Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 46 , Issue 12
Showing 1-50 articles out of 70 articles from the selected issue
  • Hiroshi Kawabe, Masaya Yanagita
    1973 Volume 46 Issue 12 Pages 3627-3632
    Published: 1973
    Released: March 27, 2006
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    The amination of chloromethylated polystyrene (CMPS) and benzyl chloride with butylamine isomers and diethylamine was investigated kinetically in dioxane, methyl ethyl ketone (MEK), and N,N-dimethylformamide (DMF). Although the amination of i- and s-butylamine conformed to the ordinary second-order kinetics in all the solvents, deceleration was observed during the course of the amination of CMPS with n-butylamine in MEK as well as in dioxane, with t-butylamine in DMF, and with diethylamine in both dioxane and DMF. The intrinsic rate constants of the amination of CMPS were generally almost the same as those of benzyl chloride. The magnitudes of the rate constants in each solvent were in this order; n-butyl>i-butyl>s-butyl>t-butyl; it was in the order of DMF>>MEK≈dioxane with all the amines investigated. These results were interpreted in terms of both the structures of the amines and the interaction between the amine and the solvent molecules.
  • Akiko Okumura, Noriko Yamamoto, Nobukazu Okazaki
    1973 Volume 46 Issue 12 Pages 3633-3635
    Published: 1973
    Released: March 27, 2006
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    Oxygen exchange between arsenate ions and water is catalyzed by arsenious acid. The catalytic effect has been studied at 14.5 °C and 30.0 °C over the pH region of 7.5–10.2. The increase in the exchange rate due to the addition of arsenious acid, Rc may be expressed as: Rck[H+][As(III)][As(V)]. The results are interpreted in terms of the rapid reversible condensation of the As(III) with the As(V) species to form the arsenitoarsenate ions.
  • Shunsuke Kobinata
    1973 Volume 46 Issue 12 Pages 3636-3640
    Published: 1973
    Released: March 27, 2006
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    The formulas for the Raman intensities of fundamental and n-th overtones were investigated theoretically, starting from the Kramers-Heisenberg dispersion formula and referring to a diatomic molecule in a harmonic potential approximation. The derived formulas were then applied to fifteen overtone bands of iodine, which have been observed in gas, and to the exciting frequency dependence of the fundamental and the first overtone intensities of iodine in a CHCl3 solution. It was shown that the formulas quantitatively explain the trend of the observed data well.
  • Masayuki Katsumoto, Kazuo Fueki, Takashi Mukaibo
    1973 Volume 46 Issue 12 Pages 3641-3644
    Published: 1973
    Released: March 27, 2006
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    The isotopic exchange between H2S and D2 on molybdenum disulfide and manganese sulfide has been studied kinetically between 420° and 500 °C. The reaction proceeded via these steps:
    & H_2S+D_2=D_2S+H_2
    & H_2+D_2=2HD
    From the analysis of the kinetic data, the rate constant of the sulfurization of both metal sulfides by “hydrogen sulfide,” ki, and that of their reduction by “hydrogen,” ki′, were calculated. The dependence of these rate constants on the sulfur activity was determined. A possible mechanism of the reaction at the surface of the sulfides is discussed in this paper.
  • Shoji Hiroma, Haruo Kuroda
    1973 Volume 46 Issue 12 Pages 3645-3647
    Published: 1973
    Released: March 27, 2006
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    The polarized absorption spectra in the 10000–37000 cm−1 region were observed on the single crystal of the water-free modification of the potassium-chloranil salt, K+·(chloranil), by using a microspectrophotomer, and the variation of the spectra with temperature was examined. The crystal gives a near-infrared absorption band associated with the charge transfer between chloranil radical anions, the maximum of which is located at 11.5×103 cm−1. The absorption bands in the 20000–37000 cm−1 region were assigned to the local-excitation bands associated with the transitions in the chloranil anion. The intensity of the charge-transfer band gradually increases on lowering the temperature. An abrupt increase of intensity occurrs in the charge-transfer band at the phase-transition point. There is a close correlation between this change and the temperature dependence of the paramagnetic susceptibility of the salt.
  • Shigeru Ikuta, Kenji Yoshihara, Takanobu Shiokawa
    1973 Volume 46 Issue 12 Pages 3648-3651
    Published: 1973
    Released: March 27, 2006
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    The relation between the fragment ion distribution and recombination energy of the incident positive ions was studied by means of charge exchange reactions. The energy range which is consistent with the molecular orbital (MO) theory proposed by Hirota to account for the mass spectra by electron impact was also investigated, and the usefulness of the theory was discussed. The energy range to which the MO theory is applicable is very limited, the fragment ions produced at the high recombination energy to which it is apparently applicable, being the C2, C3 and C1 ion groups. It is probable that these species are not produced directly from the parent but by degradation mechanisms via intermediate steps, thus causing disagreement with the MO theory. Its applicability to alkanes is open to question. The dissociation schemes on n-alkanes are presented from the expreimental results.
  • Tadaaki Kakutani, Shoji Totsuka, Mitsugi Senda
    1973 Volume 46 Issue 12 Pages 3652-3657
    Published: 1973
    Released: March 27, 2006
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    Electrochemical behavior of protoporphyrin IX dimethylester (PPDM), mesoporphyrin IX dimethylester(MPDM), Fe(III)Cl-protoporphyrin, Ni(II)-, Cu(II)-, Co(II)-, Zn(II)- and Mn(III)Cl·H2O–PPDM was investigated in dimethylformamide by use of AC polarography, cyclic voltammetry and DC polarography. These porphyrins and divalent metal complexes of PPDM gave, for the most part, three reduction waves. The first and second waves were reversible one-electron steps in each case, but the third step was an irreversible one. Mn(III)-complex gave four reduction waves and one oxidation wave. The first three reduction waves were one-electron steps and the oxidation wave was identified as that due to chloride anion. Fe(III)-complex gave five reduction waves and one oxidation wave. The first two reduction waves were one-electron steps. All these compounds showed specific adsorption at the potential more positive than −1.1 V vs. SCE. Assignment of the reduction steps of the metalloporphyrins is described. The observed order of increasing negative half-wave potentials is discussed in terms of Zerner and Gouterman’s molecular orbital calculation.
