimental conditions where the reaction could be treated as a pseudo-first-order reaction. The reactions were first-order with respect to the concentration of EDTA or EDTA-OH. However, their reaction rate were independent of the concentrations of the nickel(II)-Dien complex and of uncomplexed Dien. This fact was ascribed to the formation of a stable outer-sphere complex between the nickel(II)-Dien complex with a 1: 2 ratio and the EDTA or EDTA-OH anion, through which the substitution reaction proceeds.
  • Yoshinobu Wakamatsu, Makoto Otomo
    1972 Volume 45 Issue 9 Pages 2764-2767
    Published: 1972
    Released: March 27, 2006
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    A method has been described for the spectrophotometric determination of titanium(IV), which is based on the extraction of the titanium (IV)-Tiron chelate into n-butanol in the presence of 1,3-diphenylguanidinium salt. The extracted species containing titanium, Tiron, and diphenylguanidine in a molar ratio 1:2:4, has an absorption maximum at about 385 nm. The maximum extraction is obtained when the pH of the initial aqueous phase is controlled to about 3.0 to 4.0. Beer’s law is obeyed up to 25 μg titanium per 10 ml of n-butanol. The molar absorptivity of the extracted species is 1.4×10−4 at 385 nm. Molybdenum (VI) and chelating agents interfere with the determination of titanium.
  • Isao Yoshida, Hiroshi Kobayashi, Keihei Ueno
    1972 Volume 45 Issue 9 Pages 2768-2773
    Published: 1972
    Released: March 27, 2006
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    Based on the spectral studies in visible, ultraviolet as well as in infrared regions, the dimeric octahedral structure was proposed for bis(heptane-3,5-dionato)cobalt(II) monohydrate, [Co(DNPM)2·H2O], bis(nonane-4,6-dionato)cobalt(II) monohydrate, [Co(DNBM)2·H2O], bis(2,8-dimethylnonane-4,6-dionato)cobalt(II) monomethanolate, [Co(DIVM)2·CH3OH], and bis(tridecane-6,8-dionato)cobalt(II) monomethanolate, [Co(DNCM)2·CH3OH]. The dimeric chelates of the type [CoL2·B], where B represented water or methanol, were stable in solid state, however, they freed the base B to form a tetrahedral monomeric complex in non-donating solvents. A red-pink solution of the cobalt(II) chelates were oxidized spontaneously in the period of a few days to give a green solution of cobalt(III) chelates of type [CoL3]. Cobalt(III) chelates of 2,6-dimethylheptane-3,5-dione (DIBM) and 2,2,6,6-tetramethylheptane-3,5-dione (DPVM) in addition to the above ligands were synthesized and their spectra were discussed in comparison with the corresponding cobalt(II) chelates.
  • Toshio Matsuzaki, Morio Setaka, V. V. Gromov, Takao Kwan
    1972 Volume 45 Issue 9 Pages 2773-2775
    Published: 1972
    Released: March 27, 2006
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    Natural strontium sulfate crystals were found to show complex ESR spectra without any special irradiation. The spectra were classified into three groups, A, B, and C; the thermal and photochemical behavior of each group was distinguished from that of the others. It was proposed that Group B originates from SO3- radicals, and Groups A and C were tentatively interpreted as due to lattice defects (F-center and V-center).
  • Tadashi Nozaki, Yoshihiro Makide, Yoshifumi Yatsurugi, Yoshiyuki Endo, ...
    1972 Volume 45 Issue 9 Pages 2776-2778
    Published: 1972
    Released: March 27, 2006
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    The behavior of carbon in high-purity silicon in the dissolution and fusion of the matrix was studied by the 11C-tracer technique. Silicon samples containing 11C, either atomistically dispersed or mainly coagulated as SiC, were prepared. In alkali dissolution, no loss of 11C was observed, and carbon originally dispersed in silicon was found to behave in a similar way to colloidal carbon under subsequent treatments. By HF–HNO3–KIO4 dissolution and succeeding KMnO4 treatment, the dispersed carbon was oxidized almost quantitatively but the SiC coagulates were not completely decomposed. In alkali fusion a part of 11C was lost. By fusion with Pb3O4-B2O3, carbon in both states was converted into CO2. The results suggest a possible application of activation analysis to the measurement of the coagulation degree of carbon in high-purity silicon.
