Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 43 , Issue 2
Showing 1-50 articles out of 73 articles from the selected issue
  • Hisashi Ueda
    1970 Volume 43 Issue 2 Pages 297-300
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The kinetics of the transient species of trans-stilbene in several solvents were studied using single pulsed electron beam (0.5 μsec×300 mA) and the spectroscopic method. The species existing immediately (0–20μsec) after a pulse is found to disappear according to a sum of two first-order decay-rate equations. The temperature dependence of the formation and decay of this species shows that there are two different trans-stilbene cations, Rs and Rf, which have almost identical absorption spectra but different formation and decay rates. The rate constants for Rs were not affected by the temperature, however, those for Rf were strongly affected. Rf is not found in the solution of trans-stilbene in 1,2-dichloroethane if a small amount of CCl4 is added. Some effects of the dielectric constant were observed on the decay-rate constant of Rf. From these facts, it can be concluded that Rf is formed by an ordinary transfer of a hole from the solvent cation to the solute molecule. As Rs seems to be formed by a mechanism other than that of Rf, a possible scheme for it has been discussed.
  • Toshiko Seimiya
    1970 Volume 43 Issue 2 Pages 301-305
    Published: 1970
    Released: March 27, 2006
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    The conditions under which nylon monolayer spread on water exhibits a reproducible and well-defined F-A curve favorable for detailed investigation of the surface chemical properties of nylon were studied. For this purpose monolayers of Nylons 6 and 8 were spread from such solvents as methyl alcohol, methyl alcohol saturated with calcium chloride, aqueous solution of 90% formic acid and the mixture of phenol and benzene in 1 : 3 volume ratio. The effects of the nature of these solvents, the volume of spreading solution, surface aging and substrate pH on the properties of spread film were studied. It was found that the monolayers can be classified into two different types of film, A and B, according to the behavior of F-A curve against compression. The type A film appeared usually at the first compression of the spread film. F-A curve of A film varied according to the nature of the spreading solvent and the film was unstable. It readily underwent change to type B by being allowed to stand after the film was compressed to a certain extent, by increasing the volume of the spreading solution or merely by compressing film A to a sufficiently high surface pressure. F-A curve of type B film obtained was almost independent of the nature of the spreading solvent and repetition of compression and expansion of the film.
  • Toshiko Seimiya
    1970 Volume 43 Issue 2 Pages 306-309
    Published: 1970
    Released: March 27, 2006
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    It was reported in the preceding paper that two types of film, A and B, can be distinguished in F-A curves for monolyers of Nylons 6 and 8 on the basis of the difference in behavior in relation to compression and expansion. In the present experiment, the compression and expansion were repeated for the monolayers of Nylon 8 spread from methyl alcohol in order to study the F-A characteristics of these films in detail. It was found that, during the process of first compression, the pressure drops rapidly and the transition of film A to film B occurs beyond a certain degree of compression of the monolayer. The transition was interpreted as the condensation of the monomer residue of the nylon molecule. The equations of the state for the expanded film were found to apply better than Singer’s equation for both types of film, A and B. Further, the effect of the concentrated sulfuric acid solution (3 and 6 N) as a substrate on the F-A curve was examined. There were little difference in the behavior of the monolayers on 3 n sulfuric acid irrespective of the spreading solvent used, but the difference was marked on dilute hydrochloric acid.
  • Toshiko Seimiya
    1970 Volume 43 Issue 2 Pages 309-314
    Published: 1970
    Released: March 27, 2006
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    The interaction of the monolayers of the Nylons 6 and 8 with the acid dye Orange II was studied by measuring the surface pressure of the nylon monolayers with and without Orange II in the substrate water. No change in the surface tension with the time was observed for the aqueous solution of Orange II in the concentration and pH ranges studied. The interaction between the nylon monolayers (film B) and Orange II was examined by observing the change in the F-A curve of the nylon monolayer due to the addition of Orange II to the substrate and the spreading of the solution. The presence of dye in a spreading solution has little effect, while the pH’s of the both the spreading solution and the substrate exhibit a marked effect on F-A curves. The observed interaction is compared with the behavior of practical dyeing in bulk of the solution.
  • Kenji Ishida
    1970 Volume 43 Issue 2 Pages 314-318
    Published: 1970
    Released: March 27, 2006
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    The stochastic formulation of chemical rate equations requires that the process of chemical relaxation should be accompanied with the fluctuation of chemical composition. It is shown that the factor Γ, which Eigen and de Maeyer introduced in the thermodynamic analyses of chemical relaxations, may be interpreted as the fluctuation of chemical composition.
  • Hisashi Ueda
    1970 Volume 43 Issue 2 Pages 319-325
    Published: 1970
    Released: March 27, 2006
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    The ESR intensities from the paramagnetic species formed by mixing a naphthalene derivative with an oxide powder were studied after the mixture had been heated at various temperatures. The measurements were made at 20°C. As additives 1-nitronaphthalene, 1-naphthol, 1,4-naphtho-quinone, naphthalic acid, 1-naphthylamine, l-nitroso-2-naphthol, naphthalene, triphenylene, and anthracene were used. As oxides, alumina, Al2O3-MoO3, silicagel, TiO2, MgO, MoO3, CuO, and ZnCrO4 were used. The ESR intensities obtained by the first six oxides depended only on the ioni-zation potential of the additives, while those obtained by CuO and ZnCrO4 did not. The ESR intensities obtained when 1-naphthol was mixed with alumina samples with various surface areas-were exactly proportional to the surface areas of the alumina specimens used. It was concluded that, in the first six oxides, the additives are chemisorbed by the oxides at the active-oxygen anion sites on the surface. The introduction of either NH3 or N2O onto the adsorbed species formed on Al2O3-MoO3 particles decreased (in the case of NH3) or increased (in the case of N2O) the ESR intensities. From these facts, it is concluded that a cationic complex, (naphthalene derivative+-O2−), is formed on the surface of these six oxides. In the case of GuO, the presence of (Cu+-naphthyl-amine+) is concluded.
