Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 47 , Issue 5
Showing 1-50 articles out of 64 articles from the selected issue
  • Yoshifumi Kato, Kyusaku Nishioka
    1974 Volume 47 Issue 5 Pages 1047-1053
    Published: 1974
    Released: March 27, 2006
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    The magnetic circular dichroism and absorption spectra of PrCl3 and TmCl3 in polyvinylalcohol film are measured in the range of 300–700 nm. The absorption bands observed are five for PrCl3, the transitions from the ground state, 3H4, to the excited states, 1D2, 3P0, 3P1, 1I6, and 3P2, of Pr3+, and four for TmCl3, the transitions from the ground state, 3H6, to the excited states, 3F3, 3F2, 1G4, and 1D2, of Tm3+. In order to separate the C term of the Faraday parameters, the temperature variation of the spectra is carried out at room temperature to 77 K. The Faraday parameters are derived from the experiment by the use of three methods; the method of moments, the graphical method, and curve fitting. The characteristics of these methods are discussed, and the uncertainty of the parameters obtained is estimated to be 30% or more. A group-theoretical consideration is applied for the interpretation of the results; this consideration fairly well explains the sign of the C terms obtained for PrCl3, but not for TmCl3.
  • Akio Okamoto, Kenji Kubo, Kazuyoshi Ogino
    1974 Volume 47 Issue 5 Pages 1054-1057
    Published: 1974
    Released: March 27, 2006
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    The osmotic pressures for poly(γ-benzyl-L-glutamate) solutions in ethylene dichloride and chloroform were measured at 29 °C in the concentration range of 2–15 vol % polymer. The osmotic pressures increased monotonously with an increase in the concentration. No evidence was found for the coexistence of two phases. The results are compared with the theory of the solutions of rodlike molecules. The values of the thermodynamic interaction parameter, χ, for the systems were found to be 0.44–0.47 in the concentration range lower than 6.5 vol% polymer, where the solutions must be isotropic.
  • Makihiko Masuda, Koshiro Miyahara
    1974 Volume 47 Issue 5 Pages 1058-1063
    Published: 1974
    Released: March 27, 2006
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    By the use of 13C- and 18O-labelled carbon dioxide and D2 gas, water gas reaction over an evaporated Pt film was studied at temperatures 380–450 °C under constant elimination of water vapor with cold traps. The reaction of CO2 and H2 was as rapid as that of CO2 and D2, the mixture of H2 and D2 changing rapidly into an equilibrium mixture of H2, HD, and D2 in the course of the reaction with CO2. The mixture of C18O2 and CO2 was also rapidly equilibrated by the reaction with H2. The exchange reactions of 18O and 13C between CO2and CO in the course of the water gas reaction were similarly observed. The theory of the stoichiometric number on the rate-determining step was applied to the results. From the results and the observed rate equation of the water gas reaction, V=k[CO2]0.6[H2]−0.5, the reaction was supposed to be caused by the sequence of steps, CO2\ ightleftharpoonsCO2(a), H2\ ightleftharpoons2H(a), CO2(a)+H(a)\ ightleftharpoonsX(a), X(a)\ ightleftharpoonsCO(a)+OH(a), CO(a)\ ightleftharpoonsCO, and OH(a)+H(a)\ ightleftharpoonsH2O, and to be rate-controlled by the third and fourth steps, where (a) denotes the adsorbed state and X(a) is an intermediate to rule out the direct conversion of CO2(a)+H(a) into CO(a)+OH(a).
  • Kozo Tanabe, Takashi Sumiyoshi, Katsue Shibata, Tadamitsu Kiyoura, Jun ...
    1974 Volume 47 Issue 5 Pages 1064-1066
    Published: 1974
    Released: March 27, 2006
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    We have proposed a new hypothesis that the acid sites on binary metal oxides are formed by an excess of a negative or positive charge in the mixed oxides and that whether the charge is excess or not, and whether it is positive or negative, are determined by the coordination numbers and valences of the positive and negative elements in the model structures pictured according to two postulates. The validity of the hypothesis is, in fact, 90% for the 31 kinds of binary oxides tested, much higher than the validity (48%) of Thomas’ hypothesis. The hypothesis explains well the mechanism of the acidity generation of binary oxides and predicts whether the acid sites will be of the Brönsted or the Lewis type.
  • Takeo Okumura, Kazuo Tajima, Tsunetaka Sasaki
    1974 Volume 47 Issue 5 Pages 1067-1069
    Published: 1974
    Released: March 27, 2006
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    Ampholytic surfactant, N-alkyl-β-alanine, was synthesized and its infrared absorption spectra, surface tension, isoelectric points and critical micelle concentrations of aqueous solutions were measured at various electrolyte concentrations, pH and temperature. The measurements of isoelectric points and infrared spectra confirmed a zwitterionic sructure of N-alkyl-β-alanine. The critical micelle concentrations determined by surface tension measurements are 1.3×10−2 and 9×10−4mol/l respectively for the decyl and dodecyl homologs at 30 °C, the values decreasing with the increase in pH, electrolyte concentration and temperature.
