Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 47 , Issue 12
Showing 1-50 articles out of 65 articles from the selected issue
  • Osamu Kikuchi, Katsutoshi Aoki
    1974 Volume 47 Issue 12 Pages 2915-2921
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    MC-SCF equations have been derived with the help of Segal’s partition-basis-set technique; these equations can be used for the calculation of the potential curves of many organic reactions. They were applied to two typical organic reactions, and the results were compared with those obtained by CI methods. The corrections of the SCF-CI energies by the MC-SCF procedure were small for the present system.
  • Yoshiaki Watanabe, Yoshito Matsumura, Yusuke Izumi, Yukio Mizutani
    1974 Volume 47 Issue 12 Pages 2922-2925
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The one-step synthesis of methylisobutyl ketone from acetone and hydrogen was investigated by using palladium supported on zirconium phosphate, a bifunctional catalyst. Effects of reaction variables on both the conversion of acetone and the selectivity of methylisobutyl ketone were examined. The experiments were carried out with a continuous flow unit at 110–140°C and 7–25 kg/cm2 over a range of liquid hourly space velocity of acetone for 2–15 hr−1 with a mole ratio of hydrogen to acetone in the range 0.2–1.45. Under these conditions, the conversion of acetone was 20–40%, the selectivity of methylisobutyl ketone being as much 90–97 mol%. It is suggested that the one-step reaction proceeds via a consecutive mechanism.
  • Akira Sasaki, Jun-ichi Aihara, Yoshio Matsunaga
    1974 Volume 47 Issue 12 Pages 2926-2929
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Four tricyanovinyl aromatic compounds were spectroscopically investigated in various phases. The solidstate spectra distinctly display both intra- and inter-molecular charge-transfer bands in the visible region. The formation of the charge-transfer self-complex is, however, markedly hindered in the fluid phases. The dual charge-transfer properties were also examined for these compounds.
  • Masakatsu Uyemura, Shiro Maeda
    1974 Volume 47 Issue 12 Pages 2930-2935
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The absolute intensities of the stretching fundamentals of cyanoacetylene and cyanoacetylene-d were measured in gaseous and crystalline (77 K) states. As had been expected from the previous result for hydrogen cyanide, a striking intensity increase upon crystallization was observed not only for νCH(CD) also for the other fundamentals. The observed intensities were reduced to dipole-moment derivative with respect to the internal coordinates, ∂μ⁄∂r. Then, by taking advantage of the strictly linear geometry of hydrogen-bonded chains in the crystals, it was demonstrated that the derivative with respect to the hydrogen-bonded distance, [∂μ⁄∂rN···H], was primarily responsible for the remarkable change in ∂μ⁄∂r; this was in accordance with the previous conclusion for hydrogen cyanide. A discrepancy from this view which appeared for ∂μ⁄∂r3 was interpreted as being mainly caused by the vibronic behavior of π-electrons.
  • Hiroshi Kawabe
    1974 Volume 47 Issue 12 Pages 2936-2941
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The animation of chloromethylated polystyrene (CMPS) and benzyl chloride with diethyl amine, diethanolamine, and di-n-butylamine was investigated kinetically in N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or dioxane. The apparent second-order rate constant decreased as the amination proceeded in the amination of CMPS with diethylamine and di-n-butylamine in DMF as well as in dioxane. Although a similar deceleration was also observed in the amination of CMPS with diethanolamine in DMF and DMSO, acceleration was observed during the course of the amination in dioxane. It is assumed that the deceleration and the acceleration are due to the steric obstruction and to the formation of a hydrogen bond by the neighboring groups in the transition state respectively. The intrinsic rate constants of the amination of CMPS were almost the same as those of benzyl chloride. The rate of the amination with diethanolamine was lower than that of the amination with diethylamine because of the inductive effect of the hydroxyl group. The rate constants in different solvents were in this order; DMSO>DMF>>dioxane. The aminated CMPS with diethanolamine (pK0=7.37) was quaternized with methyl iodide or bromoacetic acid in 50% aq. DMF. The deceleration due to the electrostatic effect of the neighboring groups was observed in the quaternization.
  • Katsuhiro Tamura, Takashi Moriyoshi
    1974 Volume 47 Issue 12 Pages 2942-2947
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The rates of the acid-catalyzed rearrangements of benzopinacol and of tetraphenylethylene oxide in acetic acid have been measured in the range of 35–45°C at pressures up to 983 kg/cm2. It was proved under pressures that the rearrangement of pinacol proceeds through two routes, with three processes. The probable mechanism for each process has been discussed in the light of the activation parameters, particularly the volume parameters (ΔV\ eweq and ΔV). Consequently, it may be probably inferred that the classical carbonium ion is an intermediate in the rearrangement of oxide, but not in the other two processes, i.e., the conversion of pinacol to oxide and the direct rearrangement to pinacolone, and that the transition states in the two processes of rearrangement must be clearly distinguished.
  • Sumio Shinoda, Yasukazu Saito
    1974 Volume 47 Issue 12 Pages 2948-2952
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Kinetic deuterium isotope effects on the redox decomposition of hydroxymercurated propene, cis-, and trans-2-butenes in an aqueous solution (CH3CH(OH)CHRHg+→CH3COCH2R+Hg(0)+H+; R=H, CH3) were determined by following the reaction in situ by means of PMR spectroscopy. Taking advantage of the PMR characteristics, the identity of the reaction conditions was confirmed by comparing the rates for the reactant mixtures (e.g., CH3CH(OH)CH2Hg++CH3CD(OH)CH2Hg+). The mercurials, deuterated on either β-carbon (CH3CD(OH)CH2Hg+, CH3CD(OH)CHCH3Hg+) or α-carbon (CH3CH(OH)CDHHg+, CH3CH(OH)CDCH3Hg+), gave primary and secondary deuterium isotope effects of 1.35–1.40 and 1.17–1.19 respectively. A possible structure of the activated complex was proposed in accord with the observed nature of the intramolecular hydrogen shift.