  • Tsuguo Sawada, Hitoshi Kamada
    1970 Volume 43 Issue 2 Pages 325-330
    Published: 1970
    Released: March 27, 2006
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    Time-sampling technique has been applied to radiative lifetime measurements. The time resolution of the apparatus was about 10 nsec. The excited molecules were produced by electron bombardment of N2 and CH4. The measured lifetimes of N2+(B2Σu+), CH(A2Δ) and CH(B2Σ) are (6.5±0.5)×10−8 sec, (4.3±0.2)×10−7 sec and (7.6±0.4)×10−7 sec, respectively. Band oscillator strengths have been computed on the assumption that the electronic transition moment is constant in the range in which the transition takes place.
  • Tsuguo Sawada, Hitoshi Kamada
    1970 Volume 43 Issue 2 Pages 331-334
    Published: 1970
    Released: March 27, 2006
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    The radiative lifetimes of N2(C3IIu), NH(A3II), and NH(C1II) states were measured by the use of the time-sampling technique. The excited molecules were produced by the electron bombardment of N2 and NH3 gas. The lifetimes obtained in this experiment for N2(C3πII), NH(A3II), and NH(C1II) were (4.8±0.3)×10−8 sec, (4.1±0.2)×10−7 sec, and (4.3±0.2)×10−7 sec respectively. The oscillator strengths of the respective transitions were also calculated.
  • Ichiro Takemura, Hiroshi Sumitomo
    1970 Volume 43 Issue 2 Pages 334-339
    Published: 1970
    Released: March 27, 2006
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    Alternating copolymer was obtained in the system of β-cyanoacrolein (CAL) and α-methyl-styrene (α-MeSt). In the presence of air copolymerization proceeds even without any radical initiator at room temperature. In the radical initiated copolymerization of α-MeSt (M1) and CAL (M2), the values of monomer reactivity ratios r1=0.033 and r2=0 were obtained. Neither the rate of copolymerization nor viscosity number of the copolymer formed were influenced by the presence of air in the reaction system. The result of copolymerization in the ternary system involving methyl acrylate (MA) could not be entirely explained by the copolymerization equation given by Alfrey and Goldfinger for the three component system. It was found that the composition of the copolymer formed changed with the solvent dilution. Formation of 1 : 1 molecular complex between the monomers was evidenced by the application of the continuous variation method to α-MeSt-CAL system. It was concluded that the molecular complex due to some donor-acceptor type interaction between CAL and α-MeSt plays an important role in the copolymerization.
  • Tatsuo Yamamoto
    1970 Volume 43 Issue 2 Pages 340-344
    Published: 1970
    Released: March 27, 2006
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    The yields of isotopic hydrogen in the vapor phase radiolysis of deuterated methanol (CH3OD) were found to be G(H2)=6.1, G(HD)=5.3 and G(D2)=0.2. The molecular yields of isotopic hydrogen were also determined by adding propylene as a radical scavenger, GM(H2)=1.5, GM(HD)=0.6 and GM(D2)∼0. In order to estimate the contribution of ionic species for the formation of hydrogen, the ion-molecule reaction of CH3OD has also been investigated by using a mass spectrometer of the differential pumping type. The product ions, such as (CH3OCH3CH3OD)D+ or (CH3OD)3D+, which were considered to be formed by the higher order ion-molecule reactions were observed. The mechanism of hydrogen formation was discussed on the basis of the ionic, the molecular and the radical mechanisms.
  • Yoichi Iida
    1970 Volume 43 Issue 2 Pages 345-349
    Published: 1970
    Released: March 27, 2006
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    The infrared spectra (650–4000 cm−1) of p-chloranil and its anion-radical were measured. Appreciable frequency differences between their corresponding bands were noted. The fundamental frequencies were assigned, and the simple UBFF’s were determined for both the neutral and anion-radical molecules. Their stretching force constants for the bonds in the conjugated systems are related to the bond orders. The values of the bond orders thus obtained for p-chloranil and its anion-radical were in good agreement with those evaluated by the molecular-orbital calculation, except for the C=O bond in the anion-radical. In view of these results, it was concluded that the difference in the infrared spectra between these two molecules was almost entirely attributable to the difference in their electronic structures caused by an odd electron on the p-chloranil anion-radical. The bond lengths were also estimated on the basis of the bond orders. It was shown that the application of this method might bring valuable knowledge on the molecular and electronic structures of ion-radicals as well as of neutral molecules in general.
  • Hiroshi Yoneyama, Hideo Tamura
    1970 Volume 43 Issue 2 Pages 350-354
    Published: 1970
    Released: March 27, 2006
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    I-V curves of the α-Fe2O3 electrode containing different amounts of Ti were obtained potentio statically in H2SO4 solutions. The anodic current, indicating the dissolution reaction, was almost constant and was not affected by the aH+ of the electrolyte in the potential range 0.4–1.0V vs. SCE, but it was dependent on the conductivity of the electrode. It was suggested that the dissolution reaction of this electrode is governed by the electron-transfer mechanism, much as is that of the heavily-doped N-type Ge. The flat-band potential of the α-Fe2O3 electrode was estimated on the basis of the capacity measurement. This potential changed with the aH+ of the electrolyte.
  • Tsuguo Yamaoka, Saburo Nagakura
    1970 Volume 43 Issue 2 Pages 355-358
    Published: 1970
    Released: March 27, 2006
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    The charge-transfer interaction was studied for systems including s-triaminobenzene as electron donor. The formation of 1 : 1 stable outer (π,π) complexes at room temperature was observed for the systems including s-trinitrobenzene, trininitrotoluene and tetracyanobenzene as electron acceptors. From the analysis of the observed absorption intensities and peak positions of charge-transfer bands, the equilibrium constants of these complexes were determined and the ionization potential of s-triaminobenzene was estimated to be 7.3–7.4 eV. Chloranil was found to form a stable outer (π,π) complex with s-triaminobenzene only at low temperature, and to be led to a substitution reaction by raising the temperature. The spectrum of the reaction intermediate, the inner (σ) complex of s-triaminobenzene with chloranil, was observed at ∼500 mμ. A tentative reaction mechanism was proposed.