  • Tetsuo Miyazaki, Yoshiteru Fujitani, Zen-ichiro Kuri
    1974 Volume 47 Issue 5 Pages 1070-1074
    Published: 1974
    Released: March 27, 2006
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    The luminescence from 2,3-dimethylbutane (23DMB) containing a small amount of toluene (To) has been observed in the solid phase at 77 K during γ-irradiation or by ns pulse irradiation with X-rays. The emission spectrum from 23DMB–To (2 mol%) during γ-irradiation at 77 K consists of the fluorescence from the singletexcited toluene and the phosphorescence from the triplet-excited toluene. Both the singlet- and triplet-excited toluenes are formed by the energy transfer from the irradiated 23DMB to toluene. When nitrous oxide or propylene is added to the 23DMB–To mixture, the emission spectrum is changed and becomes very similar to that from the 23DMB–To mixture during illumination with UV lights at 77 K. The spectrum, which disappears upon the addition of nitrous oxide or propylene, consists mainly of phosphorescence. It is concluded that the triplet-excited toluene may be formed by the migration of a hole and an electron. The effects of electron scavengers, such as nitrous oxide and carbon dioxide, or hole scavengers, such as propylene or tetramethylethylene, on the fluorescence have been studied by nsec-pulse irradiation. Since the fluorescence is not appreciably affected by the addition of these scavengers, the singlet-excited toluene may be formed by the excitation transfer.
  • Hirofumi Okabayashi, Masataka Okuyama, Teizo Kitagawa, Tatsuo Miyazawa
    1974 Volume 47 Issue 5 Pages 1075-1077
    Published: 1974
    Released: March 27, 2006
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    The Raman spectra were measured for sodium alkyl sulfates and potassium aliphatic carboxylates in the solid state and aqueous solutions. Vibrational assignments of Raman lines were made, and characteristic Raman lines of the alkyl sulfate ion were identified. The ethyl sulfate ion in the aqueous solution was found to exist predominantly as the trans form about the CH2–O bond. For higher alkyl sulfate ions in aqueous solutions, Raman lines due to rotational isomers with gauche CH2–CH2 bonds were observed. Longitudinal accordion frequencies of the solid state and aqueous solutions were compared in order to discuss the conformations of hydrocarbon chains in solution.
  • Michiya Itoh, Tsutomu Mimura, Toshihiko Okamoto
    1974 Volume 47 Issue 5 Pages 1078-1080
    Published: 1974
    Released: March 27, 2006
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    In the previous paper two kinds of fluorescences due to the intramolecular exciplex (above ∼200 K) and the charge-transfer complex (below ∼160 K) were reported in a nonpolar solution of the (9,10-dicyanoanthracene)(CH2)3-(naphthalene) systems. The fluorescence quantum yields as well as the fluorescence lifetimes of the exciplex and CT complex determined at several temperatures show a discontinuous change from room temperature to 77 K. The radiative and nonradiative decay constants of these fluorescent states suggest that the radiative decay in the exciplex is comparable with the nonradiative decay, while the nonradiative process is predominant in the excited state of the CT complex.
  • Toshiko Kodama, Shigekazu Kumakura
    1974 Volume 47 Issue 5 Pages 1081-1084
    Published: 1974
    Released: March 27, 2006
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    The 1: 1 complex of pyromellitic dianhydride with trans-stilbene crystallizes in the space group P21/c with two pairs of the component molecules in a unit cell with dimensions of a=12.48, b=6.33, c=13.17 Å, and β=111.6°. The structure was solved from a three-dimensional |E|2 Patterson synthesis and refined by a block-diagonal least-squares method to a final R value of 0.12 for 1635 reflections. In the trans-stilbene molecule, the plane containing the central ethylene group makes an angle of 11.5° with the phenyl plane. The non-planarity of the trans-stilbene molecule seems to be largely due to a steric repulsion between the hydrogen atom attached to the ethylene moiety and that at the 6 and 6′ position in the phenyl group. The pyromellitic dianhydride molecule is approximately planar. The component molecules are stacked alternately in infinite columns along the a axis. The average spacing between the phenyl plane of trans-stilbene and the molecular plane of pyromellitic dianhydride is 3.59 Å, and these palnes make an angle of 4.8° with each other. The relative arrangement of the component molecules in the crystal differs from that observed in the crystal of the anthracene, pyrene, or perylene complex with pyromellitic dianhydride. The van der Waals forces are considered to be more important than the charge transfer force in determining the relative arrangement of the component molecules in this crystal.
  • Shunsuke Kobinata
    1974 Volume 47 Issue 5 Pages 1085-1088
    Published: 1974
    Released: March 27, 2006
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    The electronic structures of Cu(II) complexes with D4h effective molecular symmetry have been investigated by means of the configurational interaction method. The locally-excited configurations of the central metal ion and the charge-transfer configurations corresponding to an electron transfer from the ligand system to the central metal ion have been taken into account. A correspondence with the crystal-field treatment has been obtained using the partitioning technique of solving the secular equation. The energies of the charge-transfer configurations, the resonance integrals, and the electrostatic contribution, Dsion, were determined so as to fit the observed d-d spectra.
  • Yasuhiro Iwasawa, Sadao Ogasawara, Takaharu Onishi, Kenzi Tamaru
    1974 Volume 47 Issue 5 Pages 1089-1092
    Published: 1974
    Released: March 27, 2006
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    The mechanisms of the deuterium addition to propylene and the propylene-deuterium exchange reaction over the electron donor-acceptor (EDA) complex of polynaphthoquinone with potassium were investigated by means of mass and microwave spectrometry and gas chromatography in the range from room temperature to 200°C. The hydrogenation as well as the exchange reaction proceeded via the half-hydrogenated state of propylene formed from the adsorbed propylene and the dissociatively-adsorbed deuterium atom on the EDA complex. However, the rate of the exchange reaction decreased upon the Fe addition to the complex, while the hydrogenation was markedly accelerated. The intermediate of the propylene-deuterium exchange reaction was determined to be the half-hydrogenated isopropyl species, whereas the deuterium addition to propylene was suggested to occur via another half-hydrogenated state, the n-propyl species.