  • Isao Ono, Norisuke Hata
    1973 Volume 46 Issue 12 Pages 3658-3662
    Published: 1973
    Released: March 27, 2006
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    In order to deduce the nature of the reactive state of the photochemical isomerization of isoquinoline N-oxide in methanol or water, investigations by means of steady-light irradiation and flash spectroscopy were carried out under various conditions. Transient absorptions were observed in the spectral region between 360 nm and 600 nm; they were identified as being due to a T–T transition of isoquinoline N-oxide. Experiments on both the measurements of the quantum yields and the decay kinetics of the transient species under different conditions revealed that the excited singlet state of isoquinoline N-oxide was responsible for the isomerization. The photochemical behavior in aqueous solutions at various pH values was also examined; consequently, the photochemical isomerization was found to be independent of the hydrogen ions, although it did not occur in a strongly acidic solution (pH<3.0) because of the formation of the protonated N-oxide. The biacetyl-photosensitization for isoquinoline N-oxide led to the dissociation of the N–O bond instead of to isomerization.
  • Isamu Shimizu, Hiroshi Kokado, Eiichi Inoue
    1973 Volume 46 Issue 12 Pages 3662-3665
    Published: 1973
    Released: March 27, 2006
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    The electric conductivity of the chalcogenide glass increased with an increase in the amount of Ag which had been photo-doped. By applying the electric field to the electrodes which were set on the surface of the Ag photo-doped chalcogenide glass film, a conductive path was grown from the cathode to the anode. As a result of the connection of the electrodes with the path, the electric resistance of the cell abruptly decreased (ON state). The path was made of the metal silver reduced by electrolysis and was diminished by irradiation with light. As the path was erased, the cell was turned into the resistant state (OFF state). The cycles were repeatable many times. There was a delay time (td) in turning the cell from the OFF to the ON state by applying the electric field (E). It was empirically described by the following equation for the Ag photo-doped chalcogenide glasses:
    t_d=aexp(-b·E)
  • Akiko Katayama, Hideaki Kita
    1973 Volume 46 Issue 12 Pages 3665-3671
    Published: 1973
    Released: March 27, 2006
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    Potentiostatic and potentiodynamic transients are theoretically analysed on the basis of the electrochemical mechanism for the hydrogen electrode reaction. The interface was assumed to consist of the metal surface, the plane on which the adsorbed intermediate of H2+(a) stays, and the diffuse double layer. The repulsive force between the intermediates was introduced by proportional approximation. From the results the depolarization observed in Tafel plots is understood as a non-steady state phenomenon, and observation by the potential-sweep method offers information on both the features of the adsorbed intermediate and the kinetics of the step preceding the rate-determining step.
  • Akiko Katayama, Hideaki Kita
    1973 Volume 46 Issue 12 Pages 3671-3676
    Published: 1973
    Released: March 27, 2006
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    Potentiostatic and potentiodynamic experiments on Hg in 1 M HCl, HBr, and HI solutions were carried out to elucidate transient phenomena of the electrochemical mechanism of the hydrogen electrode reaction. The results obtained by both methods agree with the analysis of the non-steady state based on the electrochemical mechanism. The large effect of anions on the transient phenomena is satisfactorily interpreted by the change of repulsive force energy between H2+(a)’s on electrode, which is caused by the presence of specifically adsorbed anions in various degrees. The potential-sweep method reveals features of the step preceding the rate-determining step and gives the value of the repulsive force energy between H2+(a)’s as expected by the analysis.
  • Koji Yamamoto, Shigeru Tsunashima, Shin Sato
    1973 Volume 46 Issue 12 Pages 3677-3681
    Published: 1973
    Released: March 27, 2006
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    The reactions of acetaldehyde, propionaldehyde, and n-butyraldehyde photosensitized by cadmium (3P1) have been investigated at 270 °C. The pressure dependence of the main products, CO, RH (R=CH3, C2H5, and n-C3H7) and R2, was well explained by the following reaction mechanism; Cd*+RCHO→R+CHO+Cd or RH+CO+Cd. R+RCHO→RH+RCO, RCO→R+CO, CHO→H+CO, H+RCHO→H2+RCO, R+R→R2 or RH+ Olefin. Carbon dioxide was found to be a rather good quencher for triplet cadmium atoms, and was used for estimating the relative quenching efficiencies of the three aldehydes and acetone. The values obtained were 0.16, 1.0, 1.3, 1.2, and 1.4, respectively for carbon dioxide, acetone, acetaldehyde, propionaldehyde, and n-butyraldehyde, when the efficiency of cis-2-butene was assumed to be unity.
  • Azumao Toyota, Takeshi Nakajima
    1973 Volume 46 Issue 12 Pages 3681-3685
    Published: 1973
    Released: March 27, 2006
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    On the basis of the second-order Jahn-Teller effect and the semiempirical SCF MO method, we examined the energetically most favorable molecular-symmetry groups and geometrical structures with respect to C–C bond lengths of the CmHm−2 cata-condensed nonalternant hydrocarbons. In the 4n π-electron systems the first excitation energies in the fully-symmetrical nuclear arrangements were predicted to be significantly smaller than a certain critical value, and a molecular-symmetry reduction accompanied by a marked double-bond fixation in the peripheral carbon skeleton to occur. On the other hand, in the 4n+2 π-electron systems, such energies were found to be considerably large for small members and to decrease rapidly with the number of carbon atoms, resulting in the molecular-symmetry reduction for members larger than a certain critical size. The electronic spectra were calculated using the most stable geometrical structures obtained by the SCF MO method.
  • Teizo Kitagawa, Kazuo Kusaki, Tatsuo Miyazawa
    1973 Volume 46 Issue 12 Pages 3685-3687
    Published: 1973
    Released: March 27, 2006
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    The Raman spectra of ethyl methyl ether in the liquid state were measured at various temperatures from 298 K to 195 K. The energy difference between the gauche and trans isomers in the liquid state was found to be 1.1 kcal/mol. This value is appreciably higher than the value 0.77 kcal/mol for n-butane. The tendency of assuming the trans form is higher for the CH2–O bond than for the CH2–CH2 bond. The infrared intensity of the band at 465 cm−1 (gas) is largely due to the gauche isomer but the Raman intensity of the line at 471 cm−1 (liquid) is largely due to the trans isomer.