  • Hirofumi Okabayashi, Toshizo Isemura
    1970 Volume 43 Issue 2 Pages 359-361
    Published: 1970
    Released: March 27, 2006
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    The NMR spectra of t-amyloxycarbonyl-L-proline oligopeptides were measured and compared with those of two poly-L-prolines, I and II. The α-CH resonance peaks of the oligopeptides were observed at sheilding values of 5.2 and 5.4 ppm, values which were in accord with those of the α-CH resonance peaks of the poly-L-prolines I and II, respectively. The behavior of the α-CH peaks was related to the conformation of the L-proline oligopeptides. Moreover, the contribution of the two terminal L-proline residues to the α-CH resonance peaks was discussed.
  • Kunio Oda, Noritake Yasuoka, Tatzuo Ueki, Nobutami Kasai, Masao Kakudo
    1970 Volume 43 Issue 2 Pages 362-367
    Published: 1970
    Released: March 27, 2006
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    The crystal and molecular structures of di-μ-chloro-bis-(π- 1-ethoxycarbonyl-2-hydroxyallyl)-dipalladium, (C6H9O3PdCl)2 have been determined from the three-dimensional data. The crystals are triclinic; space group Pl; with one dimeric molecule per unit-cell; a=4.80, b=10.31, c=10.64 Å, α=117.4, β=102.3, and γ=84.1°. The final discrepancy index is 14.0% for 1208 reflections. The two palladium atoms are joined by two chlorine bridges to form a square planar arrangement. The molecule possesses a center of symmetry which coincides with a crystallographic center of symmetry in the crystal; the overall coordination scheme of the palladium atom is similar to that established for the π-allyl palladium chloride dimer. The dihedral angle between the plane of four atoms [Pd, Pd′, Cl, and Cl′] and the π-allyl plane is 108. There are intermolecular hydrogen-bonds between the enolic hydroxyl group of one molecule and the carbonyl-group of the other molecule related by the center of symmetry.
  • Yuji Nakano, Shuji Saito, Yonezo Morino
    1970 Volume 43 Issue 2 Pages 368-371
    Published: 1970
    Released: March 27, 2006
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    Microwave spectra of normal, 13C-, and 34S-isotopic species of ethylene episulfone have been investigated. Analysis of the spectra shows that the molecule has the C2V symmetry. The structural parameters obtained from the spectral data for the normal and 13C-ethylene episulfone are: r(C–C)=1.590±0.011 Å, r(C–S)=1.731±0.006 Å, r(S–O)=1.439±0.006 Å, ∠CSC=54°40′±15′, and ∠OSO=121°26′±30′, on the assumption that the C–H distances and the ∠HCH and ∠H2CC angles are the same as those of ethylene sulfide. Stark-effect measurements have yielded a value of 4.41±0.05 D for the dipole moment along the a axis. The structure obtained has been compared with those of other related molecules.
  • Teizo Kitagawa, Tatsuo Miyazawa
    1970 Volume 43 Issue 2 Pages 372-379
    Published: 1970
    Released: March 27, 2006
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    In preliminary studies on the frequency distribution, specific heat and Young’s moduli of the orthorhombic polyethylene crystal, methylene groups were treated as single dynamic units. Intermethylene force constants were estimated from the intermolecular potential function of methane and from deBoer’s potential function. Dynamical matrices of acoustic vibrations were constructed. A practical method was worked out for deriving the frequency distribution of acoustic vibrations from the volume enclosed in constant-frequency surfaces in a three-dimensional phase-difference space. With reference to specific heat in the lowest temperature region, inter-methylene force constants were adjusted. An efficient method was used for calculating the frequency distribution of crystal vibrations of chain-polymers. The frequency distribution of orthorhombic polyethylene crystal and specific heats in low temperature region were calculated in agreement with experimental results. A simple approximate method was used for treating Young’s moduli of orthorhombic chain-polymer crystals. Applicability of the skeletal approximation is discussed.
  • Teijiro Yonezawa, Isao Morishima, Yoshinori Akana, Kazuhiko Fukuta
    1970 Volume 43 Issue 2 Pages 379-387
    Published: 1970
    Released: March 27, 2006
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    To study the geometrical and electronic structures of molecules, the paramagnetic shifts of substiuted aniline proton resoances due to complexing with nickel of cobalt acetylacetonates, M(AA)2 (M=Ni or Co), were observed. The NMR spectra of sloutions containing an excess of niline derviatives and M(AA)2 show contact (for Ni(AA)2) and pseudocontact (for Co(AA)2)shift rations for various ligand protons. The contact shift ratios for N–H and N–CH3 protons reveal that the NH2 or NHR group of aniline dervatives is not coplanar with the aromatic ring for the coordinate molecules. This was confirmed by pseudo-contact shift studies.
  • Tamotsu Wasa, Morihiko Orita, Shingo Yoshida, Sôichirô Mus ...
    1970 Volume 43 Issue 2 Pages 388-393
    Published: 1970
    Released: March 27, 2006
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    Such a-keto acids as glyoxylic (I), pyruvic (II), α-ketobutyric (III), mesoxalic (IV), oxalacetic (V), and α-ketoglutaric acid (VI) condense with o-phenylenediamine (OPD) to form two kinds of products, depending on the pH values of the reaction mixtures. The condensation product formed at pH values lower than 4 gives a well-defined reduction wave (E1⁄2 vs. SCE at pH 2.0: −0.490 V for I, −0.587 V for II, −0.592 V for III, −0.181 V for IV, −0.590 V for V, and −0.576 V for VI) at a potential more positive than that of free α-keto acid, while the other product, formed at pH values between 4 and 8, gives an oxidation wave (E1⁄2:−0.1–−0.2 V vs. SCE for all α-keto acids at pH 6.0). From the present polarographic investigations, it was deduced that the condensation product giving the reduction wave is probably 2-hydroxyquinoxaline derivatives and that the product giving the oxidation wave is benzimidazoline derivatives. A linear relation was obtained between the wave height for the reduction of the condensation product and the concentration ((0.5–20)×10−4 M) for each α-keto acid under appropriate conditions. The reduction wave of the condensation product was used for the determination of II in a commercial product containing II as an impurity.
  • Isao Okada, Nobufusa Saito
    1970 Volume 43 Issue 2 Pages 394-397
    Published: 1970
    Released: March 27, 2006
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    The isotope effect of the thallous ion in the countercurrent electromigration of molten thallous nitrate has been measured at 219°C. The relative internal mobility difference between 203Tl+ and 205Tl+, ΔVVTl, has been determined to be 0.00035±0.00002. The mass effect μTl=(ΔVVTl)⁄(ΔMMTl), has been calculated to be −0.035±0.002, and this value has been compared with those of alkali nitrates previously determined.