  • Hajime Suzuki, Noriko Shinozuka, Shigeo Hayano
    1974 Volume 47 Issue 5 Pages 1093-1096
    Published: 1974
    Released: March 27, 2006
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    Orange OT (l-o-tolyl-azo-2-naphthol) dissolved in an aqueous ethanol solution and solubilized in various surfactant solutions, containing a citric acid-disodium hydrogen phosphate buffer, showed well-defined irreversible polarographic waves. The anionic, cationic, and nonionic surfactants used were sodium dodecyl sulfate (SDS) and sodium dodecylbenzenesulfonate (SDBS), dodecyltrimethylammonium chloride (DTMAC), and polyoxyethylene nonylphenyl ether (NP-\bar10) respectively. The values multiplying the transfer coefficient by the number of electrons involved in the activation step, (αna), were calculated from the semilogarithmic plot of the wave. The plots of αna against the half-wave potential of Orange OT for each solution showed that a marked surfactant electric-charge dependence of αna was observed with a variety of surfactant solutions; i.e., the electric-charges of the surfactant molecules or micelles remarkably affected the electrode kinetics of the solubilized Orange OT. No matter what Orange OT is an uncharged species, Orange OT solubilized in the anionic surfactant solutions seemed to behave in the electrode process as if it were an anionic species, and when solubilized in the cationic and nonionic surfactant solutions it seemed to behave as a cationic species.
  • Isao Ando, Atsuo Nishioka, Masahiro Kondo
    1974 Volume 47 Issue 5 Pages 1097-1104
    Published: 1974
    Released: March 27, 2006
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    The 13C chemical shifts of several n-alkanes (CH4, C2H6, C3H8, C4H10, C5H12, C6H14, and C7H16) were calculated using a linear combination of the gauge invariant atomic orbitals-molecular orbital theory of Pople and the INDO and MINDO/2 methods, and the results were compared with the experimental data reported by Grant et al. The calculated chemical-shift differences among the carbons in these molecules were found to agree with the observed data except in some cases, whereas the observed order of the chemical shift of the carbons in n-alkanes, which have more than two magnetically nonequivalent carbons, cannot be interpreted by means of the average excitation energy (ΔE) approximation. Histograms showing the distribution of the excitation energies from the occupied to unoccupied orbitais were obtained and compared with ΔE.
  • Akio Yamamoto, Yuji Shiro, Hiromu Murata
    1974 Volume 47 Issue 5 Pages 1105-1112
    Published: 1974
    Released: March 27, 2006
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    A force field which reproduces satisfactorily both the observed vibrational frequencies and the elastic constants has been determined for the sodium nitrate crystal using the short-range interaction model. In addition to the short-range interactions, the long-range interactions of the vibrationally-induced dipoles were also taken into consideration on the basis of the rigid-ion model; those effective charges which explain fairly well the observed TO–LO frequency splittings were obtained. The distribution of the effective charges on each atom was examined; the best set of effective charges has been found to be ZNa=0.87e, ZN=0.17e, and Zo=−0.35e.
  • Masao Matsui, Masashi Imamura
    1974 Volume 47 Issue 5 Pages 1113-1116
    Published: 1974
    Released: March 27, 2006
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    The liquid-phase radiolysis of acetone, methyl ethyl ketone, and diethyl ketone with 4He–, 12C–, and 14N–ions was carried out with the intention of discovering the specific reactions taking place in a very high LET region. The heavy ions were accelerated at various energies with an IPCR cyclotron, the LET of which was up to 80 eV/Å. The radiolytic yields of the main gaseous products, hydrogen and carbon monoxide, were found to increase appreciably with an increase in the LET and to reach the maximum values in the LET region between 50 and 70 eV/Å. The ratios of the two yields, G(H2)/G(CO), also increase substantially with an increase in the LET. These results, as well as the variations in the yields of saturated and unsaturated hydrocarbons, appear to indicate a thermal-spike effect which may bring about the thermal decomposition of free radicals, giving rise to the enhanced G(H2) and G(CO) values in the high LET region.
  • Keiichi Fukuyama, Shozo Shimizu, Setsuo Kashino, Masao Haisa
    1974 Volume 47 Issue 5 Pages 1117-1121
    Published: 1974
    Released: March 27, 2006
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    The crystal structure of (±)-1-benzyl-5-phenyl-1-azacycloheptan-4-one hydrochloride has been determined by the heavy-atom method from three-dimensional X-ray data. The crystals are monoclinic, space group P21c, with four formula units in a unit cell of dimensions: a=5.967(8), b=11.20(1), c=25.96(2) Å, and β=93.8(3)°. The structure was refined by the block-diagonal least-squares method to an R index of 0.076 for 1299 independent observed reflections. The benzyl and phenyl groups are bonded equatorially to the azacycloheptanone ring which takes a chair-like conformation. The chloride ion is hydrogen-bonded to the ring nitrogen atom at a distance of 3.075(4) Å.