  • Susumu Tajima, Nobuhide Wasada, Toshikazu Tsuchiya
    1973 Volume 46 Issue 12 Pages 3687-3689
    Published: 1973
    Released: March 27, 2006
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    The decomposition of C6H5CO+ ions produced by electron impact from seven alkyl phenyl ketones, C6H5COR (R=H, CH3, C2H5, n-C3H7, iso-C3H7, n-C4H9, n-C5H11), has been studied. By determining the heats of formation, the C6H5CO+ ions produced from the different precursors in the vicinity of the threshold are shown to have the same structure, and it is also shown that there is a linear relationship between the heat of formation of the activated complex for the reaction C6H5CO+→C6H5++CO and the vibrational degrees of freedom of the neutral fragment, R.
  • Ichiro Nakagawa
    1973 Volume 46 Issue 12 Pages 3690-3693
    Published: 1973
    Released: March 27, 2006
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    Far infrared spectra of K3[Co(CN)6] and [Co(NH3)6][Co(CN)6] and a single crystal Raman spectrum of K3[Co(CN)6] have been measured. Calculations of optically active crystal vibration frequencies have been made, on the basis of the crystal structure determined precisely. For these two types of established crystal structures (C2h5 for K3[Co(CN)6] and C3i2 for [Co(NH3)6]) [Co(CN)6] of hexacyano-complex salts, lattice frequencies have been determined. For [Co(NH3)6][Co(CN)6] the mean amplitudes of two kinds of cobalt atoms have been calculated and compared with those obtained by Iwata and Saito assuming that both complex ions behave as a rigid body.
  • Shigeki Nakayama, Keisuke Suzuki
    1973 Volume 46 Issue 12 Pages 3694-3698
    Published: 1973
    Released: March 27, 2006
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    The visible and ultraviolet absorption spectra of the p-phenylenediamine cation (PD+), the N,N-dimethyl-p-phenylenediamine cation (DMPD+), and the N,N,N′,N′-tetramethyl-p-phenylenediamine cation (TMPD+) in the presence and in the absence of an excess counter anion (X=Br, Cl, and ClO4) are studied at low temperatures. Analyses of the data show that these cation radicals are in an equilibrium represented by 2R++X\ ightleftharpoonsR++2X (or, more exactly, 2R++0.7X\ ightleftharpoonsR++2(X)0.7). It is found that the absorption maxima of the dimer and the value of the heat of dimerization are independent of the kind of counter anion. It is concluded that PD+ and DMPD+ form strong dimers (heat of dimerization, ΔH=−8.0 and −8.2 kcal/mol respectively) and that TMPD+ forms a relatively weak one (ΔH=−5.6 kcal/mol). The features of the dimer spectra reflect the strength of the interaction of the radical in the dimer. In a strong dimer, the spectrum in the low-frequency region consists of a strong intermolecular charge-transfer band (C band) and a weak local excitation band (R′ band), and the frequency shifts of the local excitation bands in the dimer (R′ and Y′ bands) from corresponding bands in the monomer (R and Y) are large. On the other hand, the spectrum in the weak dimer consists of relatively weak C and strong R′ bands, and the shifts of the R′ and Y′ bands are small. A model of the dimer is proposed in which the two cations are arranged in a parallel manner and are surrounded by the ionic atmosphere of the counter anions.
  • Masahiro Hatano, Takamichi Enomoto, Ichi Ito, Michio Yoneyama
    1973 Volume 46 Issue 12 Pages 3698-3702
    Published: 1973
    Released: March 27, 2006
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    Poly-γ-(1-naphthylmethyl)-L-glutamate was synthesized and its structure analyzed by the measurements of circular dichroism and absorption spectra. When the circular dichroism band at 219 nm in the circular dichroism spectrum of the polymer can be assigned to the band due to n–π* transition in the peptide main chain of the polymer, the calculated content of the right hand helix in the polymer is about 54% in ethylene chlorohydrin solution. It was also found that the polypeptide can form a charge-transfer complex with an organic electron acceptor in ethylene chlorohydrin solution. In the charge-transfer complex, a circular dichroism band could be observed at the wavelength corresponding to that of the charge-transfer band in the absorption spectrum of the complex. From the results, it was confirmed that the charge-transfer complex contains α-helix structure of this polypeptide. The temperature dependence of the charge-transfer complex formation was discussed in terms of the formation constant and thermodynamic parameters. The polypeptides having various portions of the 1-naphthylmethyl-D-glutamate residue were synthesized from poly-γ-methyl-D-glutamate by a polymer reaction using p-toluenesulfonic acid. The values of b0 for the polypeptides derived from poly-γ-methyl-D-glutamate were estimated by means of Moffitt-Yang’s equation, and the correlation between the b0 values and the contents of 1-naphthylmethyl residue in the polypeptides was discussed.
  • Kazuo Mochida, Akio Kagita, Yoshihisa Matsui, Yoshio Date
    1973 Volume 46 Issue 12 Pages 3703-3707
    Published: 1973
    Released: March 27, 2006
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    The apparent dissociation constant (Kapp) of a complex between β-cyclodextrin and an azo dye, sodium p-(4-hydroxy-1-naphthylazo)benzenesulfonate, was determined by spectrophotometry in a phosphate buffer solution (pH 5.91) in the absence and in the presence of various inorganic salts at 25 °C. The cyclodextrin and the azo dye formed a 1 : 1 complex with the Kapp value of 2.44×10−3 M in a 0.1 M phosphate buffer. Kapp decreased with an increase in the concentration of the phosphate buffer and with the addition of some inorganic salts, such as Li2SO4, Na2SO4, K2SO4, LiIO3, NaIO3, KIO3, and KF. These results were explained mainly in terms of the decrease in the activity of water, which takes part in the dissociation reaction of the inclusion complex, with an increase in the concentration of the inorganic salts. On the other hand, Kapp increased with the addition of such salts as KCl, KBr, KI, KNO3, KSCN, and KClO4. These results were attributed mainly to the formation of the inclusion complexes of the cyclodextrin with the anions of these salts, competing with the azo dye for the cyclodextrin-binding site.