  • Hisayuki Mizuochi, Shuichi Shirakata, Eishin Kyuno, Ryokichi Tsuchiya
    1970 Volume 43 Issue 2 Pages 397-400
    Published: 1970
    Released: March 27, 2006
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    The formation constants of chromium (III) complexes with iminodiacetic acid (IDA) and l-aspartic acid (Asp) as the terdentate ligands were determined by the pH method in the ionic strength, μ=0.1 and at 25°C: their values were logk1=10.9 and logk2=10.5 for IDA and logk1=10.1 and logk2=9.5 for Asp, respectively. That the overall formation constants of chromium(III)-IDA complexes obtained were slightly larger than those of the corresponding -Asp complexes was explained by the stronger chelate effect in the former complexes than in the latter ones. The solid chromium (III) complexes with IDA and Asp were also prepared. Based on chemical analyses and the conductivity measurement or the behavior toward the ion exchangers, the chemical formulas of these complexes are possibly K[Cr(ida)2]·3H2O and K[Cr(OH)2asp] respectively. X-Ray powder diffraction patterns indicated that the former crystalline complex has tetragonal unit lattice, the axial parameter being a=14.57 and c=12.38 Å, whereas the latter is amorphous solid.
  • Zenzi Hagiwara, Masaru Noguchi
    1970 Volume 43 Issue 2 Pages 401-405
    Published: 1970
    Released: March 27, 2006
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    With a view to the accurate determination of the separation factors of adjacent rare-earth pairs between the aqueous and resin phases, measurements have been carried out at 60°C in the exchange system involving EDTA and Dowex 50W, X-8, 50–100 mesh. Under the same experimental conditions as were used for the isolation of the rare earths by ion exchange, the separation factors at 60°C were found to be 3.43 for Nd-Sm, 1.37 for Eu-Gd, 1.84 for Tb-Y, 1.54 for Y-Dy, 2.83 for Tb-Dy, 1.84 for Dy-Ho, and 2.02 for the Ho-Er and Er-Tm pairs. Further, the observed values were discussed from the viewpoints of both thermodynamics and the real elution of the rare earths by an ion-exchange column.
  • Shoichiro Yamada, Yoshio Kuge, Kuniko Yamanouchi
    1970 Volume 43 Issue 2 Pages 406-408
    Published: 1970
    Released: March 27, 2006
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    Cobalt(III) complexes with Schiff bases (X-SAL.Y-OH) obtained from salicylaldehyde derivatives and alkanol amines (H2N.Y-OH) were synthesized as crystals. Two types of diamagnetic cobalt(III) complexes were obtained, one being green (type A) and the other red (type B). In the complexes of type A with the general formula [Co(H-SAL.R)3], where R=CH2CH2CH2OH and CH2CH2CH2OCH3, the ligands are considered to function as bidentate ligands, the terminal hydroxyl or methoxy groups not being bound with the cobalt(III) ion. In the complexes of type B with the general formula Co(X-SAL.Y-OH)(X-SAL.Y-O), where X=H and 3-CH3O, and Y=CH2CH2, CH2CH(CH3) and C(CH3)2CH2, the ligands function as terdentate ligands.
  • Yuki Fujii, Teiko Ueda, Mutsuo Kodama
    1970 Volume 43 Issue 2 Pages 409-414
    Published: 1970
    Released: March 27, 2006
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    In the present paper, the d.c. polarographic behavior of cadmium(II) and lead(II) ions in ethylenediaminemonoacetate (EDMA) solutions was studied systematically. Since these metal(II) ions in an EDMA solution behave reversibly in a polarographic electrolysis, the compositions and the stability constants of cadmium(II)- and lead(II)-EDMA complexes could be estimated successfully from the shift of the half-wave potential of these metal(II) ions due to the complex formation with EDMA. The cadmium (II) ion was found to form complexes of 1-to-1 and 1-to-2 compositions with EDMA, and the electrode reaction mechanism was established to be:
    (Remark: Graphics omitted.)
    The successive formation constants of cadmium(II)-EDMA complexes, (K1)cdx and (K2)cdx were determined to be 3.01×108 and 5.65×104 respectively. On the other hand, the lead(II) ion forms only one complex with 1-to-l composition. In the presence of the chloride ion, the lead(II) ion was found to form a mixed ligand complex involving the chloride ion as well as a normal complex, PbX+, and the electrode reaction could be formulated as:
    (Remark: Graphics omitted.)
    The equilibrium constants, (K1)Pbx(=[PbX+]/([Pb2+]·[[X])) and KpbxCl(=[PbXCl0]/([PbX+]·[Cl])), were determined to be 1.69×108 and 1.01×10 respectively. The effect of the zinc(II) ion on the half-wave potential of the cadmium(II) ion in an EDMA solution was also studied. From the positive shift of the half-wave potential due to the presence of the zinc(II) ion, the formation constant of the zinc(II)-EDMA complex with a 1-to-1 composition was estimated to be 1.58×108.
  • Akira Uehara, Eishin Kyuno, Ryokichi Tsuchiya
    1970 Volume 43 Issue 2 Pages 414-418
    Published: 1970
    Released: March 27, 2006
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    l-Leucine-N,N-diacetic acid (abbreviated as LDA) and the complexes thereof were prepared as follows: K[Cr(OH)(lda)(H2O)]·3H2O (violet) (I), [Cr(lda)(H2O)2] (bluish violet) (II), [Cr(lda)(H2O)2]·2H2O (grayish violet) (III), (enH2)1⁄2[Cr(OH)(lda)(H2O)2] (green) (IV), [Cr(lda)(o-phen)]·2H20 (brownish orange) (V), K[Cr(lda)(acac)]·H2O (blackish violet) (VI) and K[Co(OH)(lda)(H20)]·H2O (bluish violet) (VII), where lda, en, o-phen and acac are the abbreviations of l-leucine-N,N-diacetate ion, ethylenediamine, o-phenanthroline and acetylaceto-nate ion, respectively. Except for Complex IV, LDA behaves as a quadridentate ligand. In Complex IV, it acts as a terdentate one. It was found from electronic absorption spectra that in Complex I, LDA behaves as a quadridentate in a solid state and as a terdentate ligand in an aqueous solution, whereas in cobalt(III) complex VII corresponding to I, LDA behaves as a quadridentate. Stepwise liberation of the coordinated water molecules in Complexes II and III could be detected by means of Derivatograph. Complex VII showed “Dehydration-Dimerization Reaction” upon being heated.