  • Nobuhiko Muto
    1974 Volume 47 Issue 5 Pages 1122-1128
    Published: 1974
    Released: March 27, 2006
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    The effect of counterions on the titration behavior of poly(itaconic acid) (PIA) was studied by titrating PIA in aqueous solutions containing alkali metal salts and a tetramethylammonium salt at 25°C. The acidity of the primary carboxylic groups of PIA increases in the order (CH3)4N+<Li+<Na+<K+, whereas that of the secondary carboxylic groups increases with the decrease in the crystallographical radii of the counterions, in the order (CH3)4N+K+<Na+<Li+, in agreement with the results for ordinary polycarboxylic acids. The order K+>Na+>Li+ on the binding strength to the primary carboxylate groups in the first dissociation step is interpreted in terms of the radii of the hydrated cations; it can be ascribed to the stable ring structure of the monoanion of the itaconic acid residue, resulting from the hydrogen bonding between two adjacent carboxylate groups. In apparent complete dissociation, about 80, 60, and 40% of the itaconate residues bind to Li+, Na+, and K+ ions, respectively, when it is assumed that no (CH3)4N+ ions are bound to the carboxylate groups.
  • Tamaichi Ashida, Masao Kakudo
    1974 Volume 47 Issue 5 Pages 1129-1133
    Published: 1974
    Released: March 27, 2006
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    The structures of the prolyl residues as found in the crystals of various oligopeptides were studied, and a few interesting structural features were found, (i) The Cα–C′–N angle of the peptide group formed by the N atom of the pyrrolidine ring and the Cα and C′ atoms of the preceding residue is widened to about 118° from the usual value of 114° due to the steric repulsion between the Cα and the two hydrogen atoms bonded to the Cδ atom of the pyrrolidine ring, (ii) The Cγ atoms of some pyrrolidine rings have some sort of disorder, and the Cβ–Cγ and Cγ–Cδ bonds seem to be shortened and the Cβ–Cγ–Cδ angles seem to be widened than usual, (iii) Almost half of the pyrrolidine rings have an approximate C2 (half-chair) symmetry, the twofold axis passing through the N atom and the midpoint of the Cβ–Cγ bond. The others have an approximate Cs (envelope) symmetry, the mirror plane passing through either the Cβ or Cγ atom with equal probabilities. In this case the NCαCαCγCδ or NCαCβCδgroups are almost planar, respectively, (iv) The conformation of Cγ-exo against the C′ atom bonded to the Cα atom is mainly found in the residues having the α-helix type torsion angles, while the Cγ-endo is in those having the collagen type torsion angles.
  • Jim Nakagawa, Isao Suzuki, Takehiko Shimanouchi, Tsunetake Fujiyama
    1974 Volume 47 Issue 5 Pages 1134-1138
    Published: 1974
    Released: March 27, 2006
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    The ν26 band of methyl fluoride has been measured with a high-resolution infrared spectrometer. The molecular constants are obtained with the least-squares method. The effect of the x,y-type Coriolis interaction is discussed and the theoretical spectra are compared with the observed spectrum.
  • Katsumi Kaneko, Katsuya Inouye
    1974 Volume 47 Issue 5 Pages 1139-1142
    Published: 1974
    Released: March 27, 2006
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    The electrical conductivity of α-FeOOH, β-FeOOH, and γ-FeOOH was measured in dry air at room temperature in the frequency range of dc to 10 MHz under various pressures of 9–150 kg/cm2. The logarithm of conductivity, log σ, shows a linear relationship with the ratio of true density to apparent density, d0/d′, of the samples compressed at different pressures. σ1 at 7 MHz, determined by extrapolating the logσ vs. d0/d′ plots to unity of d0/d′, is proportional to the number of the nearest iron atoms with identical spin. The conductivity increases with increasing frequency f. The ac conductivity σac which equals σ minus σdc, where σdc is the dc conductivity, is proportional to fs (0.6<s<0.8) in the lower frequencies than 1 MHz. This behavior is presumed to be due to the hopping of a d-electron in the t2g-orbital of Fe2+ to the t2g-orbital of adjacent Fe3+, through a slight overlapping of t2g-orbitals of Fe2+ and Fe3+.
  • Hiroatsu Matsuura, Tatsuo Miyazawa
    1974 Volume 47 Issue 5 Pages 1143-1147
    Published: 1974
    Released: March 27, 2006
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    The Brillouin scattering from tetragonal pentaerythritol crystals was measured by using a helium–neon laser and a pressure-scanned Fabry-Perot interferometer. The Brillouin components from the longitudinal acoustic mode and the transverse acoustic mode polarized parallel to the scattering plane were observed for various crystal directions with the scattering vector in the (001) and (010) planes. From the observed Brillouin shifts, the frequencies and velocities of sound waves with the wavelength of 290 nm were obtained, and the elastic constants were determined, in units of 1011 dyn/cm2, as C11=3.94±0.01, C13=0.76±0.03, C16=0.005±0.05, C33=1.33±0.02, C44=0.44±0.03, and 2C66+C12=5.13±0.03. The present hypersonic values of the elastic constants were compared with previous values by the ultrasonic technique.
  • Norio Kaneko, Hiroaki Takahashi, Keniti Higasi
    1974 Volume 47 Issue 5 Pages 1148-1151
    Published: 1974
    Released: March 27, 2006
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    Far infrared spectra from 400 to 30 cm−1 of triglycine sulfate and its deuterated analogue were measured and the bands due to the librational modes of glycine molecules were identified. Polarized Raman spectra below 300 cm−1 of triglycine sulfate single crystals were measured and the symmetry species of the observed lattice vibrations were determined. Temperature dependence of the lattice vibrations was examined. Significant changes were detected in both infrared and Raman spectra on crossing the Curie temperature, indicating a flipping motion of glycine I in the paraelectric phase and suggesting the ferroelectric transition in triglycine sulfate to be of an order-disorder type.