  • Takeshi Ohno, Shunji Kato
    1974 Volume 47 Issue 12 Pages 2953-2957
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The interaction between ligands in the excited state and in the ground state was examined by exploring the photophysical behaviors of ligands in the bis- and the tris-bidentate complexes. Although no exciton splitting was observed in the absorption spectra of [Zn(bipy)3](NO3)2 and [Zn(phen)2(H2O)2](NO3)2 at 77 K, the fluoresccence yields of both complexes increased in comparison with those of the corresponding mono-bidentate complexes. It is probable that this change is caused by a delocalization of the excited singlet state, because a variation in Franck-Condon factors and a depolarization of the fluorescence accompanied it. In addition to the ligand-ligand interaction 1,10-phenanthroline and 2,2′-bipyridyl suffered from coordination effects. They have larger fluorescence yields and smaller phosphorescence yields than the free molecules. The decrease on the transition rate of the intersystem crossing is probably due to the changes in the energy levels of 1(n-π*) and 3(n-π*), caused by the metal-ligand bond using a “non-bonding” orbital in the free ligands.
  • Hironori Arakawa, Yoshihiko Morooka, Atsumu Ozaki
    1974 Volume 47 Issue 12 Pages 2958-2961
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Oxidation of olefin by peroxo molybdenum complex selectively yields epoxide at room temperature. The nature of the interaction of olefin with molybdenum and that of the peroxo molybdenum complex has been investigated in terms of coordination constant K of olefin and rate constant k2 of decomposition of the peroxo molybdenum-olefin complex, attention being paid to the substituent effect of olefin. The coordination constant increases with the extent of alkyl substitution on double bonded carbon, a tendency opposite to that on Pd(II), or Rh(I). The coordination state of olefin on molybdenum seems to differ from that on Pd(II) or Rh(I), for which π-back donation of metal d-electron is accepted to play an important role. The coordination complex on molybdenum is accordingly assigned to a π-complex with some electron donated to molybdenum. A remarkable steric effect of alkyl substituent is observed, disclosing a difference from the oxidation of uncoordinated olefin. Since k2 increases with K, revealing a similar substituent effect of olefin, the peroxo oxygen seems to be electrophilic, and the peroxo oxygen-molybdenum bond seems to be rather covalent than ionic, thus giving rise to epoxidation.
  • Keiichi Ohno, Yuji Shiro, Hiromu Murata
    1974 Volume 47 Issue 12 Pages 2962-2968
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The vibrational spectra of dichloroethylmethylsilane and 2,2-dichlorobutane have been measured. The vibrational assignments of these molecules have been made in relation to the rotational isomerism. The normal vibration calculations based on the modified Urey-Bradley force field have been carried out and have confirmed for both molecules that, in the liquid state, the trans and gauche isomers coexist, while the trans isomer alone persists in the crystalline state.
  • Yukishige Kitano, Kiyotomi Kobori, Masamitsu Tanimura, Yukio Kinoshita
    1974 Volume 47 Issue 12 Pages 2969-2971
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The crystal structure of dichlorobis(acetoxime)palladium, PdCl2(C3H6NOH)2, has been determined from three-dimensional single-crystal X-ray photographic data. The crystals belong to the monoclinic system (space group P21/a), with two formula units in a cell with dimensions: a=8.709±0.007, b=13.996±0.005, c=4.756±0.006 Å, and β=95.60±0.05°. The structure was established by the heavy-atom method and was refined by the block-diagonal least-squares procedure. The Pd atoms are spaced at intervals of 4.76 Å along the c-axis and have a trans planar coordination, with two Cl atoms at 2.30 Å and two N atoms of the oxime groups at 2.03 Å. The oxime plane is twisted about the Pd–N bond by 72.7° from the coordination plane defined by the Pd, Cl, and N atoms. The complex molecules are hydrogen-bonded with each other in strings of an indefinite length along the c-axis, and the hydrogen-bond distance between the O atom of the oxime and the Cl atom is 3.07 Å.
  • Shigeyoshi Miyagishi
    1974 Volume 47 Issue 12 Pages 2972-2976
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The critical micelle concentration (CMC) of dodecyl ammonium halides and the degree of dissociation of the micelle (α) of dodecylammonium chloride were determined as functions of the concentrations of the organic additives by measuring the conductivity and the emf of the following cell: calomel/1 M-KCl/sample solution/AgCl, Ag. The CMC was raised more in the presence of acetone and dioxane than in that of acetamide, formamide, urea, and methanol, and was diminished by adding alcohols (C2–C4). The effect of the alcohols on CMC decreased in the order of the diminished hydration of the counterion, acetone and dioxane were considered to affect the dodecylammonium iodide solution specifically. The dissociation of the micelle was enhanced in the presence of organic additives. Further, we estimated the solubilized amount of the additives from the degree of dissociation of the micelle and attempted to make quantitative estimation of the increment of CMC produced by organic additives.
  • Yoshihisa Suzuki, Tadao Toki
    1974 Volume 47 Issue 12 Pages 2977-2978
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Solubility data have been obtained for the inosine–HCl–H2O and inosine–H2SO4–H2O systems at 5°C. The acid hydrolysis of inosine was satisfactorily prevented under the present conditions. Three new acid salts of inosine have been obtained: (1) C10H12N4O5·HCl·(l/2)H2O in the A-form, (2) C10H12N4O5·HCl·(1/2)H2O in the B-form, and (3) C10H12N4O5·H2SO4·2H2O. Their X-ray powder diffraction data are given. All of them are incongruent and decomposed by pure water; however, they are stable in air during storage at room temperature.