  • Kozaburo Ueda, Toshikazu Ibata, Matsuji Takebayashi
    1972 Volume 45 Issue 9 Pages 2779-2782
    Published: 1972
    Released: March 27, 2006
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    The copper chelate-catalyzed decomposition of o-methoxycarbonyl-α-diazoacetophenone was carried out in benzene. The reaction gave a dimer of a carbonyl ylide intermediate. The intermediate was trapped with dipolarophiles such as trans-dibenzoylethylene, ethyl fumarate, isoprene and dimethyl acetylenedicarboxylate, yielding 1,3-dipolar adducts in a stereospecific and stereoselective manner. Similar results were obtained in the catalytic decomposition of o-(n-butoxycarbonyl)-α-diazoacetophenone. The configuration of adducts and the mechanism of the reaction are discussed.
  • Sigeru Torii, Hideo Tanaka, Tsutomu Okamoto
    1972 Volume 45 Issue 9 Pages 2783-2787
    Published: 1972
    Released: March 27, 2006
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    Anodic oxidation of methyl 5-acetyl-2-furoate 4 in methanol leads to ring-opened diesters 8 and 9, and lactone 10 in addition to methyl 5-acetyl-2,5-dimethoxy-2,5-dihydro-2-furoates 7. Formation of 8, 9, and 10 can be rationalized as arising from 7. On the other hand, oxidation of methyl 5-methoxy- and 5-bromo-2-furoates, 5 and 6, also give 9 and 10. The reactions involve initial production of cationic intermediates 13 and 15, which are readily solvolized to give 8, 9, and 10. A mechanism of the formation of the intermediates 13 from 5, 6, and 7 is discussed.
  • Naoto Wada, Katsumi Tokumaru
    1972 Volume 45 Issue 9 Pages 2787-2790
    Published: 1972
    Released: March 27, 2006
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    Thermal decomposition of trans-α-phenylcinnamoyl peroxide and t-butyl trans- and cis-α-phenylperoxycinnamates and photolyses of 1,1 -diphenyl-2-iodoethylene and 1,1,2-triphenyl-2-iodoethylene were carried out in benzene under oxygen and their products were determined. The intermediate vinylic radicals, on reaction with oxygen, undergo oxidative cleavage and dioxygenation of their unsaturated bonds. As an example, 1,2-diphenylvinyl radicals give benzaldehyde together with benzoin.
  • Michio Kondo
    1972 Volume 45 Issue 9 Pages 2790-2793
    Published: 1972
    Released: March 27, 2006
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    The nuclear magnetic resonance spectra of six o-disubstituted benzenes containing a carbonyl group have been analyzed. The chemical shifts of the proton-6, adjacent to the carbonyl group, show a solvent dependence, indicating changes in the intramolecular interactions between the two ortho substituents.
  • Tatsuo Numata, Shigeru Oae
    1972 Volume 45 Issue 9 Pages 2794-2796
    Published: 1972
    Released: March 27, 2006
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    When optically active bromomethyl p-toly sulfoxide was treated with sodium methylmercaptide or sodium ethoxide, optically active α-substituted methyl p-toly sulfoxides were obtained in good yields. By contrast, reaction with secondary amines produced achiral p-toluenesulfenamides, methylenediamines, and amine hydrobromides in nearly quantitative yields. The reaction with an amine is presumed to proceed through the initial nucleophilic substitution at α-carbon of the sulfoxide to form aminomethyl p-toly sulfoxide, followed by rearrangement to the corresponding sulfenate, and subsequent attack of the amine at the sulfur atom of the sulfenate to form the final product. Meanwhile, a facile interconversion of alkoxymethyl p-toly sulfoxide and corresponding sulfenate was also observed.