  • Akiyoshi Matsuzaki, Saburo Nagakura, Keitaro Yoshihara
    1974 Volume 47 Issue 5 Pages 1152-1157
    Published: 1974
    Released: March 27, 2006
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    Proton donor-acceptor interactions in excited states were studied by measuring mainly time-resolved fluorescence spectra for β-naphthol–TEA in toluene and in acetonitrile, and for β-naphthylamine–TEA in nonpolar mixed solvents. The Stern-Volmer relation was found to be satisfied for β-naphthol–TEA in toluene. The rate constant and activation energy of hydrogen bond formation in the excited state of this system were obtained to be 2.2×109 M−1 s−1 at 30 °C and 1.6 kcal/mol, respectively, indicating that the process is diffusion-controlled. The time dependences of the intensities of the fluorescence bands due to the free and complexed β-naphthol were measured with the solutions containing various concentrations of triethylamine in acetonitrile. From the analysis of the result, it is shown that this system is led to the ion-pair formation via the hydrogen-bonded species in the excited state. For β-naphthylamine–TEA in nonpolar mixed solvents, the bands due to hydrogen-bonded species in the ground and excited states were observed at 370 and ∼390 nm in the absorption and fluorescence spectra, respectively.
  • Toshiaki Ohta, Masamichi Yamada, Haruo Kuroda
    1974 Volume 47 Issue 5 Pages 1158-1161
    Published: 1974
    Released: March 27, 2006
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    X-Ray photoelectron spectra of p-benzoquinone, chloranil, bromanil, iodanil, hydroquinone, tetrachlorohydroquinone and chloranilic acid were observed by using the samples freshly deposited in the high vacuum of the spectrometer. The chemical shifts of C ls and O ls levels determined from the XPS spectra are compared with the chemical shifts predicted according to the electrostatic potential model by use of the charge distributions calculated by CNDO/2 method. The charge distributions in the quinone derivatives are successfully estimated by using the observed binding energies of C ls and O ls levels.
  • Katumitu Hayakawa, Sumio Nakamura
    1974 Volume 47 Issue 5 Pages 1162-1167
    Published: 1974
    Released: March 27, 2006
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    The catalytic decomposition of hydrogen peroxide by the ammine-copper(II) complex ions has been studied using kinetic measurements, UV and visible spectroscopy, electron-spin resonance spectroscopy, and polarography. It was found that there were two reaction paths in the catalytic decomposition of hydrogen peroxide. In the first case, a linear part was observed in the plot of the amount of oxygen evolved vs. time. In this case, a brown intermediate was formed which was later found to be a diamagnetic peroxo-copper complex and to contain some of the stable oxygen anion radical just after the mixing of the reactants. The activation energy of the reaction was found to be 23±1 kcal mol−1. In the second case, no linear part was observed in the kinetic curve. In this case, the reaction had a reaction order in hydrogen peroxide varying from the first- to the second-order depending on the initial concentrations of the reactants. The nature of the brown compound and the active species of the reaction is discussed.
  • Shigeharu Naka, Fumihiko Nakakita, Yoshiko Suwa, Michio Inagaki
    1974 Volume 47 Issue 5 Pages 1168-1171
    Published: 1974
    Released: March 27, 2006
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    The change from metastable cubic to stable tetragonal form was investigated on the submicron BaTiO3 which was prepared by the hydrolysis of titanium tetraisopropoxide in barium hydroxide solution and by crystallization in the glass of BaO–TiO2–SiO2–Al2O3 system. The precipitated BaTiO3 was found to be the aggregates of minute grains of about 100 Å, to have large amount of strain and to absorb about 6% of OH and alcoholic radicals, some of them absorbed chemically. It is in a metastable cubic form. After the heating above 800 °C, it changed to stable tetragonal form in association with weight loss and decrease in lattice strain. The samples heated at 800–900 °C did not show the Curie point on the DTA curve although they were tetragonal. The samples heated at 1300 °C had the Curie point about 122 °C. The glass-devitrified BaTiO3 was also cubic and had large lattice strain. In order to change to tetragonal form, the heating above 1000 °C was needed. The metastable cubic form of submicron BaTiO3 seemed to be stabilized by the absorbants on the surface which balanced with large amount of strain in the lattice.
  • Niro Matsuura, Kisaburo Umemoto, Masao Takizawa, Yukio Sasaki
    1974 Volume 47 Issue 5 Pages 1172-1175
    Published: 1974
    Released: March 27, 2006
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    The polarographic behavior of the hexaamminecobalt(III) ion was studied in solutions of polyphosphate with different numbers of chains. The decrease in the diffusion current, id with an increase in the phosphate (Cp)-to-hexaamminecobalt(III) (CCo) mole ratio was found to be proportional to 1/4 the power of the molecular weight, M, of the Co(NH3)63+-polyphosphate. This fact shows the associated ions between Co(NH3)63+ ions and polyphosphate anions are transported to the electrode by diffusion at a rate depending on the square root of the molecular weight of the diffusion depolarizer. From the shift of the half-wave potential in the presence of excess polyphosphate, the chemical compositions of the associated ion-pairs were determined as a function of log Cp/CCo.