  • Mutsuo Kodama, Teiko Ueda
    1970 Volume 43 Issue 2 Pages 419-423
    Published: 1970
    Released: March 27, 2006
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    The substitution reactions of diethylenetriaminepentaacetic acid (DTPA) with nickel(II) chelates of iminodiacetic acid (IDA) and aspartic acid (Asp) and of cyclohexane-1,2-diamine-N,N,N′,N′-tetraacetic acid (CyDTA) with the nickel(II) chelate of aspartic acid were studied by employing the polarographic method. All the reactions studied were found to proceed through the following two simultaneous reaction paths:
    (Remark: Graphics omitted.)
    where NiX0 and NiX22− denote nickel(II)-IDA or Asp chelates of 1-to-l and 1-to-2 compositions respectively, and where Zm indicates a completely-deprotonated DTPA or CyDTA anion. From a comparison of the rate constants of substitution reactions involving the nickel(II)-aspartate chelate with the corresponding rate constants of substitution reactions involving the nickel(II)-iminodiacetate chelate, the six-membered ring of the nickel(II)-aspartate chelate, as compared with its five-membered ring, was concluded to be more labile in the substitution reaction.
  • Hiroshi Ogino, Masatake Takahashi, Nobuyuki Tanaka
    1970 Volume 43 Issue 2 Pages 424-428
    Published: 1970
    Released: March 27, 2006
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    Conformation of trimethylenediaminetetraacetatocobaltate(III) (Cotrdta) was inferred from the measurement of proton nuclear magnetic resonance spectra. It was found that K[Co-trdta]·2H2O crystals are mixtures consisting of equimolar amounts of the crystals of K[(+)546-Cotrdta]·2H2O and those of K[(−)546Cotrdta]·2H2O; that is, so-called “spontaneous resolution” was found. The absolute configuration of optically active Cotrdta was determined by the measurements of optical rotatory dispersion (ORD) and circular dichroism (CD) curves and by the reaction with ethylenediamine to form tris(ethylenediamine) cobalt(III) cation.
  • Koko Maeda, Taro Hayashi
    1970 Volume 43 Issue 2 Pages 429-438
    Published: 1970
    Released: March 27, 2006
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    A stable free radical, 2,4,5-triphenylimidazolyl, which was produced by oxidation of 2,4,5-triphenylimidazole, dimerizes to yield two dimers, a photochromic dimer and a piezochromic dimer. The photochromic dimer shows thermochromism and photochromism at temperatures between −196°C and about 200°C both in solution and in solid state. The piezochromic dimer shows piezochromism in solid state and thermochromism both in solution and in solid state. Spectro-scopic and kinetic studies showed that photochromism, thermochromism and piezochromism are caused by radical dissociation of the dimers of triphenylimidazolyl on irradiation, heating and grinding. Dimers of substituted triphenylimidazolyl also showed these phenomena which are due to the same mechanism as that of the dimers of triphenylimidazolyl.
  • Chikahiko Eguchi, Kin-ya Akiba, Naoki Inamoto
    1970 Volume 43 Issue 2 Pages 438-442
    Published: 1970
    Released: March 27, 2006
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    The reaction of stable alkylidenephosphoranes with nitrosyl chloride in THF gave α-substituted α-hydroxyiminomethyltriphenylphosphonium chloride (A) in high yields. In the case of active alkylidenephosphoranes, “transylidation” took place simultaneously and a mixture of A and α-substituted methyltriphenylphosphonium chloride was obtained along with corresponding amounts of nitrile and triphenylphosphine oxide. By thermal decomposition, all α-hydroxyiminomethyltriphenylphosphonium chlorides (A) afforded nitriles and triphenylphosphine oxide.
  • Kaoru Hanaya
    1970 Volume 43 Issue 2 Pages 442-446
    Published: 1970
    Released: March 27, 2006
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    3-Methyl-4-chromanone (VIII) was reduced with a metal hydride complex, by the Meerwein-Ponndorf method and by catalytic hydrogenation. When VIII was reduced with a metal hydride complex and the Meerwein-Ponndorf method, trans-3-methyl-4-chromanol (IX) was produced as the main product. In the catalytic hydrogenation, VIII gave a cis-3-methyl-4-chromanol (X) as the main product over Raney nickel, but over the palladium catalyst the trnas isomer was larger than the cis isomer. These results indicate that, on Meerwein-Ponndorf and metal hydride reductions, the more stable product was formed as the main product; in the catalytic hydrogenation over the Raney nickel catalyst, VIII seems to be adsorbed mainly on the opposite side of the methyl group of the C-3 position and is hydrogenated to give the cis isomer, whereas, over the palladium catalyst, hydrogenation seems to proceed under the effect of “product development control over the catalyst” and the trans isomer is produced in a high yield.
  • I. P. Varshney, Geeta Badhwar
    1970 Volume 43 Issue 2 Pages 446-447
    Published: 1970
    Released: March 27, 2006
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    The seeds of Albizzia lebbek Benth. from Madhya Pradesh have been found to contain a mixture of saponins which on hydrolysis gives echinocystic acid (I), oleanolic acid (II) as major sapogenins and an unidentified sapogenin (not albigenin) in traces. The albigenic acid (III) earlier reported to be present has been shown to be an alcoholic hydrochloric acid isomerisation product of echinocystic acid.