  • Tamejiro Hiyama, Shinsaku Fujita, Hitosi Nozaki
    1972 Volume 45 Issue 9 Pages 2797-2801
    Published: 1972
    Released: March 27, 2006
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    The benzene-sensitized photoreaction of 4,5-dipropyl- (IIa) and 4,5-tetramethylene-1,3-dioxolen-2-one (lIb) in isopropyl alcohol gives two reduction products, cis- (V) and trans-4,5-disubstituted 1,3-dioxolan-2-one (VI). The irradiation of octa- (IId) and decamethylene-bridged vinylene carbonate (IIe) results in transannular hydrogen atom transfer from a methylene group to the olefinic bond and a subsequent recombination affording three tricyclic products, IX, X, and XIX. An examination of the stereochemistry of the products has indicated the participation of a diradical intermediate.
  • Kunio Okamoto, Tomomi Kinoshita
    1972 Volume 45 Issue 9 Pages 2802-2809
    Published: 1972
    Released: March 27, 2006
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    As tertiary and secondary systems with optical activity, tetrahydrolinalyl (methylethylisohexylcarbinyl) chloride or p-nitrobenzoate and 2-octyl p-toluenesulfonate have been selected, and their titrimetric and polarimetric rate constants (kt and kp) for SN1 phenolyses have been measured in the presence of triethylamine (or sodium phenoxide) in 50 wt% phenol–benzene. At higher amine (or phenoxide) concentrations, the kt and kp coincide with each other for tetrahydrolinalyl chloride (at 25.0°C) or p-nitrobenzoate (at 100.0°C), and also for 2-octyl tosylate (at 75.0°C), exhibiting the typical features of the nN1 solvolysis rate constant. In the absence of the amine (or sodium phenoxide), the kt diminishes to show a gap between the kp and the kt, indicating the occurrence of an ion-pair return in the phenolysis for both systems. Under the same reaction conditions as those of the rate measurement, tetrahydrolinalyl chloride and p-nitrobenzoate yield the phenyl ether, with a predominant racemization accompanied by some net inversion of the configuration, whereas 2-octyl tosylate gives 2-octyl phenyl ether, o-, and p-2-octylphenols, with a net inversion of the configuration accompanied by a slight racemization. These steric results indicate that phenol can be considered as a typical solvolytic solvent. The product distributions have been assessed for the reactions of 2-octyl chloride (200°C) and of tetrahydrolinalyl chloride (25.0°C) with the molecule of phenol under the SN1 phenolysis conditions, by extrapolating the product composition curves to a zero concentration of the phenoxide. For both systems, the phenol molecule is predominantly O-alkylated (74 and 99% respectively), accompanied by minor amounts of C-alkylation. In contrast to the phenol reaction, the phenoxide ion undergoes more C-alkylation (42 and 50% respectively).
  • Makoto Ichii
    1972 Volume 45 Issue 9 Pages 2810-2813
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The rates of AlCl3·CH3NO2-catalyzed phenethylations of benzene (50°C) or toluene (25°C) with 2-arylethyl (ring-substituted phenethyl) chlorides were measured in homogeneous nitromethane solutions. The reactions are first-order in the aromatic component, first-order in the phenethyl chloride, and second-order in aluminum chloride. Substituent effects in the phenethyl chlorides give linear relationships with Hammett’s σ constants. A displacement mechanism involving a nucleophilic attack by the aromatic substrate on the phenethyl chloride-catalyst system is proposed for the reactions. Competitive phenethylations of benzene and toluene were also carried out at 50°C. Both the isomer distribution and the relative reactivity of toluene to benzene are affected by the ring-substituents, the effects of which are correlated closer with the substrate selectivity. These results suggest that the transition state in the rate-determining step for the phenethylations is in nature an (oriented) π complex rather than a σ complex.
  • Ryuki Hisada, Hiroshi Minato, Michio Kobayashi
    1972 Volume 45 Issue 9 Pages 2814-2816
    Published: 1972
    Released: March 27, 2006
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    Benzoyl p-toluenesulfonyl peroxide (BTP) with 18O-labeled carbonyl oxygen and 18O-labeled sulfonyl oxygen were prepared. They were decomposed in benzene in the presence or in the absence of trifluoroacetic acid,and the phenyl p-toluenesulfonyl carbonate (PTC)-18O produced was isolated and analyzed. It was found that the carbonyl oxygen-18 of BTP was retained as the carbonyl oxygen of PTC, whereas the sulfonyl oxygen-18 of BTP was equilibrated with the peroxidic oxygen. The mechanism of the carboxy-inversion was discussed.