  • Kohji Tadasa, Naomi Imai, Tetsuo Inaba
    1974 Volume 47 Issue 12 Pages 2979-2981
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The kinetics of the H2–NO pyrolysis was studied at 400°C; the reaction was found to be first-order in H2 and to be independent of NO. It is suggested that the reaction proceeds by means of a free-radical chain mechanism: H2+NO(surface)→HNO+H(1), H+NO\ ightleftharpoonsHNO (2), 2HNO→2OH+N2 (3) OH+H2→H2O+H(4) and 2HNO→H2O+N2O(5). This reaction scheme resembles that proposed for the CH2O–NO pyrolysis at 500°C except for the initiating step (1), which takes place on the wall of the vessel in the H2–NO pyrolysis.
  • Masumi Yamakawa, Kiyoshi Ezumi, Yoshiko Mizuno, Tanekazu Kubota
    1974 Volume 47 Issue 12 Pages 2982-2985
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The singlet-triplet absorption spectra of various pyridine N-oxide derivatives with an electron-donating substituent have been observed by applying the oxygen-intensification technique. The nature of the lowest triplet (T1 states of these N-oxides and the substituent effect on the T1 state of pyridine N-oxide have been discussed experimentally and theoretically. The T1 states of the above substituted pyridine N-oxides were assigned to a π-π* transition of a 3La (CT) nature; 3A1 for the p-substituted pyridine N-oxides. All the singlet-triplet absorption bands as well as the singlet π-π* bands recorded here show a blue shift in polar solvents; this phenomenon is also discussed. Last, the mutual relation between the contact charge-transfer bands and the singlet-triplet absorption bands, both enhanced by compressed oxygen, has been discussed, since, for pyridine N-oxides with p-N(CH3)2, p-OCH3, and m-NH2, we could not record the singlet-triplet absorption band clearly.
  • Takeo Okumura, Akio Nakamura, Kazuo Tajima, Tsunetaka Sasaki
    1974 Volume 47 Issue 12 Pages 2986-2990
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A tritiated ampholytic surfactant, N-dodecyl-β-alanine, C10H21–(CHT)2–NH2+–(CH2)2–COO, was synthesized, and the amount of adsorption on an aqueous surface was measured directly by the radiotracer method. The adsorption isotherm near the neutral pH region showed a saturation value of 3.73×10−10 mol/cm2 above the concentration of about 1/5 of the critical micelle concentration in the absence of added salt, and a value of 4.74×10−10 mol/cm2 above the critical micelle concentration in the presence of 1 mol/l NaCl. In the presence of 1 mol/l NaCl, no effect of pH on the adsorption was found. The Gibbs adsorption isotherm applicable to the aqueous ampholytic surfactant was derived. The observed amounts of adsorption in the presence and absence of NaCl were in good agreement with the values calculated from the Gibbs adsorption isotherm, using the surface tension data measured by the Wilhelmy plate method.
  • Mitsuo Higuchi, Takatoshi Koyakumaru, Ryoichi Senju
    1974 Volume 47 Issue 12 Pages 2990-2993
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A series of aminoethyl derivatives of poly (vinyl alcohol) was synthesized, and their adsorption behavior onto a cellulosic fiber was investigated. The results indicate that the primary factor causing adsorption is the charge interaction at the solid-liquid interface; the adsorption was suppressed as the concentration of a foreign salt (NaCl) exceeded 0.02 M, and polymers bearing no cationic group poly(vinyl alcohol) and its aminoethyi derivatives in the un-ionized state) exhibited no appreciable adsorption. The results also demonstrate that the primary variable controlling the amount of adsorption is the charge density on the polymer; the amount of adsorption increases steeply with an increase in the charge density up to a maximum, and then decreases with the increase in the charge density.
  • Tetsuo Morimoto, Mahiko Nagao, Junichiro Imai
    1974 Volume 47 Issue 12 Pages 2994-2997
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The interaction between water and the fully-hydroxylated surfaces of silica,alumina and silica-alumina has been investigated by measuring the physisorption isotherms of water at three temperatures and by computing the isosteric heat of adsorption and the site energy distribution therefrom. The number of adsorption site evaluated on the surfaces of each of the two component oxides decreases exponentially with the increase in the site energy, whereas that of the silica-alumina samples gives a peak at a relatively high energy region, suggesting the presence of strong water-physisorption sites characteristic to silica-alumina. These results can be elucidated on the basis exponentially of the postulation that new sites having protonic acid character appear when the two component oxides contact with each other, as described previously. Furthermore, it is found that the strength of such new sites for physisorption of water increases with decreasing content of alumina in silica-alumina.
  • Tsutomu Koide, Masami Tsujino, Kazuhiro Sawada, Tsutomu Oda
    1974 Volume 47 Issue 12 Pages 2998-3000
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The phase transition point of solid hexabromoethane was found at 177°C, above which the crystal is a body centered cubic lattice with two molecules in a unit cell, having a cell length of 7.80 Å at 185°C. From an analysis of entropy change, it seems that random orientations of the molecular axis would occur at the transition point. The influence of halogen substitution is discussed. It was concluded that the phase transition will be dominated mainly by the geometrical properties of the molecules.