  • Akiko Sohma, Sekio Mitsui
    1970 Volume 43 Issue 2 Pages 448-452
    Published: 1970
    Released: March 27, 2006
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    The effects of catalysts and an additive, sodium hydroxide, on the catalytic hydrogenation of benzalacetophenone oxide (I) have been studied for the purpose of elucidating the selectivity of the catalysts on the hydrogenation. The catalytic hydrogenation over palladium or Raney nickel led to the formation of the hydroxyketones as the primary products resulting from the hydrogenolysis of the epoxide ring. 1,3-Diphenylpropane-1,2-diol (III) was obtained by the catalytic hydrogenation over palladium, while 1,3-diphenylpropane-1,3-diol (VI) and III were yielded over Raney nickel. Under the basic conditions III was predominantly produced even over Raney nickel. Over platinum oxide, 2,3-epoxy-1,3-diphenylpropan-1-ol (VIII) was the primary product of the hydrogenation of the carbonyl group of I. In the hydrogenolysis of VIII, 1,2-diol (III) was produced regardless of the species of the catalysts.
  • Ahmedhusen Shaikh, Akiko Chinone, Masaki Ohta
    1970 Volume 43 Issue 2 Pages 453-455
    Published: 1970
    Released: March 27, 2006
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    The reactions of S-carboxymethylisothioamide RC(=NR′)SCHRCOOH with acetic anhydride proceeded through various courses depending on the reaction conditions and the structure of thioamides. When S-carboxymethylisothiobenzanilide (IIa) was treated with a mixture of acetic anhydride and triethylamine in the cold, an intermediate (A), presumably 2-hydroxy-2,3-diphenylthiazolidin-4-one (V), was isolated which was readily converted to benzoylthioacetanilide (IIIa). Attempts to convert A or IIIa to a mesoionic compound failed. Under the same reaction conditions as for IIa, S-carboxymethylisothiobenz-p-chloroanilide (IIb) afforded benz-p-chloroanilide, while corresponding p-anisidide (IIc) gave only tarry product. Attempts to obtain a mesoionic product from pyrrolidine-2-thione or thiocaprolactam and bromoacetic acid were unsuccessful. However, condensation of pyrrolidine-2-thione with α-chlorophenylacetic acid followed by treatment with a mixture of acetic anhydride and triethylamine gave eight-membered rearranged product (XII).
  • Masaharu Yoshikawa, Mitsuru Sakuraba, Koji Kusashio
    1970 Volume 43 Issue 2 Pages 456-461
    Published: 1970
    Released: March 27, 2006
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    The treatment of a 2′,3′-O-isopropylidene nucleoside with phosphorus trichloride in the presence of trimethyl phosphate and subsequent hydrolysis gave a nucleoside 5′-phosphite in an excellent yield. Triaryl phosphates, trialkylphosphine oxides, and trialkyl phosphites were also found to be potential accelerators of the reaction. Their effects were comparable to that of trimethyl phosphate. The similar treatment of a 5′-O-acetyl nucleoside gave mixed nucleoside 2′- and 3′-phosphites in an approximate mole ratio of 4 : 6. The reaction intermediate, nucleoside phosphorodichloridite, was subjected to partial hydrolysis, giving the corresponding monochloridite. The product was readily oxidized to give the 5′-nucleotide. Chlorine was generally suitable as an oxidizing agent, but iodine gave better results for guanosine derivatives than did chlorine or bromine. The treatment of an unprotected nucleoside with phosphorus oxychloride in a trialkyl phosphate, prior to the reaction with phosphorus trichloride, could be used for the synthesis of a nucleoside 2′(or 3′),5′-diphosphate in a good yield.
  • Toshikazu Nagai, Tetsuo Maeno, Niichiro Tokura
    1970 Volume 43 Issue 2 Pages 462-465
    Published: 1970
    Released: March 27, 2006
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    The migratory aptitude of the aryl group in the unimolecular ion decomposition reaction of p-substituted diaryl sulfones has been examined. Both electron-donating and -withdrawing substituents showed to be capable of increasing the migratory aptitude. On the other hand, a kinetic treatment allowed a satisfactory Hammett correlation (ρ=0.3) on the total abundances of the fragment ions. The energy of the cleaved bond and the production stability were shown to be important factors in the effect of the substituent on the ion decomposition.
  • Yoshimoto Abe, Ichiro Kijima
    1970 Volume 43 Issue 2 Pages 466-469
    Published: 1970
    Released: March 27, 2006
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    Alkoxysiloxy derivatives of titanium and polymeric substances with Ti–O–Si bonds were prepared. The reaction of titanium tetra-isopropoxide or bis (acetylacetonato)di-isopropoxytitanium with tri-t-butoxysilanol led to the formation of the derivatives of [(ButO)3SiO]nTi(OPri)4−n (n=2 and 3) and those of [(ButO)3SiO]2Ti(AcAc)2 respectively. In both of these series, the absorption peak of the Ti–O–Si bond in the IR spectrum shifted toward a lower wave number from the compounds of n=2 to those of n=3. The reaction of titanium tetra-isopropoxide with di-t-butoxysilanediol, as expected, gave a polymeric substance. In the reaction with bis(tri-t-butoxysiloxy)-silanediol, however, an unexpected cyclic compound consisting of the Ti–O–Si bond was obtained; its presence was confirmed by a study of the IR and NMR spectra, by elemental analysis, and by molecular-weight determination. In order to obtain a linear polymer, the reaction of the titanium acetylacetonato chelate with the silanediols was carried out to give a reddish-brown, highly viscous liquid or solid. These polymeric substances were soluble in common organic solvents and have an appreciable hydrolytic stability, but only a moderate thermal stability.
  • Teruzo Asahara, Manabu Sen\={o}, Sadayoshi Tanaka
    1970 Volume 43 Issue 2 Pages 469-472
    Published: 1970
    Released: March 27, 2006
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    The anionic telomerizations of styrene with some aromatic amines catalyzed by sodium metal were investigated. o-Toluidine, m-toluidine, p-toluidine, 2,4-xylidine, 2,5-xylidine and 3,4-xylidine were used as the aromatic amines. Each amine reacted with styrene to give an addition product, which was identified as N-substituted 2-phenylethylamine. Though both α-hydrogen atoms on α-carbon atoms and hydrogen atoms attached to nitrogen atoms of the aromatic amines are weakly acidic, only the latter hydrogen atoms were detached by alkali species under the present experimental conditions. The formations of the products were discussed from the standpoint of anionic telomerization.