  • Michio Kobayashi, Hiroshi Minato, Yoshiko Miyaji, Takuji Yoshioka, Koj ...
    1972 Volume 45 Issue 9 Pages 2817-2821
    Published: 1972
    Released: March 27, 2006
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    Methyl, ethyl, n-butyl, n-octyl, benzyl, and allyl p-toluenesulfinates were photolyzed in n-hexane or without solvent. The products analyses indicate that the photolyses of these esters involve the fission of ArSO–OR bond, producing a sulfinyl radical and an alkoxy radical. In the case of the allyl ester, isomerization to the corresponding sulfone took place to some extent. When optically active l-menthyl l-p toluenesulfinate was irradiated, its optical activity decreased fairly quickly while very little photolysis was observed. This photo-racemization was ascribed to the reversible formation of sulfinyl radical and menthyloxy radical. When di-n-butyl sulfite was photolyzed, the products found were explained by assuming the initial formation of n-butoxysulfinyl radical and n-butoxy radical. When n-butyl chlorosulfite was photolyzed, the products found indicate the initial fission of the S–Cl bond instead of the S–O bond.
  • Haruki Tsuruta, Katsuhiko Kurabayashi, Toshio Mukai
    1972 Volume 45 Issue 9 Pages 2822-2828
    Published: 1972
    Released: March 27, 2006
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    The thermal decomposition of sodium salt of (2,4,6-cycloheptatrien-1-yl)acetaldehydes tosylhydrazone (4, 6, and 8) afforded 9-substituted bicyclo[4.2.1]nona-2,4,7-triene (9, 11, and 14) and 9-substituted barbaralane (10, 12, and 15). In the case of 8, products containing two nitrogen atoms (17 and 18) were isolated. The structure and the photochemical reaction of 17 provided strong support for the intermediacy of the tetracyclo[4.3.0.02,9.05,7]-nona-3-ene (37) derivative for the formation of the bicyclo[4.2.1]nona-2,4,7-triene derivatives. The difference in energy surface between C9H10 and C10H10 hydrocarbons was discussed.
  • Yasuo Iwanami, Taketsugu Seki
    1972 Volume 45 Issue 9 Pages 2829-2834
    Published: 1972
    Released: March 27, 2006
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    Phenacyl derivatives of two naturally-occurring pteridines and their 4-amino analogues (III and V) have been synthesized for their structural study. Since these compounds are obtained by the condensation of ethyl benzoylpyruvates (II) with tri- or tetraaminopyrimidine (I), a carbon-nitrogen double bond, which is adjacent to the phenyl group of the side chain, may be expected in the ring (Remark: Graphics omitted.). However, their NMR spectra show that the double bonds of all the products are displaced onto the side chain (Remark: Graphics omitted.), the carbonyl of which is hydrogen-bonded with the secondary amino group thereby formed. This form of V makes striking contrast to alkyl isoxanthopterin-6-acetates (X), in which the corresponding double bond remains undisplaced. The intermediate products of V (IV) and V were hydrolyzed with acid or alkali into 6-methyl-isoxanthopterin (VI) and benzoic acids (VII).
  • Takashi Kojima, Yoshiteru Sakata, Soichi Misumi
    1972 Volume 45 Issue 9 Pages 2834-2836
    Published: 1972
    Released: March 27, 2006
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    An annelated[14]annulenedione (V) was prepared by the Castro reaction of cuprous salt of o-iodocinnamoylacetylene (IV) in order to examine the aromatic character of the inner fourteen membered ring. The NMR spectra of V in arsenic trichloride and deuterotrifluoroacetic acid suggest that significant downfield shift of the inner protons HB is due to a paramagnetic ring current arising from polarization of two carbonyl groups in the inner ring, compared with the spectra of a reference compound VI.