  • Yoshihiro Nakato, Takeshi Chiyoda, Hiroshi Tsubomura
    1974 Volume 47 Issue 12 Pages 3001-3005
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Ionization potentials (Ip’s) of several organic compounds have been determined by the method of photocurrent measurements in gas and organic solvents. It has been found that the vapor-phase Ip’s, calculated from those determined from the onsets of the photo-currents in solutions by using Born equation for the solvation energies of the cations and a common term for the energy of the electron in solution, agree well with those measured in the vapor phase. Based on this result, the Ip’s of molecules in the gas phase can be derived from those measured in the solution. This method is useful for the determination of Ip’s of large molecules which cannot be obtained in the gas phase. Some of the Ip’s obtained are: 5.6 for 1,1,4,4-tetrakis(dimethylamino)butadiene, 5.7 for 3,3′-dimethyl-2,2′-bibenzothiazolinylidene, 6.4 for β-carotene, 6.1 for chlorophyll a, 6.3 for dihydridobis(π-cyclopentadienyl)tungsten (eV unit). The conditions of lowering the Ip’s of organic molecules are discussed.
  • Michiro Hayashi, Kazunori Kuwada
    1974 Volume 47 Issue 12 Pages 3006-3009
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The microwave spectra of six isotopic species of diethyl ether were measured in relation to the molecular form and dipole moment. Transitions of the TT(trans-trans) isomer could be assigned and the rs structure of this isomer was obtained by the substitution method. The structural parameters of the TT isomer of diethyl ether are; r(CO) 1.408 Å, r(CC) 1.516 Å; α(COC) 112°25′, α(OCC) 108°37′ for the skeleton; r(CH) 1.093 Å, α(CCH) 110°11′, α(OCH) 110°10′, α(HCH) 107°29′ for the CH2 group and r(CH) 1.090 Å, α(CCHs) 110°35′, α(CCHa) 110°15′, α(HsCHa) 108°48′, α(HaCHa) 108°4′ for the CH3 group. The dipole moment was determined to be 1.061±0.018 D from the Stark effect measurement for the TT isomer. A discussion was made on the structure and the dipole moment of the TT isomer of diethyl ether in comparison with those of the similar molecules.
  • Tohru Nagai, Hiroaki Takahashi, Keniti Higasi, Leslie E. Sutton, David ...
    1974 Volume 47 Issue 12 Pages 3010-3013
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Atom polarisations, apparent dipole moments and dielectric relaxation times of 1,4-benzoquinone in various solvents were determined together with those of some of its derivatives in benzene solution. Solvent effects on the apparent dipole moments of 1,4-benzoquinone and its derivatives were examined in comparison with the absorption spectra in the submillimetre region.
  • Shoji Hiroma, Haruo Kuroda
    1974 Volume 47 Issue 12 Pages 3014-3020
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The potassium-chloranil (K+·CA), sodium-chloranil (Na+·CA) and sodium-bromanil (Na+·BA) salts were found to form hydrates when their crystalline powders are exposed to a humid air. In the single crystal spectrum of K+·CA, the charge-transfer band significantly increased its intensity on hydration, exhibiting the same polarization as in the spectrum of the water-free state. It was concluded that CA ions in the hydrate crystal are closely stacked on each other to form columns as in the water-free crystal and the charge transfer interaction between CA ions is stronger in the hydrate crystal than in the water-free crystal. The spin concentration of K+·CA markedly decreased on hydration, it being 2.2×1022 spins per mol in the state of hydrate while 5.5×1023 spins per mol in the water-free state. The hydration resulted in an increase of the intensity of charge-transfer band and a decrease of the spin concentration also in the cases of Na+·CA and Na+·BA. It is also shown that organic solvents such as acetone, methy ethyl ketone and dichloromethane can enter into the crystal lattice of K+·CA to form the solvent-containing crystals.
  • Yukito Murakami, Kazunori Sakata, Kenji Harada, Yoshihisa Matsuda
    1974 Volume 47 Issue 12 Pages 3021-3024
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The solution spectra of two tris(dipyrromethenato)manganese(III) complexes and of one bis(dipyrromethenato) manganese (II) as well as the diffuse reflectance spectrum for the latter were examined. The high spin state was confirmed for all the manganese complexes by magnetic susceptibility measurements. For the tris-complexes, one broad low energy band (∼9500 cm−1) is assigned to the 5A1g5B1g transition and one pair of higher energy bands (∼14000 cm−1) are attributed to the 5B2g5B1g and 5Eg5B1g transitions for a D4h symmetry as a consequence of Jahn-Teller effect. In the bis-complex, manganese(II) is placed in a tetrahedral ligand field and one group of ligand-field bands lying below 16000 cm−1 are assigned to: 4T1(4G)←6A1(6S), 4T2(4G)←6A1(6S), and 4E, 4A1(4G)←6A1(6S) in an increasing order of energy. The exceedingly high intensity of these bands is ascribed to the covalent nature of coordinate bonds. A strong IR band due to the skeletal stretching mode of the dipyrromethene moiety was observed in the 1600 cm−1 range and shifted slightly toward lower energy upon metalcoordination.
  • Yukito Murakami, Kazunori Sakata
    1974 Volume 47 Issue 12 Pages 3025-3028
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The zinc (II) chelates of five dipyrromethenes which have methyl substituents to a various extent, as well as that of 5,5′-diphenyldipyrromethene, have been prepared. The behaviors of methyl resonances upon metalcoordination were classified into three cases: (1) a down-field shift, but not greater than that of the corresponding ligand hydrochloride (3,3′-CH3); (2) nearly no change in chemical shift (4,4′-CH3); and (3) a profound up-field shift, the methyl resonance of the corresponding ligand hydrochloride showing a down-field shift on the contrary (5,5′-CH3). A marked change in chemical shift for the methine proton upon zinc(II)-coordination is related to conjugation in the chelate ring–the presence of aromaticity. As a whole, methyl resonances for the zinc chelates are consistent with the tetrahedral coordination geometry. Electronic absorption peaks for the zinc chelates, which were located in the lowest energy region with the highest intensity, were assigned to the intra-ligand π→π* transition and the metal→ligand charge-transfer as well. Vibrational absorption bands appearing in the 1600 cm−1 range and in the 400–350 cm−1 region have been assigned to the skeletal stretching mode of the dipyrromethene moiety and the metal-ligand stretching mode, respectively, for the zinc chelates.