  • Hitomi Suzuki, Kiyomi Nakamura
    1970 Volume 43 Issue 2 Pages 473-480
    Published: 1970
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Pentamethylbenzene has been nitrated with fuming nitric acid to give mainly a mixture of nitropentamethylbenzene and 2,3,4,5-tetramethylbenzyl nitrate. Other isomeric nitrates were not formed in any significant amount. 6-Nitro-2,3,4,5-tetramethylbenzyl nitrate, 2,3,4,5-tetramethylbenzyl alcohol, 2,3,4,5-tetramethylbenzaldehyde, 2,2′,3,3′,4,4′,5,5′,6-nonamethyldiphenylmethane, and 2,2′,3,3′,4,4′,5,5′-octamethyl-6-nitroxymethyldiphenylmethane were the minor products. Pentaethylbenzene gave a mixture of nitropentaethylbenzene and α-methyl-2,3,4,5-tetraethylbenzyl nitrate along with some products of oxidation. Preferential side-chain attack occurred at the primary alkyl group ortho to the unsubstituted ring position. Thus, 1-methyl-2,3,4,5-tetraethylbenzene was found to give benzyl nitrate and α-methylbenzyl nitrate nearly in equal amounts, while 3-methyl-1,2,4,5-tetraethylbenzene was found to give them in an approximate ratio of 1 : 3. 1,3,4-Trimethyl-2,5-diisopropylbenzene underwent extensive nitrodealkylation, and 3,4-dimethyl-2,5-diisopropylbenzyl nitrate was the only side-chain substituted product identified.
  • Hitomi Suzuki
    1970 Volume 43 Issue 2 Pages 481-484
    Published: 1970
    Released: March 27, 2006
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    The action of fuming nitric acid upon chloropentamethylbenzene, bromopentamethylbenzene, and iodopentamethylbenzene has been investigated. 5-Halo-2,3,4,6-tetramethyl- and 6-halo-2,3,4,5-tetramethylbenzyl nitrate were the principal products. 4-Halo-2,3,5,6-tetramethylbenzyl nitrate was never formed in any significant amount. The orientation was consistent with the previously suggested mechanistic scheme. PMR spectral data for nine halotetramethylbenzyl chlorides and nitrates have been presented.
  • Tsutomu Sakai, Kazuo Yoshihara, Yoshio Hirose
    1970 Volume 43 Issue 2 Pages 484-487
    Published: 1970
    Released: March 27, 2006
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    The constituents of the volatile oils of three Zanthoxylum species were studied on the basis of the preceding exhaustive analysis of fruit oil from the Japanese pepper. It seems that the fragrance quality among the genera Zanthoxylum depends on the content of citronellal in the essential oil. That is, the unripe fruit oil of Japanese pepper with the strongest characteristic aroma contained the largest amount of citronellal. Ripe fruit oil of Z. simulans containing a trace amount of citronellal had a poor flavor.
  • Koji Hirai, Niichiro Tokura
    1970 Volume 43 Issue 2 Pages 488-491
    Published: 1970
    Released: March 27, 2006
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    The reactions of methanedisulfonyl chloride (II) with ketene diethylacetal (III), 1 -morpholinocyclohexene (IV), and 1-piperidinopropene (V) in the presence of triethylamine were studied. The products obtained were the double cycloadduct, spiro bithietane tetroxide (VI), and the substitution products (X and XV). These findings suggest that triethylamine dehydrochlorinates methanedisulfonyl chloride to produce disulfene. However, as yet we cannot say whether the formation of disulfene is the one-step dechydrochlorination mechanism (ClSO2CH2SO2Cl → SO2=C=OS2) or the two-step one (ClSO2CH2SO2Cl → ClSO2CH=SO2 → SO2=C-SO2).
  • Yasuo Satoh, Akira Horiuchi, Akira Hagitani
    1970 Volume 43 Issue 2 Pages 491-495
    Published: 1970
    Released: March 27, 2006
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    The synthesis of 2-oxo- 5β-steroids (5β-cholestan-2-one and methyl 2-oxocholanate) and their derivatives have been described. Both oxo-steroids were prepared from 2β-acetoxy-3-oxo- 5β-ste-roids according to the following synthetic pathways: (a) condensation with ethylmercaptan to diethylmercaptol, desulfurization, hydrolysis and oxidation, (b) condensation with ethylmercaptan to diethylmercaptol, hydrolysis to hydroxy-ethylmercaptol, desulfurization and oxidation, and (c) isomerisation to 3α-acetoxy-2-oxo derivative and deacetylation with zinc powder to 2-oxo derivative. In these pathways, it was found that method (b) gave the best yield. On the other hand, desulfurization of the hydroxy-mercaptols with one-half the weight of Raney nickel used for that of method (b) gave 2β-hydroxy- 3β-ethylthio derivatives as intermediates. Reductive cleavage of these hydroxy-ethylthio derivatives with Raney nickel produced 2β-hydroxy- 5β-steroids in good yields. In the halogenation of these 2-oxo derivatives, the products were 1β-halo-2-oxo- 5β-sterodis, not 1α- or 3-halo isomers.
  • Masao Ogawa, Ryoji Ishioka
    1970 Volume 43 Issue 2 Pages 496-500
    Published: 1970
    Released: March 27, 2006
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    The tellurium tetrachloride-cyclohexene adduct, 2-chlorocyclohexyltellurium trichloride (I) and bis(2-chlorocyclohexyl) tellurium dichloride (II), both gave, on pyrolysis, chlorocyclohexane as the chlorinated compound. An intermolecular hydrogen transfer is required for the formation of chlorocyclohexane from I. Chloro-n-propyltellurium trichloride (III) and bis(chloro-n-propyl)-tellurium dichloride (IV) were formed by the addition of tellurium tetrachloride to propylene. The pyrolysis of III afforded allyl chloride, 1,2-dichloropropane, and hydrogen chloride, while tellurium was simultaneously reduced. Besides these products, isopropyl chloride was also obtained from IV. Some properties of the adduct and the effect of the temperature on the thermal decomposition were studied.