  • Makoto Nagashima, Hideji Fujii, Masao Kimura
    1973 Volume 46 Issue 12 Pages 3708-3711
    Published: 1973
    Released: March 27, 2006
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    The structure parameters of tetramethyltin have been determined by gas-phase electron diffraction to be as follows: rg(Sn–C)=2.1436±0.0030 Å, rg(Sn···H)=2.7642±0.0125 Å, rg(C–H)=1.1179±0.0090 Å, l(Sn–C)=0.0496±0.0098 Å, and l(Sn···H)=0.1532±0.0132 Å. The experimental molecular intensity has been well reproduced by the molecular model in which the methyl groups are rotating freely, or nearly freely. The scattering factors, based upon the relativistic Hartree-Fock-Slater or the Hartree-Fock atomic potential, have given a theoretical background in better agreement with the experimental one and have led to a more reasonable Sn–C mean amplitude than did the scattering factors based upon the Thomas-Fermi-Dirac or the Thomas-Fermi atomic potential.
  • Kozue Kaibara, Keiji Saito, Hideo Kimizuka
    1973 Volume 46 Issue 12 Pages 3712-3714
    Published: 1973
    Released: March 27, 2006
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    The self-diffusion coefficient of an ion and the membrane permeability were studied with a system consisting of two identical electrolyte solutions separated by a cation exchange membrane. The membrane permeability to cation was estimated from the membrane conductance data. The result indicated that the membrane permeability increased with a decrease in electrolyte concentration. The self-diffusion coefficients and the concentrations of Na+, Cs+, and Ca2+ in the membrane were also measured by the radiotracer method. At concentrations less than 0.1 M, the self-diffusion coefficients more or less increased with increasing concentrations, while the concentrations within membrane remained almost constant. The membrane permeability to ion estimated from the conductance data was in excellent agreement with that calculated by the relation in which the membrane permeability is given as the self-diffusion coefficient times the partition coefficient divided by the membrane thickness.
  • P. Naser
    1973 Volume 46 Issue 12 Pages 3715-3719
    Published: 1973
    Released: March 27, 2006
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    The viscosity and thermal conductivity coefficients of monomethylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA), and their binary mixtures have been measured in the temperature range 25–250 °C. In addition, determinations of thermal conductivity of ternary mixtures at 33 and 88 °C and of several quaternary mixtures (with ammonia) at 33 °C have been made. The results are discussed in the light of modern kinetic theory of gases. Finally, the coefficients of self-diffusion and mutual diffusion in binary mixtures of these gases are estimated from the experimental viscosity results.
  • Tadaaki Kakutani, Mitsugi Senda
    1973 Volume 46 Issue 12 Pages 3720-3723
    Published: 1973
    Released: March 27, 2006
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    Electrochemical kinetic parameters were determined for the first two reduction steps of some porphyrins and divalent metalloporphyrins in DMF containing 0.5 M TEAP at 25 °C by use of radio frequency polarographic method. The results were discussed in view of their molecular structures and the diffuse double layer effect on the kinetic parameters.
  • Kazuaki Yamanari, Jinsai Hidaka, Yoichi Shimura
    1973 Volume 46 Issue 12 Pages 3724-3728
    Published: 1973
    Released: March 27, 2006
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    Solubility of the racemic and optically active isomers of [Co(ox)en2]X, [CoCO3en2]X, cis-[Co(NO2)2en2]X and M[Co(edta)] in water was determined at 5–60 °C (X=Cl, Br, and I; M=NH4 and K). The correlation between solubility of the spontaneously resolved racemic complex and of the corresponding optically active isomer is discussed. Spontaneous resolutions were observed for [Co(ox)en2]X (X=Cl, Cl·H2O, and Br·H2O), cis-[Co(NO2)2-en2]X (X=Cl and Br) and M[Co(edta)]·2H2O (M=NH4 and K).
  • Yasuo Ishimura, Yasuomi Nonaka, Yuzo Nishida, Sigeo Kida
    1973 Volume 46 Issue 12 Pages 3728-3733
    Published: 1973
    Released: March 27, 2006
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    Copper(II) complexes were prepared with a series of tridentate ligands, NH2(CH2)mCHRNH(CH2)n OH (R=H or CH3; m=1 or 2; n=2 or 3). Compounds obtained can be classified into three groups: (1) CuLCl2, (2) CuL(ClO4) and (3) CuL2X2, (L and L′ represent the neutral and the anionic ligands, respectively, and X denotes Cl or ClO4). (1) and (3) were found to be mononuclear in which L functions as a bidentate ligand donating with the two nitrogen atoms. (2), except for the complex with L′=NH2(CH2)3NH(CH2)2O have the binuclear structure with alkoxo bridges. The absorption bands at about 350 nm are characteristic of the binuclear structure with alkoxo or hydroxo bridges.
  • Akinori Jyo, Morihisa Yonemitsu, Nobuhiko Ishibashi
    1973 Volume 46 Issue 12 Pages 3734-3737
    Published: 1973
    Released: March 27, 2006
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    Ion-selective electrodes responsive to maleic and phthalic acids were prepared. The organic solvent solution of the ion-pair of the objective monovalent acid anion with a Crystal Violet or a tris(bathophenanthroline)-iron(II) ion was used as the electrode membrane. The responses of both electrodes were linear down to 10−4–10−4.5 M, with an ideal Nernstian slope of 57–58 mV per activity decade at 20 °C. Together with the potential slope, the pH dependence of the potential showed that the electrode responded to the monovalent anion of maleic or phthalic acid. The interferences of acetate, benzoate, and chloride were extremely low, whereas iodide and perchlorate interfered greatly. The maleic acid electrode works well without the interference of fumaric aicd. The phthalic acid electrode also functions without any interferences by isophthalic or terephthalic acid.
  • Ryokichi Tsuchiya, Akira Uehara, Eishin Kyuno
    1973 Volume 46 Issue 12 Pages 3737-3744
    Published: 1973
    Released: March 27, 2006
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    The thermal olation of the following four types of complexes in a solid phase was investigated by means of derivatography: 1) cationic complexes, [Co(OH)(n3-o)(H2O)]X, 2) anionic complexes, M[Co(OH)(n-o3)-H2O)], 3) double complexes, [Co(OH)(n3-o)(H2O)][Co or Cr(OH)(n-o3)(H2O)] and 4) neutral complexes, [Co(OH)(n-o)2(H2O)], where n3-o, n-o3 and (n-o)2 denote gly-en (glycinate ion and ethylenediamine) or dtma (diethylenetriaminemonoacetate ion), the analogues of nta (nitrilotriacetate ion) and α-amino acid ions, respectively. The thermal data such as initiation temperature, enthalpy change and activation energy of the olation were estimated from the respective derivatograms. From the results the effect of various ligands or counter ions (outer-sphere ions) on the olation was discussed.