  • Masami Haruta, Zen-ichi Yoshida, Hisanobu Ogoshi
    1974 Volume 47 Issue 12 Pages 3029-3032
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The dissociation constants of eleven 2-hydroxy-4 or 5-substituted acetophenones were determined in a 22.5% water–dioxane-mixed solvent system at 25 and 40°C by potentiometric titration. They were then discussed in terms of the electronic effect of the substituents and the linear-free-energy relationship. The stability constants bis(2-hydroxy-4 or 5-substituted acetophenonato)copper(II) were also determined under the same experimental conditions; a linear relationship between the dissociation constants and the stability constants was obtained for bis(2-hydroxy-4 or 5-substituted acetophenonato)copper(II). No significant difference has been found in the effects of 4- and 5-substituted groups on the stability constants.
  • Tairoku Yano, Hiroshi Kobayashi, Keihei Ueno
    1974 Volume 47 Issue 12 Pages 3033-3036
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Stability constants were determined at 25 °C for the metal chelates of racemic cis- and diequatorial trans-2,3-diamino-trans-decalins, cis- and trans-2,3-diaminotetralins and 3,3-dimethyl-1,2-diaminobutane (BEDA), where Cu(II), Ni(II) and Zn(II) are metal ions. Alicyclic trans-diamines afforded 1 :1 complexes more stable than those with cis-isomers, regardless of the metal ions. Stability of the metal chelates with BEDA is comparable to that of the trans-diamines. The difference in stability of the trans- and cis-diamine complexes increased in the order Cu-, Zn- and Ni ions. Upon formation of 1 : 2 complexes, it became greater with Ni ion, but practically no difference was observed with the others. An explanation was given on the basis of stereochemistry of the diamines and coordination structures of the divalent metal ions.
  • Hiroshi Yokoi
    1974 Volume 47 Issue 12 Pages 3037-3040
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The ESR and visible absorption spectra of a number of bis(N-salicylidenealkylaminato)copper(II) complexes with different kinds of alkyl groups were measured in toluene. The coordinations of these complexes in toluene are distorted towards a tetrahedral geometry to varying extents; the relationship between the degree of the distortion and the ESR and visible absorption parameters was systematically investigated. Especially, the experimental fact that the absolute values of the hyperfine coupling constant with the copper nucleus decrease with an increase in the degree of distortion was discussed. A configurational equilibrium between two species with different degrees of the distortion was found to exist for the complexes with R=isopropyl and cyclohexyl in toluene.
  • Hisashi Okawa, Isao Ando, Sigeo Kida
    1974 Volume 47 Issue 12 Pages 3041-3044
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Binuclear oxovanadium(IV) and copper(II) complexes, M2(fsalap-R)(OMe) (R=H, CH3, Cl, and NO2) were synthesized and characterized, where H3fsalap-R denotes 2,6-bis[N-(2-hydroxy-5-substituted-phenyl)iminomethyl]-4-methylphenol and the metal ions are connected by the phenolic oxygen and a methanolate ion. The cryomagnetic properties of the complexes except Cu2(fsalap-NO2)(OMe) could be interpreted on the basis of the Bleaney-Bowers equation. It was found that the -2J values for the oxovanadium(IV) complexes increase in the order (VO)2(fsalap-CH3)(OMe)<(VO)2(fsalap-H)(OMe)<(VO2)(fsalap-Cl)(OMe), while those for the copper (II) complexes decrease in the order Cu2(fsalap-CH3)(OMe)>Cu2(fsalap-H)(OMe)>Cu2(fsalap-Cl)(OMe). These facts could be reasonably explained in terms of the difference in structures and spin-exchange mechanisms between the oxovanadium(IV) and the copper(II) complexes. (VO)2(fsalap-NO2)(OMe) showed a very strong antiferromagnetic spin-exchange interaction (−2J=545 cm−1) compared with the other complexes (180–280 cm−1). On the other hand, the magnetism of Cu2(fsalap-NO2)(OMe) could be interpreted in terms of the Ising model.
  • Tomoko Ichinose, Yuzo Nishida, Hisashi Okawa, Sigeo Kida
    1974 Volume 47 Issue 12 Pages 3045-3048
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Three binuclear copper(II) complexes, Cu2(fsal-NMe2)(NCS)3, Cu2(fsal-NEt2)(NCS)3 and Cu2(fsal-pa)(NCS)3, have been synthesized and characterized, where Hfsal-NMe2, Hfsal-ENt2 and Hfsal-pa denote the Schiff bases prepared by the condensation reaction of 2,6-diformyl-4-methylphenol with N,N-dimethylethylenediamine, N,N-diethylethylenediamine and 2-pyridylmethylamine, respectively. It was demonstrated that the complexes essentially consist of a binuclear unit of the thiocyanato-bridged skeleton, (Remark: Graphics omitted.). The cryomagnetic properties could be explained on the basis of the equation for the tetranuclear cluster formed with two binuclear units linked by the out-of-plane bonding. The magnetisms and structures of the complexes were discussed in comparison with those of the Cu2(fsal–NR2)X3 (X=Cl, Br).
  • Takeo Kurauchi, Masanori Matsui, Yukio Nakamura, Shun’ichiro Ooi ...