  • Takaharu Honjo, Masanobu Horiuchi, Toshiyasu Kiba
    1974 Volume 47 Issue 5 Pages 1176-1180
    Published: 1974
    Released: March 27, 2006
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    The synergism appearing in the liquid-liquid extraction and the extraction chromatography of trace amounts of manganese(II), cobalt(II), and zinc(II) has been investigated with TTA (thenoyltrifluoroacetone) in various solvents with or without TOPO (tri-n-octylphosphine oxide). For example, the pH1⁄2 of the extraction of Co(TTA)2 differed with the solvent used; it was, for example, 4.1 for nitrobenzene, 4.6 for cyclohexane, and 5.2 for benzene, when examined with 0.1 M TTA. When 0.01 M TOPO was present under the same conditions, the above values became 3.3, 2.4, and 3.1 respectively. The synergism was thus found to become more effective as a less polar solvent was used. The extraction constants of the three metals with only 0.1 M TTA–cyclohexane increases in the order of Mn(II)–Zn(II)–Co(II); however, when 0.001 or 0.01 M TOPO was present, all the extraction curves of the three metals became identical, even in the acidic region of pH 1–4. The overall stability constants of the adducts, M(TTA)2–(TOPO)n, increased in the order of Zn(II)–Co(II)–Mn(II), unlike the case of M(TTA)2. The adducts were found to have two TOPO for Mn(II) and Co(II), but only one for Zn(II). The extraction equilibria were found to be attained within two minutes. Unlike as in the batch extraction, the columnextraction chromatography gave a dissimilar order of the extractability of three metals (Zn(II)–Mn(II)–Co(II)) when 0.1 M TTA–cyclohexane was the stationary phase on Kel–F in the presence of TOPO. The mutual separation could not be achieved among these metals in the presence of TOPO, and the synergism was found to be rather unfavorable for the separation of metals. The relation between the batch extraction and the extraction chromatography was also discussed briefly on the basis of the distribution data obtained.
  • Yoshio Umezawa, Michio Hirota, Shizuo Fujiwara
    1974 Volume 47 Issue 5 Pages 1181-1183
    Published: 1974
    Released: March 27, 2006
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    DC polarographic behaviors of a variety of inorganic anions are examined systematically. Irrespective of chemical species, the shapes of current-potential curves are classified into three groups as a function of reduction potentials: i) E1⁄2>0 V(SCE); The so-called minima cannot be observed beyond the ecm potentials, ii) 0 V>E1⁄2>ecm; The minima can be observed, iii) E1⁄2<ecm; The distortion at the rising portion of the DC polarograms can always be observed. These results suggest that whether the minima can be observed or not is due to the difference in the relative position of half-wave potentials with respect to the ecm potential. Furthermore, it is likely that the distortion at the rising portion of the DC polarogram of Group iii) is similar in origin to that of the minima of Group ii). The present results are discussed in terms of the electron density and electronic energy level of electrons in the metal electrode. The discussion based on the phenomenological equation of Butler was also given for the sake of comparison to explain the observed phenomena.
  • Masahiko Saburi, Sadao Yoshikawa
    1974 Volume 47 Issue 5 Pages 1184-1189
    Published: 1974
    Released: March 27, 2006
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    The preparation and structural assignments of N-methyl-(S)- and -(R)-alaninatocobalt(III) complexes with N,N′-bis(β-aminoethyl)-1(R),2(R)-diaminocyclohexane (abbreviated as (R)-baetchxn) are described. The Λ2-(SSR) isomer has been obtained for Co(N-Me-(S)-ala)((R)-baetchxn)2+ ion. The two isomers, which have been found for the Co(N-Me-(R)-ala)((R)-baetchxn)2+ ion under equilibrium condition at pH 7, are assigned as the Λ2(SSR) and Λ2(SSS) configurations, taking into account the stereospecific coordination of the (R)-baetchxn. The stereoisomerism of Δ2-Co(N-Me-(S)-ala)(trien)2+ ion is also discussed. The structures of two species observed in the PMR measurements of Co(N-Me-(R)-ala)((R)-baetchxn)2+ ion and assigned to Λ2(SSR) and Λ-β-(SSS) configurations, respectively, are determined, based on the chemical shifts of α-methine protons of N-methylalaninate moieties.
  • Sumihiro Hase, Yoshio Matsushima
    1974 Volume 47 Issue 5 Pages 1190-1192
    Published: 1974
    Released: March 27, 2006
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    Muramic acid 6-phosphate was prepared from benzyl 2-acetamido-2-deoxy-3-O-[D-1′(methoxycarbonyl)-ethyl]-α-D-glucopyranoside via two reaction stages: diphenylphosphorylation under restricted conditions, followed by hydrolysis. When the reaction mixture was chromatographed on a Dowex 1×8 (formate form) column, the product was obtained as fine needles. Among the periodate oxidation products of the compound, glycolaldehyde phosphate was detected, while formaldehyde was not. Equimolar amounts of muramic acid and inorganic phosphate were produced by an alkaline phosphatase. The physical data are consistent with those of authentic muramic acid 6-phosphate.
  • Kimiko Nagai, Mitsuru Nakayama, Akihiko Matsuo, Shizuko Eguchi, Sh&uci ...
    1974 Volume 47 Issue 5 Pages 1193-1196
    Published: 1974
    Released: March 27, 2006
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    dl-Borneol and dl-isoborneol, when separately submitted to the action of boron trifluoride etherate at room temperature, gave different ethers; the one from borneol was characterized as bornyl isobornyl ether, and the other from isoborneol, as diisobornyl ether. The ethers were also obtained from borneol and isoborneol in the reaction with zinc chloride. When d-borneol was used, an optically-active bornyl isobornyl ether was obtained.