  • Mitsuo Sato, Takao Kwan
    1973 Volume 46 Issue 12 Pages 3745-3748
    Published: 1973
    Released: March 27, 2006
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    The interaction of bis(O,O′-diethyldithiophosphato)oxovanadium(IV), VOdtp2, with pyridine has been studied in toluene by means of the optical absorptions. It has been found that the visible absorption band characteristic of VOdtp2 was shifted toward longer wavelengths upon the formation of the complex species identified as VOdtp2·Py and VOdtp2·Py2. The equilibrium constants and enthalpy and entropy changes for the formation of VOdtp2·Py were determined from the spectral characteristics, measured as a function of the solvent composition and the temperature. The results obtained were then discussed in comparison with those for the base addition of other oxovanadium complexes.
  • Osamu Yamauchi, Yasuo Nakao, Akitsugu Nakahara
    1973 Volume 46 Issue 12 Pages 3749-3752
    Published: 1973
    Released: March 27, 2006
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    The structure-stability relationship between the copper(II) complexes of several dipeptide amides consisting of glycine and/or β-alanine has been investigated by potentiometric titration. The amides of glycylglycine, glycyl-β-alanine, and β-alanylglycine (abbreviated as H2L) have been found to form complexes of the type Cu(H2L)2+ with logK1 values 4.80–5.22. The −logKC1 values for deprotonation of the peptide group are 5.05–5.42 and comparable to those of tripeptides, whereas the −logKC2 values for the terminal amide group are 7.96 for glycylglycine amide and 8.99 for glycyl-β-alanine amide. This indicates that, at neutral pH, the –CONH2 group coordinates to copper(II) mainly through the carbonyl oxygen. β-Alanyl-β-alanine amide-copper(II) system gave precipitates at an early stage of titration. The structures and relative stability of the complexes of types Cu(H2L)2+, Cu(HL)+, and CuL have been discussed from comparative studies of their stability constants.
  • Takayoshi Kawai, Haruko Otsuka, Hitoshi Ohtaki
    1973 Volume 46 Issue 12 Pages 3753-3756
    Published: 1973
    Released: March 27, 2006
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    The hydrolytic reactions of nickel(II) ion were studied at 25 °C in water and dioxane-water mixtures containing 3 M (Li)ClO4 as an ionic medium. Emf measurements were carried out in the range of the total nickel(II) ion concentration of 0.02469–0.7891 M in water, 0.02488–0.7996 M in a 0.1 mole fraction (35.21% w/w) dioxane-water mixture and 0.05170–0.9016 M in a 0.2 mole fraction (55.01% w/w) dioxane-water mixture, respectively. Some supplementary measurements were performed in a 0.5 mole fraction (83.02% w/w) dioxane-water mixture. Only the Ni4(OH)44+ complex was found in all solvent systems and its formation constant in log*β44 was −27.32±0.08 (in water), −27.11±0.08 (in a 0.1 mole fraction dioxane-water mixture), and −27.04±0.05 (in a 0.2 mole fraction dioxane-water mixture). In order to test the relative change of the formation consatnt of the Ni4(OH)44+ complex over the whole solvent composition examined, the variation of the formation constant was measured with the continual change of solvent composition at constant Z. Approximate values of the solubility products of Ni(OH)2 and NiOHClO4 precipitates were estimated from maximum values of Z.
  • Eiji Niki, Tsutomu Yonezawa
    1973 Volume 46 Issue 12 Pages 3757-3764
    Published: 1973
    Released: March 27, 2006
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    The pressure effect of nitrous oxide and nitric oxide due to nitrogen gas was investigated with use of a nondispersive infrared gas analyser. The results are in line with the theoretical curves derived from the Elsasser theory. The calculated expression is partly improved and the error of calculations is estimated in regard to carbon dioxide.
  • Takaharu Honjo, Shigeru Ushijima, Toshiyasu Kiba
    1973 Volume 46 Issue 12 Pages 3764-3767
    Published: 1973
    Released: March 27, 2006
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    The behavior of milligram amounts of silver, bismuth, cadmium, and zinc in liquid-liquid extraction has been studied with 20% trioctylamine (TOA) in carbon tetrachloride. The results have also been applied to the separation of the four metals as their TOA complexes by extraction chromatography. After passing a sample solution of 2 M HCl through a column (φ1cm×1 30 cm) consisting of a stationary phase of TOA–CCl4 on Kel-F, the metal ions were retained and then eluted with 5.5 M HCl at the rate of 0.5–1 ml/min at 20±1 °C. Silver was found in 90–180 ml of the effluent; Bi was flowed down in 200–500 ml of the same effluent. The cadmium and Zn were held so firmly on the column that they could not be removed under the above conditions. Therefore, water was passed through to release these metals. Zinc was first flowed down with 0–50 ml, and then Cd, with 200–500 ml of water. When 5M HNO3 was used as the eluting solution instead of water, the Cd was immediately removed from the column. The percentage recovery of these metals in the extraction chromatography was estimated as 101% (Ag), 99% (Bi), 97% (Cd), and 94% (Zn) respectively. The distribution ratios of these metals, as obtained by the extraction chromatography of the TOA–carbon tetrachloride (Kel-F)–HCl system, were in quite good agreement with those obtained by the batch extraction.