    1974 Volume 47 Issue 12 Pages 3049-3056
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Green-to-blue six-coordinate mixed complexes, Cu(acac)2(en) and Cu(etac)2(diamine)(acac=acetylacetonate anion; etac=ethyl acetoacetate anion; diamine=ethylenediamine, trimethylenediamine, 2,2′-bipyridine or 1,10-phenanthroline) have been isolated by the reactions of the respective parent β-diketonate with the corresponding diamine in dry dichloromethane. On the other hand, the reaction of Cu(acac)2 with en in the mole ratio of one-to-two in dichloromethane saturated with water has resulted in purple crystals of Cu(acac)2(en)2·2H2O. This compound has been shown by X-ray analysis to consist of a square-planar copper(II) cation, coordinated by two ethylenediamine molecules, and two planar acetylacetonate anions, the plane of which is not perpendicular to, but slanted against, the CuN4 plane. One oxygen atom of the anion participates in the N–H···O hydrogen bonding with an NH2 group of the ethylenediamine molecule, while the other occupies the axial position of Cu(en)22+ (Cu···O: 2.79(1) Å). Therefore, the compound can be designated by the formula [Cu(en)2]·(acac)2·2H2O. The water hydrogen atoms seem to take part in the hydrogen bonding with the anion oxygen atoms.
  • Toshikazu Nishide, Kazuko Ogino, Junnosuke Fujita, Kazuo Saito
    1974 Volume 47 Issue 12 Pages 3057-3063
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Several cobalt(III) complexes containing amino-alcohol (amOH) chelate rings, [Co(amOH)(NH3)4]X3, [Co(amOH)(en)2]X3 and [Co(amOH)(R-chxn)2]X3 (en=ethylenediamine, chxn=trans-1,2-diaminocyclohexane, X=Cl, Br or ClO4, amOH=2-aminoethanol, 2-amino-1-propanol, 1-amino-2-propanol, etc.) were synthesized and separated into optical isomers. Their circular dichroism (CD) spectra change remarkably by the change in pH of the solution. The changes were ascribed to the dissociation of the alcoholic proton of coordinated amOH. The complexes containing a deprotonated chiral amO chelate ring exhibit strong vicinal CD bands in the first and second absorption band region. The signs and the magnitudes of these CD bands seem to depend mainly on the conformation of the amO chelate ring.
  • Nobuyuki Tanaka, Taisaku Kano, Hiroshi Ogino, Akifumi Yamada
    1974 Volume 47 Issue 12 Pages 3064-3067
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Kinetic studies of the reactions between nitrate ions and Cr(II)–Y complexes, where Y represents cyclohexanediaminetetraacetic acid (CyDTA), trimethylenediaminetetraacetic acid (TRDTA), and N-(2-hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), have been carried out. The reaction mechanisms of these complexes at the dropping mercury electrode were found to be expressed by the following equations:
    (Remark: Graphics omitted.)
    The formation constant, K, and the rate constants, k1 and k2, were determined in 0.1 M acetate buffer solutions of μ=0.5 by procedures including a curve-fitting method; the results were K=2.0×104 M−1, k1=0.55 M−1 s−1 and k2=2.8 M−1 s−1 for Cr(II)–CyDTA, K=2.4×10−5 M−1, k1=1.0×102 M−1 s−1, and k2<3 M−1 s−1 for Cr(II)–TRDTA and k1∼2×103 M−1 s−1 for Cr(II)–HEDTA.
  • Eiichi Miki, Kunihiko Mizumachi, Tatsujiro Ishimori
    1974 Volume 47 Issue 12 Pages 3068-3070
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The 15NO-complexes for M2[ReX5(NO)] (M=Rb, Cs, and pyH; X=Cl and Br) were prepared. The 15N-isotopic shift for their N–O stretching vibrations, ca. 40 cm−1, supports the view that the oxidation state of the NO group is I, while that of the rhenium atom is II. The Re–(NO) stretching and the Re–(NO) bending vibrations were observed in the 610–620 cm−1 region. A new compound, cis-(pyH)[ReCl4(NO)2], was prepared, the oxidation state of its rhenium atom being considered to be I, and that of the NO group, I.
  • Ren Iwata, Yoshihiro Makide, Takeshi Tominaga
    1974 Volume 47 Issue 12 Pages 3071-3073
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The retention indices of perhaloalkanes (perbromochlorofluoroalkanes, etc.) were measured by using a gas chromatograph with a squalane, Silicone DC 550, or Methoxy polyethylene glycol 350 column, and the correlation of the retention index with various physicochemical parameters was investigated. The retention index was found to correlate linearly with the composition of the halogen atoms in the perhaloalkane molecules; the correlation diagram appears to be of special analytical importance. The relationship between the retention index and the boiling point was also studied. The retention index was correlated linearly with the molar refractivity of the perhaloalkanes, irrespective of the polarity of the columns. The molar refractivity appears to be the inherent parameter which is most adequate for considering the regularity of the retention index. The effect of the polarity of the stationary phase on the retention index was also investigated.
  • Mamoru Ai, Sadao Suzuki
    1974 Volume 47 Issue 12 Pages 3074-3077
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The oxidations of 1-butene, butadiene, and hydrogen in a large excess of air were carried out over various V–P oxide catalysts with different P2O5 contents. The oxidation activities were compared with the dehydration activity for isopropyl alcohol, which was used as a measure of the acidity of the catalysts. The surface area and the acidity per unit of surface area sharply decrease with an increase in the P2O5 content up to about 20 mol% P2O5, while with a further increase in the P2O5 they remain almost unchanged. The activity per unit of surface area for the oxidation of butene and butadiene, as well as that for the isomerization of butene, changes in the same direction as the acidity per unit of surface area. The equilibrium constant for the adsorption of olefin changes analogously. The activity per unit of surface area for the oxidation of hydrogen is not affected by the P2O5 content. The effects of the P2O5 introduced into V2O5 on the activity and selectivity are discussed from the viewpoint of the acidic nature of the catalysts.