  • Hiroshi Minato, Masayoshi Oku, Nobuyuki Higosaki
    1970 Volume 43 Issue 2 Pages 500-505
    Published: 1970
    Released: March 27, 2006
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    t-Butylmagnesium chloride was found to initiate the polymerization of vinyl chloride efficiently at −22–30°C. The best solvent was diethyl ether, but the degree of polymerization was the highest when no solvent was used (\barPn=1940 at 20°C). The apparent activation energy for the rate of polymerization was 13.2 kcal/mol and the frequency factor was 9.06×104. The rate of polymerization, Rp, was equal to const. ×[VC]3.90×[t−BuMgCl]1.98. Isopropylmagnesium bromide initiated the polymerization with less efficiency, and phenylmagnesium bromide was completely ineffective. Vinyl chloride and styrene were copolymerized in ether by t-butylmagnesium chloride at 30°C. The mole % styrene included in the copolymer was considerably different from those obtained by benzoyl peroxide at 48°C or by di-t-butylperoxy oxalate at 30°C.
  • Yoshiaki Ohgo, Seiji Takeuchi, Juji Yoshimura
    1970 Volume 43 Issue 2 Pages 505-509
    Published: 1970
    Released: March 27, 2006
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    Reduction of various olefines by a solution of pentacyanocobaltate and glycine or optically active α-amino acid was studied. There is no essential difference between the reactivity of [Co(CN)5H]3− to olefines and that of the solution of pentacyanocobaltate and α-amino acid. Atropic acid was reduced with the solution containing optically active α-amino acid (l-isoleucine) to give slightly optically active hydratropic acid. It was found that the main reactive species in the solution of [Co(CN)5]3− and α-amino acid was [Co(CN)5H]3− (this might be the reason for the asymmetric reduction not taking place effectively), and the reversible change between [Co(CN)5]3− and [Co-(CN)5H]3− was observed depending on the pH of the solution.
  • Shinji Kurokawa
    1970 Volume 43 Issue 2 Pages 509-514
    Published: 1970
    Released: March 27, 2006
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    When 3-acetylguaiazulene was heated with sulfur at 200°C, three new azulenoids were obtained, in addition to the S-guaiazulene formed by the loss of the acetyl group; the structures were established as 2-acetylguaiazulene, 6-acetyl-, and 7-acetyl-3,5,8-trimethylazuleno [6,5-b] thiophenes. From the experimental results it became obvious that a sulfur atom linked one methyl carbon atom of the isopropyl group with the C6-azulene-ring carbon atom in 3-acetylguaiazulene, resulting in the formation of a thiophene ring, and also that the loss and the migration of the acetyl group took place in 3-acetylguaiazulene as well. The acetyl migration in this compound was ascertained to be a simple thermal reaction and to occur in one direction, from C3 to C2.
  • Takayoshi Iio, Sho Takahashi
    1970 Volume 43 Issue 2 Pages 515-520
    Published: 1970
    Released: March 27, 2006
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    The conformations of four polypeptides containing ordered sequences of L-alanyl(A) and glycyl (G) residues, (A)n, (A3G)n, (A2G)n, and (AG2)n, are investigated in solution. The optical rotatory dispersion and infrared spectra showed that all the polymers assume both an α-helical conformation and a β-conformation in solution. The stability of the α-helix decreases in the oder: (A)n, (A2G)n, (A3G)n, and (AG2)n; this may be explained in terms of the interaction between methyl groups of L-alanyl residues regularly arranged on the surface of the α-helix.
  • Yoshio Kohara, Michio Kobayashi, Hiroshi Minato
    1970 Volume 43 Issue 2 Pages 520-524
    Published: 1970
    Released: March 27, 2006
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    p-Toluenesulfonylation of toluene and anisole in the presence of AlCl3, SbCl5 or TiCl4 was investigated in methylene chloride, nitromethane and nitrobenzene. Substitution took place at 8.6–13.4% and 86.6–91.4% para positions for toluene in methylene chloride, but 42.0–45.7% ortho and 54.2–58.0% para isomers were obtained in nitromethane and nitrobenzene. Sulfonylation of toluene with p-CH3C6H4SO2+ ClO4 afforded 44.8–46.3% ortho and 53.7–55.2% para isomers. Partial rate factors for toluene were pf=52.5 in methylene chloride, of=12.6±0.9, pf=31.4±2.0 in nitromethane, and of=16.0±1.7, pf=38.3±4.2 with p-CH3C4H4SO2+ClO4. A plausible mechanism is proposed, in which the attacking species is TsCl-MCln complex in methylene chloride, but it is an ion pair, ArSO2+MCln+1, in nitromethane and nitrobenzene.
  • Michiyo Morishita, Fumio Sakiyama
    1970 Volume 43 Issue 2 Pages 524-530
    Published: 1970
    Released: March 27, 2006
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    Several synthetic peptide derivatives containing tryptophan were examined for the selective cleavage at the tryptophyl residue, according to a new scheme involving ozonization and subsequent treatment with hydrazine. The ozonization reaction of the tryptophyl residue was carried out in the presence and in the absence of resorcinol in formic acid. Then the reaction of the ozonized product with hydrazine was performed at pH 3.6 to bring about the tryptophyl bond cleavage. The yield of the present cleavage reaction ranged from 35 to 68% on the basis of the starting peptide derivative used. The cleavage reaction could be followed spectroscopically in parallel with the exposure of the amino group acylated by the tryptophyl residue. The 2,3,4,5-tetrahydropyridazone derivative derived from the parental tryptophyl residue was identified by a comparison of both its chromato-graphic behavior and its ultraviolet spectrum with those of the standard sample. Thus it was confirmed that the present cleavage proceeded through the proposed reaction sequence.
  • Tsutomu Tsuchiya, Kiyohiko Suo, Sumio Umezawa
    1970 Volume 43 Issue 2 Pages 531-537
    Published: 1970
    Released: March 27, 2006
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    Methyl 3-azido-3-deoxy-α and β-D-xylopyranoside are prepared. The oxidation of the 2-O-benzoylated derivative of the above-mentioned α-anomer with the Pfitzner-Moffatt reagent leads to the facile elimination of the elements of benzoic acid and the formation of the 4-azido derivative of 5,6-dihydro-α-pyran-5-one. The 3-ethoxycarbonylamido derivative obtained from the above mentioned 3-azido derivative is oxidized similarly to afford the 4-ethoxycarbonylamido derivative of 5,6-dihydro-α-pyran-5-one. The mechanisms of these elimination reactions are discussed.
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