  • Takaharu Honjo, Toshiyasu Kiba
    1973 Volume 46 Issue 12 Pages 3768-3772
    Published: 1973
    Released: March 27, 2006
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    Cobalt(II), nickel(II), copper(II), zinc(II), mercury(II), lead(II), and cadmium(II) were extracted with STTA (1,1,1-trifluoro-4-(2-thienyl)-4-mercapto-3-buten-2-one) in cyclohexane, and their colored complexes were chromatographed on a thin-layer of silica gel with various organic solvents. The developing solvents used were 18 kinds of pure solvents and 10 different binary solvent mixtures of 1 :1, v/v. An excellent separation could be achieved after development with carbon tetrachloride, carbon disulfide, ethyl acetate, and cyclohexane–chloroform, chloroform–carbon disulfide, and carbon tetrachloride–carbon disulfide mixtures. The Rf value generally increased in the following orders: Cd(II), Zn(II), Pb(II), (STTA)<Hg(II)<Co(II, III)<Cu(II)<Ni(II) (with carbon tetrachloride); Cd(II), Zn(II), Pb(II), (STTA)<Co(III)<Hg(II)<Cu(II)<Ni(II) (with carbon disulfide); Cd(II), (STTA)<Zn(II)<Pb(II)<Hg(II), Co(III), Cu(II), Ni(II) (with ethyl acetate); and Cd(II), Zn(II), Pb(II), (STTA)<Hg(H)<Co(III)<Cu(II)<Ni(II) (with the cyclohexane-chloroform, chloroform-carbon disulfide, and carbon tetrachloride–carbon disulfide mixtures). A few μg Ni(STTA)2 chelates on the plate could be determined quantitatively by measuring the spot area from the curve drawn on a millimeter-graph sheet after driving a densitometer across the spot. Some aspects of the behavior of the STTA chelates on the thin-layer of silica gel have also been discussed.
  • Takaharu Honjo, Satoshi Yashima, Toshiyasu Kiba
    1973 Volume 46 Issue 12 Pages 3772-3779
    Published: 1973
    Released: March 27, 2006
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    The solvent extraction of trace amounts of various metal ions with STTA (1,1,1-trifluoro-4-(2-thienyl)-4-mercapto-3-buten-2-one) in the presence or in the absence of TOPO (tri-n-octylphosphine oxide) has been investigated. The results are as follows: (a) The apparent extraction constant of each metal–STTA chelate in cyclohexane, logK, increases, and their pH 1⁄2 values decrease, in the order of: Cd(II)-In(III)-Zn(II)-Fe(III)-Ni(II)-Ag(I)-Bi(III)-Co(II)-Pb(II)-Cu(II)-Hg(II). This order was found to hold also in the back-extraction, except for cobalt, which was not back-extracted even with 1–12 M HCl. The other metals, Au(III), and Pd(II), could also be extracted as their STTA chelates. (b) The kind of the solvent has an effect to the lowest pH value where the metal STTA chelates begin to be extracted; the lowest pH is shifted to a higher value in the order of: C6H12, CCl4, MIBK, C6H6 and CHCl3. (c) The distribution coefficient, Pr, and the enol dissociation constant, Ka, of STTA were logPr=2.99 (10−3 M STTA in cyclohexane-0.1 M NaClO4-pH 1.0) and logKa=−4.38 (10−4 M STTA in 0.12 M HCl, 0.1 M CH3COOH (pH 4.5) and 0.1 M NaOH-C2H5OH (1/5, v/v) solution) at 20 °C. (d) The extraction equilibrium of Zn seemed to be rapid, that of Ni showed its rate-determining step to be the formation of Ni(STTA)+, and that of Co seemed to be accompanied by a transformation of Co(STTA)2 to Co(STTA)3. (e) In the metal–STTA(0.001 M)-TOPO(0.01 M)–cyclohexane system, the |ΔpH1⁄2| was found to be 0.45 for Ni, 1.95 for Zn, and 0.25 for Co. The Co–STTA–TOPO chelate could be back-extracted to some degree with 1 M HCl. The extracted species were ascertained to be Zn(STTA)2, Zn(STTA)2TOPO, Ni(STTA)2, Co(STTA)2, Co(STTA)3, and Co(STTA)2TOPO. The stability constant of Zn(STTA)2 TOPO was found to be 6.05.
  • Eiichi Miki, Kunihiko Mizumachi, Tatsujiro Ishimori, Hisateru Okuno
    1973 Volume 46 Issue 12 Pages 3779-3784
    Published: 1973
    Released: March 27, 2006
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    Twelve 15NO-complexes of iron, cobalt, ruthenium, and iridium were prepared. The correlations of the isotopic shifts of their IR spectra with a metal–(NO) bond angle were investigated. For several nitrosyl complexes, the absorption bands due to the skeletal vibrations between the metal and the NO group were clearly assigned. Of the two absorption bands in the region 250–650 cm−1, the absorption band with a smaller isotopic shift could be assigned to the metal–(NO) stretching vibration and that with a larger isotopic shift to the metal–(NO) bending vibration.
  • Masahiro Takizawa, Akitsugu Okuwaki, Taijiro Okabe
    1973 Volume 46 Issue 12 Pages 3785-3789
    Published: 1973
    Released: March 27, 2006
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    The oxidation of sodium thiosulfate with ozone in an aqueous solution was investigated as a part of a series of studies on the chemical behavior of such low-valence sulfur compounds as thiosulfate and sulfite. The ozone oxidation was carried out by blowing a mixed gas of ozone and oxygen continuously into a 0.3–0.6 mol/l solution of sodium thiosulfate at 10–80°C. In a neutral solution, thiosulfate is converted to sulfate, sulfite, tri- and tetrathionates, hydrogen sulfide and sulfur dioxide, and finally to sulfate, tri- and tetrathionates. The yield of the sulfate is only 40% of the total sulfur. In an alkaline solution, however, thiosulfate is oxidized to sulfite as an intermediate, and finally to sulfate.
    The oxidation of sodium sulfite, and potassium salts of tri- and tetrathionate with ozone was also studied in order to elucidate its mechanism.
  • Masao Sugawara, Tomihito Kambara
    1973 Volume 46 Issue 12 Pages 3789-3791
    Published: 1973
    Released: March 27, 2006
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    The ion-pair of magnesium(II)–8-hydroxyquinoline-5-sulfonic acid chelate anion with zephiramine (Z+Cl) was extracted into chloroform. The ternary complex has an absorption maximum at 390 nm in the organic layer. The optimum pH range for the extraction is 10.1–11.4. For the first extract, Beer’s law holds for 4.6–20.6 μg of magnesium(II) in 10-ml organic layer, the molar absorptivity being 6.73×103 cm−1 mol−11. The composition of the ternary complex is estimated to be [Mg2+(QS2−Z+)2(HQSZ+)]o. The extraction equilibrium is given by
    Mg^2++3[(HQS^-Z^+)]_o+2OH^-\ ightleftharpoons[Mg^2+(QS^2-Z^+)_2(HQS^-Z^+)]_o+2H_2O
    where QS denotes 8-hydroxyquinoline-5-sulfonic acid and o the organic phase. The equilibrium constant K is given by logK=16.95±0.13.