  • Kazuo Matsuura, Kazuo Senna, Younosuke Araki, Yoshiharu Ishido
    1974 Volume 47 Issue 5 Pages 1197-1200
    Published: 1974
    Released: March 27, 2006
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    The photochemical addition of lactonitrile to 3,4,6-tri-O-acetyl-D-glucal, 2,3,4,6-tetra-O-acetyl-2-hydroxy-D-glucal, methyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside, and methyl 5-deoxy-2,3-O-isorpopylidene-β-D-erythro-pent-4-enofuranoside afforded 1′-cyanoethyl 4,6-di-O-acetyl-2,3-dideoxy-α-(6a) and -β-D-erythro-hex-2-enopyranoside(6b), 1′-cyanoethyl 2,4,6-tri-O-acetyl-3-deoxy-α- and -β-D-erythro-hex-2-enopyranoside, 6a and 6b, and 1′-cyanoethyl [methyl (4R)-5-deoxy-2,3-O-isopropylidene-β-D-erythro-pentofuranosid]-4-uloside respectively, all in good yields. These facts can be explained by assuming the catalytic effect of a certain acidic species which might extricated from lactonitrile during the irradiation.
  • Kimiaki Imafuku, Junko Oda, Kenshi Itoh, Hisashi Matsumura
    1974 Volume 47 Issue 5 Pages 1201-1202
    Published: 1974
    Released: March 27, 2006
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    The dehydrogenation reaction of 2-(1-cyclohexenyl)cyclohexanone was carried out in the presence of 5% palladium-on-charcoal at temperatures 280, 300, and 320 °C, the reaction time being 1/2—8 hr. o-Cyclohexylphenol and o-phenylphenol were obtained as dehydrogenation products, and dibenzofuran as the cyclization product via o-phenylphenol. In a short reaction time, 2-cyclohexylcyclohexanone was formed together with the dehydrogenation products. The compound disappeared, the amount of two phenols and dibenzofuran increasing with reaction time. The dehydrogenation process is discussed.
  • Masatsugu Kajitani, Yoshiaki Sasaki, Junko Okada, Kazuo Ohmura, Akira ...
    1974 Volume 47 Issue 5 Pages 1203-1206
    Published: 1974
    Released: March 27, 2006
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    The catalytic hydrogenation of cyclic olefins was investigated over various nickel catalysts. The hydrogenation of cyclohexene was promoted by basic reaction conditions and depressed by acidic ones, the hydrogenation of cyclooctene being only slightly influenced by the acidity. The results of competitive hydrogenation indicate that cyclooctene is adsorbed more strongly on nickel catalysts than cyclohexene. The external olefinic bond is preferentially hydrogenated to the internal olefinic bond.
  • Tadashi Sato, Eigoro Murayama
    1974 Volume 47 Issue 5 Pages 1207-1208
    Published: 1974
    Released: March 27, 2006
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    The regio- and stereo-selectivities were observed in the radical and peracid epoxidations of limonene, endo-, and exo-dicyclopentadienes. The observations were considered in view of the proposed mechanisms for these reactions.
  • Yukio Ohto, Haruo Shizuka, Shizen Sekiguchi, Kohji Matsui
    1974 Volume 47 Issue 5 Pages 1209-1214
    Published: 1974
    Released: March 27, 2006
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    Aryloxy-s-triazines gave o- and/or p-hydroxyaryl-s-triazines upon irradiation; however, from arylamino-and arylthio-s-triazines, no photo-rearrangement product was obtained. The p-CH3, p-Cl, and p-OCH3 groups in the phenoxy moiety did not prevent the photoreaction of aryloxy-s-triazines; however, the p-CHO, p-COCH3, p-COOC2H5, and p-NO2 groups prevented the photoreaction. As to substituents in the s-triazine moiety, such groups as –Cl, –OCH3, –OC6H5, and –CH3 did not prevent the photoreaction; however, C6H5 and amino groups prevented the reaction. In the photolysis of 2,4-dimethoxy-6-(1-naphthyloxy)-s-triazine, 1-hydroxy-2-naphthyl- and 4-hydroxy-1-naphthyl-s-triazines were obtained, with the preferential formation of the former. On the other hand, from 2,4-dimethoxy-6-(2-naphthyloxy)-s-triazine, 2-hydroxy-1-naphthyl-s-triazine was obtained upon irradiation. In a similar manner, 2- and 4-acetyl-1-naphthols were obtained from 1-naphthyl acetate, and 1-acetyl-2-naphthol was isolated from 2-naphthyl acetate.
  • Juji Yoshimura, Yuichi Sugiyama, Kenji Matsunari, Hiroshi Nakamura
    1974 Volume 47 Issue 5 Pages 1215-1218
    Published: 1974
    Released: March 27, 2006
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    Addition of methanesulfenyl chloride or sulfur chloride to 3,6-dimethylene-(1a) and 3,6-dibenzylidene-1,4-dimethyl-2,5-piperazinediones (1b) gave the Markownikoff products. The addition of methanesulfenyl chloride to 1a proceeded stepwise within 1 hr, and gave a mixture of (Z,Z)-, (Z,E)-, and (E,E)-isomers of the corresponding 3,6-bis(methylthiomethylene) derivative, accompanied by gradual elimination of hydrogen chloride. 3,6-Di-chloro groups of the adduct were substituted with water, ethanethiol and ethanol to give the corresponding hydroxy, ethylthio, and ethoxy derivatives, respectively. A similar substitution with ethanedithiol and hydrogen sulfide followed by aeration gave 7,9-dimethyl-1,6-bis(methylthiomethyl)-8,10-dioxo-2,5-dithia-7,9-diazabicyclo[4,2,2]-decane and the corresponding 3,6-epitetrathio derivative, respectively. The same mode of reaction of sulfur chloride with 1a and 1b gave a few 1,6-disubstituted-7,9-dimethyl-8,10-dioxo-3,4-dithia-7,9-diazabicyclo[4,2,2]-decanes. Mass fragmentations of new compounds were also described.