  • Iwao Tabushi, Zen-ichi Yoshida, Yasuhiro Aoyama
    1974 Volume 47 Issue 12 Pages 3079-3083
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Relative stabilities of 1-bicyclo[2.2.2]octyl (9), 1-benzobicyclo[2.2.2]-octenyl (10), 1-dibenzobicyclo[2.2.2]octadienyl (11), and 1-tribenzobicyclo[2.2.2]octatrienyl(12) radicals were obtained by means of the relative rates of the free radical bromine abstraction from the corresponding bridgehead bromides by a silyl radical. It was found that 9 and 12 were more stable than expected. The observed order of stability 9>10>12>11 can not be explained by the usual concepts alone. The extra stabilization of 9 or 12 (or destabilization of 10 or 11) was interpreted in terms of the local symmetry (or local asymmetry) of these radicals.
  • Seizo Tamagaki, Keishi Sakaki, Shigeru Oae
    1974 Volume 47 Issue 12 Pages 3084-3088
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Thiocarbonyl S-imide of 4,5-benzo-1,2-dithiole-3-thione reacted with primary and secondary amines of various types to give both rearranged and amine-exchanged imines. By kinetical studies a plausible mechanism involving the addition and elimination of amine on the tetravalent sulfur atom was proposed.
  • Tetsuo Otsuki
    1974 Volume 47 Issue 12 Pages 3089-3093
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The photochemical reaction of 2-alkoxy-1,4-naphthoquinones with numerous types of olefins was investigated. The reaction was found to proceed smoothly in possible combinations of quinones and olefins to give photo-addition compounds in good yields. The structure of the addition compounds was determined to be 10 by their elemental analyses, mass, IR, PMR, and chemical reactions. The photo-addition reaction is characterized by the formation of a tetrahydropyran ring. This type of photo-addition reaction has not been previously known. The scope and limitations of the new photochemical reaction were described.
  • Hiroyasu Inoue, Naomi Asaoku
    1974 Volume 47 Issue 12 Pages 3094-3097
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    It has been found that dichlorophene (bis-(2-hydroxy-5-chlorophenyl)methane) and hexachlorophene (bis-(2-hydroxy-3,5,6-trichlorophenyl)methane) have abnormally high acidities as compared with the corresponding reference compounds, i.e., 2-methyl-4-chlorophenol and 2,4,5-trichlorophenol respectively. The values of pKa for the first and second ionizations of dichlorophene in a mixed solvent of ethanol and water (1 : 1) were determined to be 9.10 and 13.1, and those of hexachlorophene, to be 5.87 and 11.9, at 18 °C. On the basis of the infrared spectra, these observations could be interpreted in terms of the additional stabilization of the resulting monoanions of these bis-phenolmethanes by means of the intramolecular hydrogen bondings between the OH and O groups.
  • Seiichi Inoue, Ryohei Yamaguchi, Kenji Saito, Kikumasa Sato
    1974 Volume 47 Issue 12 Pages 3098-3101
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A new, efficient synthesis of coenzyme Q is described. The bromination of 2,3-dimethoxy-5-methyl-p-benzoquinone gives 6-bromo-2,3-dimethoxy-5-methyl-p-benzoquinone, which is then converted to the corresponding hydroquinone diacetate by the action of zinc dust in acetic anhydride. 6-Bromo-2,3-dimethoxy-5-methylhydroquinone diacetate is reacted with 1,1-dimethyl-π-allylnickel bromide in hexamethylphosphoramide at 60 °C to afford a 70% yield of 2,3-dimethoxy-5-methyl-6-prenylhydroquinone diacetate, which is hydrogenolyzed with lithium aluminum hydride in ether and then oxidized with aqueous ferric chloride to give coenzyme Q1 in 76% yield. Similarly, coenzyme Q2, Q9, and Q10, and 6′, 10′, 14′-hexahydrocoenzyme Q4 are synthesized by the reaction of the aryl bromide with π-geranyl-, π-solanesyl-, π-decaprenyl-, and π-phytylnickel bromide respectively and by subsequent treatment with LiAlH4 and FeCl3. The stereochemistry of the products is also described.
  • Akira Ninagawa, Haruo Matsuda, Sumio Matsuda
    1974 Volume 47 Issue 12 Pages 3102-3105
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The dimeric and trimeric 2-(p-tolyloxy)ethyl acetateformaldehyde polymer model compounds and the halogenated compound of the dimer were synthesized. 2,2′-Methylenebis(5-methyl-1,2-phenyleneoxy)diethyl acetate was synthesized by the reaction of 2-(p-tolyloxy)ethyl acetate with formaldehyde in acidic media. 2-[2-(2-Acetoxyethoxy-3-chloro-5-methylbenzyl)-4-methylphenoxy]ethyl acetate was prepared by the reaction of 6-chloro-4,4′-dimethyl-2,2′-methylenediphenol with 2-chloroethanol, followed by treatment with acetic anhydride, and 2-[2,6-bis(2-acetoxyethoxy-5-methylbenzyl)-4-methylphenoxy]ethyl acetate from 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol.
  • Hitomi Suzuki, Hajime Yoneda, Terukiyo Hanafusa
    1974 Volume 47 Issue 12 Pages 3106-3108
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    9,10-Dimethylanthracene gave 9-nitromethyl-10-methylanthracene as a major product, when treated with fuming nitric acid in dichloromethane at low temperatures. In contrast, 9,10-diethylanthracene yielded 9-nitro-10-hydroxy-9,10-diethyl-9,10-dihydroanthracene, which in refluxing alcohol was readily converted into 9,10-dialkoxy-9,10-diethyl-9,10-dihydroanthracene. Possible reaction sequences for the side-chain nitration have been discussed.