  • Toyokichi Kitagawa, Akio Ichimura
    1973 Volume 46 Issue 12 Pages 3792-3795
    Published: 1973
    Released: March 27, 2006
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    The polarographic behavior of 9-nitroanthracene and 9,10-dinitroanthracene has been studied in dimethylformamide. 9-Nitroanthracene shows consecutive two one-electron diffusion-controlled reduction waves followed by fast chemical reactions. 9,10-Dinitroanthracene, however, shows only one reversible two-electron diffusion-controlled wave. The effect of the supporting electrolyte cation on these reduction waves was also investigated. In alkali metal or alkaline earth metal perchlorate as a supporting electrolyte, the half-wave potentials shift to the anodic side. The relationship between the half-wave potential and the ionic potential of the cation was discussed.
  • Etsuro Kobayashi
    1973 Volume 46 Issue 12 Pages 3795-3799
    Published: 1973
    Released: March 27, 2006
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    In order to develop fireproof materials, an attempt was made to prepare guanidium condensed phosphates ((H5CN3)n·Hn+2PnO3n+1, n=1–10) by means of a reaction between dicyandiamide (H4C2N4) and ammonium dihydrogen phosphate (NH4H2PO4) in an autoclave; then the conditions of the synthesis were investigated, and the components of the product were also identified. In the synthesis of gaunidium salt by means of a reaction between dicyandiamide and ammonium salt, generally only ammonium salts of strong acid have been used; also, high yields of guanidium salt could not be obtained with the (NH4)2H2PO4 used previously. In the present study, a mixture of 1 mol of H4C2N4 and 2 mol of NH4H2PO4 was heated in an autoclave at 130–300°C; 70–80% of the dicyandiamide was then converted into guanidium salt under the most suitable conditions. The majority of the product is soluble in water (the insoluble part is less than 3.5% at 150–220°C), and the solution is almost neutral. The components of the soluble part were 25–26% N and 20–24% P, the mole ratio of N to P being 2.8–2.5; this ratio decreased with an increase in the reaction temperature. On the other hand, the phosphates in the product consist of ortho-, pyro-, tri-, and middlepoly phosphates (n=4–10). The guanidium condensed phosphates thus obtained can be utilized as useful flame retarders for paper and wood, as guanidium orthophosphate can be.
  • Shinkiti Koto, Kazuo Yago, Shonosuke Zen, Satoshi Omura
    1973 Volume 46 Issue 12 Pages 3800-3804
    Published: 1973
    Released: March 27, 2006
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    Condensation of 3,4-O-carbonyl-2,6-dideoxy-3-C-methyl-L-ribohexopyranosyl chloride (III) with methyl 2-deoxy-2-(2,4-dinitroanilino)-β-D-glucopyranoside and the subsequent removal of blocking groups gave the anomeric isomers of methyl 6-O-(2,6-dideoxy-3-C-methyl-L-ribohexopyranosyl)-2-amino-2-deoxy-β-D-glucopy-ranoside (VIIa, VIIb). On the other hand, the condensation of III with methyl 3,6-dideoxy-3-(N-methylcarboethoxyamino)-2-O-p-phenylazobenzoyl-β-D-glucopyranoside (XI) followed by removal of the acyl groups and N-methylation afforded the anomeric forms of methyl 4-O-(2,6-dideoxy-3-C-methyl-L-ribohexopyranosyl)-3,6-dideoxy-3-dimethylamino-β-D-glucopyranoside (XVa, XVb).
  • Teruo Matsuura, Yoshikatsu Ito, Isao Saito
    1973 Volume 46 Issue 12 Pages 3805-3809
    Published: 1973
    Released: March 27, 2006
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    Imidazolines were found to be dehydrogenated to imidazoles by irradiation at 2537 Å or above 2900 Å in acetone. The n,π* triplet acetone acts as a hydrogen-abstracting agent giving 4- and/or 5-imidazolinyl radicals which in turn are transformed into imidazoles. This scheme is supported by the fact that the AIBN-initiated dehydrogenation of imidazolines gave corresponding imidazoles, that oxygen quenched the photochemical dehydrogenation, and that in some cases coupling products between the imidazolinyl and the acetone ketyl radicals were formed. Various data indicate that the imidazolinyl radical reverts to the parent imidazoline by hydrogen transfer from the acetone ketyl radical during the course of photolysis.
  • Kiyotomi Kaneda, Takashi Itoh, Yuzo Fujiwara, Shiichiro Teranishi
    1973 Volume 46 Issue 12 Pages 3810-3814
    Published: 1973
    Released: March 27, 2006
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    Rhodium complexes can cause the catalytic oxidation of cyclohexene to give ketone, alcohol, and epoxide. The product distribution is dissimilar to that of the metal-catalyzed decomposition of cyclohexene hydroperoxide(V). Ketone and alcohol are derived from the decomposition of the intermediate hydroperoxide (V) but epoxide is not formed by the oxygen transfer reaction from V. Oxidation of methylcyclohexenes was also studied and discussed in relation to the effect of methyl substituent.
  • Rikuhei Tanikaga, Aritsune Kaji
    1973 Volume 46 Issue 12 Pages 3814-3817
    Published: 1973
    Released: March 27, 2006
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    Irradiation of 2-nitrophenyl phenyl sulfoxide (I) gave 2-nitrosophenyl phenyl sulfone (II) as the sole product. The rearrangement was not affected by a quencher, but took a different course in the presence of a sensitizer or a halogen-containing solvent. When I with an electron-donating substituent at a 4′-position or electron-withdrawing one at a 4-position was irradiated, the corresponding II was obtained in a lower yield. 2-Nitrophenyl phenyl sulfide was photochemically stable. From the results, it is proposed that in the excited singlet state of I the oxyanion of a nitro group attacks the positive sulfur atom, and oxygen transfer takes place.