  • Makoto Sugihashi, Ryosuke Kawagita, Tetsuo Otsubo, Yoshiteru Sakata, S ...
    1972 Volume 45 Issue 9 Pages 2836-2841
    Published: 1972
    Released: March 27, 2006
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    Several benzo- and/or naphtho-derivatives of triptycene were prepared in a manner of addition reaction of dehydronaphthalene (XIII) or a new type of aryne, dehydroanthraquinone (XVI) generated from 3-aminoanthraquinone-2-carboxylic acid (XV), with a few acenes. The absorption bands in longer wavelength region of their UV spectra and the chemical shift of bridgehead protons in their NMR spectra led to a conclusion that the spectra of those annelated triptycenes are elucidated in terms of a superposition and a sum of magnetic effects of separated component chromophores, respectively, and thereby indicate a negligible existence of the across-space π-electron interactions, if any, among three aromatic nuclei.
  • Hamao Umezawa, Tsutomu Tsuchiya, Ryujiro Muto, Sumio Umezawa
    1972 Volume 45 Issue 9 Pages 2842-2847
    Published: 1972
    Released: March 27, 2006
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    6-O-(3-Amino-3-deoxy-α-D-glucopyranosyl)-2-deoxystreptamine, previously synthesized, was masked with ethoxycarbonyl, isopropylidene, and benzyl groups to give 6-O-(2-O-benzyl-3-deoxy-3-ethoxycarbonylamino-4,6-O-isopropylidene-α-D-glucopyranosyl)-N,N′-diethoxycarbonyl-2-deoxystreptaniine, which was condensed with 6-azido-2,4-di-O-benzyl-6-deoxy-3-O-methyl-α-D-glucopyranosyl chloride by a modified Koenigs-Knorr reaction to give a mixture of α,α- and α,β-diglycoside compounds. Hydrogenation of the azido group and removal of the masking groups gave a mixture of 3′-O-methylkanamycin and its diastereomer. The 3′-O-methylkanamycin was devoid of antibacterial activity.
  • Sumio Umezawa, Yoshio Nishimura, Hirokuni Hineno, Kohei Watanabe, Soic ...
    1972 Volume 45 Issue 9 Pages 2847-2851
    Published: 1972
    Released: March 27, 2006
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    3′-Deoxykanamycin has been totally synthesized from 6-O-(2-O-benzyl-3-deoxy-3-ethoxycarbonylamino-4,6-O-isopropylidene-α-D-glucopyranosyl)-N,N′-diethoxycarbonyl-2-deoxystreptamiine and 6-azido-2,4-di-O-benzyl-3,6-dideoxy-α-Dribo–hexopyranosyl chloride. It has been found that the 3′-deoxykanamycin has strong antibacterial activity not only against common bacteria but also against kanamycin-resistant bacteria.
  • Motonori Ohno, Sadaji Tsukamoto, Satoru Makisumi, Nobuo Izumiya
    1972 Volume 45 Issue 9 Pages 2852-2855
    Published: 1972
    Released: March 27, 2006
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    An improved method has been described for the solid-phase synthesis of tryptophan-containing peptides. Hydrogen chloride in formic acid has been introduced as a reagent for the cleavage of the t-butyloxycarbonyl group owing to the stableness of tryptophan and Ni-formyltryptophan in this system. The effectiveness of the new reagent has been demonstrated in the synthesis of the tryptophan-containing heptapeptide, lysylalanylglycyl-leucylglycyltryptophylleucine.
  • Shigeru Oae, Yoshiyuki Tsuchida, Kenji Tsujihara, Naomichi Furukawa
    1972 Volume 45 Issue 9 Pages 2856-2858
    Published: 1972
    Released: March 27, 2006
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    The reactions of elemental sulfur and diaryl disulfide with the compounds bearing a semipolar S→N linkage were investigated. Elemental sulfur was found to react with N-arenesulfonylsulfilimine and sulfoximine affording the corresponding sulfide and the sulfoxide respectively. Diaryl disulfide also was found to undergo similar reactions with these compounds. In the reaction of diaryl disulfide with N-arenesulfonylsulfilimine, N,N-bis-(arylthio)arenesulfonamide was obtained as a main product besides the corresponding sulfide. The mechanisms of these reactions are discussed.