  • Chung-gi Shin, Katsumi Nanjo, Eiichi Ando, Juji Yoshimura
    1974 Volume 47 Issue 12 Pages 3109-3113
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A new synthetic route to α,β-unsaturated N-acyl-α-amino acid esters (N-acyl-α-dehydroamino acid esters) is described. The dehydroamino acid esters were prepared by the dehydration of α-(N-acylhydroxyamino) acid esters (10), derived from the acylation of α-hydroxyamino acid esters (2 and 6), and by the elimination of carboxylic acid from α-(N-acyl-O-acetyl), α-(N,O-diacetyl, dipropionyl and diethoxycarbonyl-hydroxyamino) acid esters, obtained by the acylation of 2, 6 and 10, in the presence of triethylamine.
  • Fumio Suzuki, Michinori Oki, Hiroshi Nakanishi
    1974 Volume 47 Issue 12 Pages 3114-3120
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Several 9-isopropyltriptycene derivatives were prepared by addition of benzynes to 9-isopropylanthracenes. Rotation about the C9-Cpr bond of these compounds is found to be frozen at room temperature on the NMR time scale. Those compounds which carry a substituent at 1-position exist as dl-isomers, at least overwhelmingly. No sign of existence of meso-isomer is found. On the other hand, 9-isopropyl-2,4-dimethyltriptycene exists as a mixture of d, l, and meso isomers, composition of which is almost 1 : 1 : 1. Repulsive nonbonding interaction is a decisive factor to determine the conformational preference. Approximate methods for line shape analysis of two methyl groups in an isopropyl group are discussed. Activation energies for rotation about the C9-Cpr bond increase with the increase in the size of 1-substituent except for the methyl group. The smaller effective size of the methyl group than that expected from the van der Waals radius is attributed to cogwheeling arrangement of methyl and isopropyl groups at the transition state of rotation and/or the higher energy level of the ground state due to the severe interaction between methyl and isopropyl groups.
  • Sakae Uemura, Akira Onoe, Masaya Okano
    1974 Volume 47 Issue 12 Pages 3121-3124
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Treatment of nonconjugated olefins such as cis- and trans-2-butenes, cis-2-octene, and cyclohexene with MoCl5 in CCl4 gave vic-dichloroalkanes whose cis-isomer was formed predominantly, the ratio of cis- to trans-addition being 4.9–12.1, together with monochloroalkanes. Preferential formation of exo-cis-dichloride was observed in the case of norbornene and norbornadiene. Bromochlorination and chloroiodination of olefins, and aromatic bromination and iodination were carried out with mixtures of MoCl5 and halogens. The reaction scheme for chlorination is discussed.
  • Yasuaki K\={o}zai, Yoshiyuki Ikeda, Masakazu Yoshida
    1974 Volume 47 Issue 12 Pages 3125-3127
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    After the discovery of the polycondensation of glycine to form the glycine oligomer by heating in the presence of urea in a sealed tube, we investigated in order to establish the optimum reaction conditions as well as to study the reaction mechanism. The optimum conditions are attained when a mixture of 0.0133 mol (1 g) of glycine and 0.0016 mol (0.1 g) of urea is heated at about 160 °C for 20–30 hr. Under these conditions, an oligomer, composed of glycine units, with a polymerization degree of 17–18 is obtained with a 50–52% yield. The mechanism of oligomer formation is considered to be as follows: first, the urea is melted and part of it is used for converting the glycine to the corresponding amide. The glycinamide thus formed and the glycine dissolve locally in the molten urea, resulting in condensation between them. A repetition of the condensation leads to longer peptide chains.
  • Yoshimori Omote, Toshihiko Komatsu
    1974 Volume 47 Issue 12 Pages 3128-3130
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The trapping of o-quinones produced during the oxidation of 4-substituted catechols(I, R=CH3, CH2CH2CO2H, CH2CH2NH3Br, CH2CH(NH3Cl)CO2CH3) in the presence of cyclopentadiene affords adducts, which are changed into 8-substituted 5,6-diacetoxy-1,4-dihydro-1,4-methanonaphthak nes(IV, R=CH3, CH2CH2CO2H, CH2CH2NHCOCH3, CH2CH(NHCOCH3)COCH3) by treatment with acetic anhydr de-pyridine Dopaquinone (IIe) is trapped with cyclopentadiene, followed by acetylation and methylation with acetic anhydride–pyridine–methanol (13 : 2 : 2) to give the N-acetyl-2-(5,6-diacetoxy-1,4-dihydro-1,4-methanonaph-thyl-8)-L-alanine methyl ester (IVd).
  • Hiroharu Suzuki, Kenji Itoh, Isamu Matsuda, Yoshio Ishii
    1974 Volume 47 Issue 12 Pages 3131-3135
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Stepwise addition of two isocyanates to N-trimethylstannyl(diphenylmethylene)amine, Ph2C=NSnMe3, gives 3,4-dihydro-1,3-dialkyl-4,4-diphenyl-6-trimethylstannoxy-1,3,5-triazin-2(1H)-one (II) by a polar [4+2] cycloaddition of the 1/1 adduct and the second isocyanate. The isothiocyanate adducts of Ph2C=NSnMe3 react with either isocyanates or isothiocyanates to yield the corresponding consecutive insertion products (IV).
  • Daishiro Ikeda, Tsutomu Tsuchiya, Sumio Umezawa, Hamao Umezawa
    1974 Volume 47 Issue 12 Pages 3136-3138
    Published: 1974
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The total synthesis of butirosin B (5) is described. Its 3′,4′-dideoxy derivative (11) has been synthesized, a cyclic carbamate derivative (2) being used as the key compound. The dideoxy derivative (11) was prepared by hydrogenation of a 3′,4′-unsaturated derivative (10) obtained by the reaction of a di-O-mesyl derivative (9) with sodium iodide and zinc dust. The dideoxy derivative (11) was found to have significant activity against resistant bacteria producing phosphotransferase I.
feedback
Top