  • Mohamed Helmi Elnagdi, Masaki Ohta
    1973 Volume 46 Issue 12 Pages 3818-3821
    Published: 1973
    Released: March 27, 2006
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    3-Methyl-2-pyrazolin-5-one(Ia) reacts with acrylonitrile to yield either 4,4-di(β-cyanoethyl)-5-hydroxy-3-methylpyrazole(IV) or 1,4,4-tri(β-cyanoethyl)-3-methyl-2-pyrazolin-5-one(V) depending on the amount of reagent and the reaction conditions. Ia reacts with ethyl acrylate or crotononitrile to yield the 4-alkylated derivatives VIII and IX respectively. 3-Methyl-l-phenyl-2-pyrazolin-5-one(Ib) reacts with acrylonitrile to yield only 4,4-di(β-cyanoethyl) derivative XII which on hydrolysis affords the corresponding dicarboxylic acid (XIII). 3-Amino-1-phenyl-2-pyrazolin-5-one(Ic) adds to two molecules of ethyl acrylate or acrylonitrile to yield the 4,4-disubstituted derivatives XIV and XV, but only to one molecule of benzalacetophenone to yield the 4-substituted 3-amino-2-pyrazolin-5-one derivative XVIII. The pyrazolopiperidine derivative(XVI) was obtained on treatment of Ic with ethyl crotonate in the presence of sodium ethoxide.
  • Noboru Yamazaki, Fukuji Higashi
    1973 Volume 46 Issue 12 Pages 3821-3824
    Published: 1973
    Released: March 27, 2006
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    Amines were treated with the N-phosphonium salts of pyridine prepared by the oxidation of the phosphorous acid and its esters with mercuric chloride in pyridine; they yielded the corresponding amides in good yields upon acidolysis with carboxylic acids, together with metallic mercury in a nearly quantitative yield. The reaction was studied using phosphorous acid and its several esters, and was presumed to proceed via the activation of amines by the N-phosphonium salts of pyridine which were characterized by IR spectroscopy. This process for the activation of amino groups was successfully extended to peptide synthesis in pyridine at low temperature using diphenyl phosphite.
  • Tadashi Narita, Teruo Yamaguchi, Teiji Tsuruta
    1973 Volume 46 Issue 12 Pages 3825-3828
    Published: 1973
    Released: March 27, 2006
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    An addition reaction of diethylamine to styrene catalyzed by lithium diethylamide was found to proceed stoichiometrically to produce 1-diethylamino-2-phenylethane. The rate of the reaction was expressed by the equations: υ=k[Styrene][Et2NLi]1.3 and υ=k[Styrene][Et2NLi], the ratios of [Et2NH]0 to [Et2NLi]0 being 3.0 and 10 respectivly. On the basis of the kinetic studies, the mechanism of the addition reaction was elucidated. The nucleophilic character of this reaction was clearly demonstrated by the σ–ρ Hammett plot. The second-order rate constant for the addition reaction of styrene was found to be of the same order of magnitude as that of butadiene. The presence of butadiene in the reaction system showed no effect on the reactivity of styrene.
  • Haruo Matsuyama, Hiroshi Minato, Michio Kobayashi
    1973 Volume 46 Issue 12 Pages 3828-3830
    Published: 1973
    Released: March 27, 2006
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    In the presence of bis(trifluoromethyl) disulfide, methylphenylsulfonium bis(methoxycarbonyl)methylid is readily attacked by a nucleophile (an alkyl sulfide or a pyridine) and the corresponding new ylid is produced. In the NMR spectrum of a mixture of an ylid, an alkyl sulfide, and a catalytic disulfide, a remarkable broadening in the signals of the α-hydrogen of the sulfide was observed. A mechanism is suggested, which involves a complex from the two reactants and the catalyst.
  • Tetsuo Otsubo, Shigeyoshi Mizogami, Yoshiteru Sakata, Soichi Misumi
    1973 Volume 46 Issue 12 Pages 3831-3835
    Published: 1973
    Released: March 27, 2006
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    The NMR spectra of multilayered [2.2]paracyclophanes (I–XVI), in which benzene rings are closely stacked, have been examined. The assignment of the signals was made not only by integral strength, but also by solvent effect and the Nuclear Overhauser effect. The steric compression effect of transannular methyl groups on aromatic protons was observed in methylated cyclophanes. Enhanced ortho substitution shift was also observed. All the aromatic protons shift to remarkably higher field due to the anisotropy of stacked benzene rings as the number of layers increases. The shielding effect caused by these rings was empirically estimated.
  • Eisuke Munekata, Tetsuo Shiba, Takeo Kaneko
    1973 Volume 46 Issue 12 Pages 3835-3839
    Published: 1973
    Released: March 27, 2006
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    In the synthetic study of bacitracins, peptide fragments corresponding to a branched part of bacitracin F, i.e., (S)-2-(2-methylbutyryl)thiazole-4-carboxylic acid 1-succinimidyl ester (III) and L-leucyl-γ-t-butyl-D-glutamyl-L-isoleucine (IV), were prepared. As a macrocyclic part of bacitracin A and F of cycloheptapeptide formula, cyclo- (Nα-benzyloxycarbonyl-L-lysyl-Nδ-cyclopentyloxycarbonyl-D-ornithyl-L-isoleucyl-D-phenylalanyl-L-histidyl-β-benzyl-D-aspartyl-L-asparaginyl) (V) was synthesized through cyanomethyl ester method.
  • Tetsuo Suami, Seiichiro Ogawa, Hayashi Uchino, Masaru Uchida
    1973 Volume 46 Issue 12 Pages 3840-3844
    Published: 1973
    Released: March 27, 2006
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    Hydrazinolysis of DL-1,4-dibromo-1,4-dideoxy-chiro-inositol (3a), followed by catalytic hydrogenation and acetylation, afforded di-N-acetyl-tetra-O-acetyl-neo-inosadiamine-1,3 (6a) and -scyllo-inosadiamine-1,3 (7) in 18% and 24% yields, respectively. From the intact hydrazinolyzate of 3a, two new stereoisomeric 1,3-biimino-1,3-dideoxy-inositols (4a and 5a) could be isolated, and their structures were established by correlating to the corresponding inosadiamines. A similar hydrazinolysis of 3,6-di-O-p-tolylsulfonyl-muco-inositol (12) gave sole crystalline 1,3-biimino compound (13a), whose structure was followed from its conversion into known di-N-acetyltetra-O-acetyl-myo-inosadiamine-4,6 (14). PMR spectra of four 1,3-biimino compounds were discussed.
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