  • Kaoru Harada, Wung-wai Tso
    1972 Volume 45 Issue 9 Pages 2859-2862
    Published: 1972
    Released: March 27, 2006
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    Optical resolution of DL-aspartic acid by using copper complexes of L-alanine, D-alanine, L-glutamic acid, D-glutamic acid, and L-proline in aqueous solution is described. In this investigation the effects of (1) the concentration of reactants and (2) the ratio of the optically active amino acid to racemic aspartic acid in the reaction mixture were studied.
  • Teruzo Asahara, Manabu Sen\={o}, Shinsaku Shiraishi, Yoshikazu Arita
    1972 Volume 45 Issue 9 Pages 2862-2866
    Published: 1972
    Released: March 27, 2006
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    The polymerization of methyl methacrylate in the presence of sodium tetrapropylenebenzenesulfonate(ABS) in an aqueous system without any ordinary initiators was examined kinetically. The rate of polymerization of methyl methacrylate is dependent on the initial concentrations of methyl methacrylate and ABS, and expressed by the equation:
    Rp∝[ABS]0.37[MMA]0.32
    The apparent activation energy of the polymerization is about 3 kcal/mol. It was confirmed by electron microscopic observation that the number of polymer molecules is in the same order as that of the micelle particles in the polymerization system.
  • Kanji Omura, Akira Nishinaga, Teruo Matsuura
    1972 Volume 45 Issue 9 Pages 2866-2871
    Published: 1972
    Released: March 27, 2006
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    Photooxidation of 4-hydroxy-3,5-diiodophenylpyruvic acid (I) in methanol was found to yield a hydroperoxide (IV). This hydroperoxide reacted anaerobically with 3,5-diiodotyrosine (II) to form thyroxine (III). A photo-product, presumably IV, apparently accelerated the oxidation of I. Methanol, among several organic solvents, was found to be the best solvent for the photooxidation. Similar oxidations with 4-hydroxy-3-iodo-5-methoxyphenylpyruvic acid (V) and 4-hydroxyphenylpyruvic acid (VI) showed that the rate of oxidation decreased in the order I>V>VI. A product of the photooxidation of I, probably the hydroperoxide IV, also acts as an accelerator in the photooxidation of the desiodo analog VI of I.
  • Nobukatsu Katsui, Akira Matsunaga, Kenji Imaizumi, Tadashi Masamune, K ...
    1972 Volume 45 Issue 9 Pages 2871-2877
    Published: 1972
    Released: March 27, 2006
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    The structure and configuration of rishitinol (2), isolated from tuber tissues of white potatoes (Solanum tuberlosum × S. demissum) infected by an incompatible race of Phytophtora infestans, were deduced from spectral and chemical data and confirmed by the synthesis of its recemate. 5,8-Dimethyl-1-tetralone-3-carboxylic acid (13) prepared from 2,5-dimethylbenzyl chloride was esterified, reduced, and then dehydrated to the dihydronaphthalene derivative (20), which was converted into the oxyisopropyl derivative (21). The hydroboration of 21 followed by hydrogen peroxide oxidation afforded a multi-component mixture, from which dl-rishitinol (25=dl-2) was isolated along with isomeric glycols (2224).
  • Otohiko Tsuge, Shuji Kanemasa
    1972 Volume 45 Issue 9 Pages 2877-2882
    Published: 1972
    Released: March 27, 2006
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    Thiobenzoyl isocyanates react with benzylidenanilines, benzylidenalkylamines and dianils to yield the corresponding mono- and bis (4+2) cycloadducts. Benzoyl isocyanates do not react with benzylidenanilines, but they are easily added to benzylidenebenzylamine to give the (4+2) cycloadducts in good yields. Cycloaddition of these isocyanates to anils is dependent upon the basicity of the nitrogen atom of C=N bond. Neither benzoyl isocyanates nor thiobenzoyl isocyanates are added to the C=C bond of cinnamylidenanilines, but they react with the C=N bond to afford the (4+2) cycloadducts.
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