  • Juji Yoshimura, Tetsuo Sekiya, Yoshio Ogura
    1974 Volume 47 Issue 5 Pages 1219-1223
    Published: 1974
    Released: March 27, 2006
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    Methyl 6-deoxy-6-guanidino-α-D-glucopyranoside, 6-deoxy-6-guanidino-D-galactose, 3-deoxy-3-guanidino-D-allose (7), and 3-deoxy-3-guanidino-D-glucose were synthesized by guanidination of the corresponding amino-sugars. The acetate of 7 was proved to exist in a bicyclic structure; 2′,4′,6′-tri-O-acetyl-D-allopyrano[l′,2′,3′;4,5,6]-2-acetylimino-1,3-diacetyl-perhydropyrimidine, whereas others exist as the usual pyranoses. Properties of the new compounds and the synthetic methods were examined.
  • Y\={o}ji Hashida, Hiroki Ishida, Shizen Sekiguchi, Kohji Matsui
    1974 Volume 47 Issue 5 Pages 1224-1227
    Published: 1974
    Released: March 27, 2006
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    The kinetics of the diazo-coupling reactions of benzenediazonium fluoroborates with 1,3,5-trimethoxybenzene and 2-naphthol have been studied in non-aqueous media including both protic and dipolar aprotic solvents. In the case of the reaction with 1,3,5-trimethoxybenzene, no significant solvent effect on the reaction rate was observed. However, in the case of the reaction with 2-naphthol, the reaction rate was affected markedly by the solvent; in dipolar aprotic solvents, the reaction proceeded much faster than in protic solvents. The observed results are interpreted in terms of the difference in solvation toward the naphtholate ion.
  • Tsutomu Yamanaka, Shumpei Sakakibara
    1974 Volume 47 Issue 5 Pages 1228-1232
    Published: 1974
    Released: March 27, 2006
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    [Asu1,6]-oxytocin, an analogue of deamino-oxytocin in which the disulfide bond is replaced by an ethylene linkage, is completely resistant to deterioration during storage under concentrated conditions. In the present study, three new analogues of this material, [Phe3, Asu1,6]-oxytocin, [Val4, Asu1,6]-oxytocin, and [Gly7, Asu1,6] -oxytocin, were synthesized to find out a hormonal compound possessing a specifically higher uterotonic activity. Among them, the [Gly7]-analogue was found to be the most promising compound; it showed a relatively higher uterotonic activity (245 IU/mg) in the rat, with a faint antidiuretic activity (0.02 IU/mg) and a weak depressor activity.
  • Shiro Kobayashi, Tadashi Ashida, Takeo Saegusa
    1974 Volume 47 Issue 5 Pages 1233-1237
    Published: 1974
    Released: March 27, 2006
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    Kinetic studies on the oxonium formation reaction between superacid esters (ROSO2X) and tetrahydropyran (THP) were carried out by means of NMR spectroscopy. The reaction was found to be an equilibrium process.
    (Remark: Graphics omitted.)
    The rate constant (k) of SN2 reaction and the equilibrium constant (1⁄K=kk′) were determined. The solvent effect was examined and k was found to be in the order: nitrobenzene>chlorobenzene≈CH2Cl2>liquid SO2. The effects of R and X in ROSO2X were studied. Relative reactivities of primary alkyl series in the reaction of ROSO2C1 with THP were: Me: Et: n-Pr=4.63: 1.0: 0.294 in CH2Cl2 and Me: Et: n-Pr=3.19: 1.0: 0.452 in nitrobenzene. The effect of X on k was in the order Cl≈CF3>F, the 1⁄K value being also extremely low when X=F. The result was discussed in relation to the kinetics of the polymerization of tetrahydrofuran (THF) by ROSO2X.
  • Yukito Murakami, Junzo Sunamoto, Koji Kano
    1974 Volume 47 Issue 5 Pages 1238-1244
    Published: 1974
    Released: March 27, 2006
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    The deacylation reactions of p-nitrophenyl carboxylates by 10-hydroxy-11-hydroxyimino[20]paracyclophane (Oxime-I) have been investigated in an alkaline aqueous acetone. Oxime-I was acylated by p-nitrophenyl laurate (PNPL) and decanoate (PNPD), but was not affected by p-nitrophenyl acetate (PNPA) and hexanoate (PNPH). Meanwhile, 2-hydroxycyclodecanone oxime (Oxime-II) and acetoxime (Oxime-III) did not undergo any reaction with all of the present carboxylic esters under the same conditions. These results suggest that the acylation reactions of Oxime-I with PNPD and PNPL proceed primarily through incorporation of the substrates into the cyclic oxime cavity. The formation of an intra-complex was also suggested by an evidence that the copper(II) ion markedly retarded the reaction rate of PNPL with Oxime-I below the catalyst-absence level. The binding constant for PNPL with Oxime-I was considerably large in comparison with the usual micelle-substrate or synthetic polymer-substrate complexes. On the basis of thermodynamic parameters for the binding and the subsequent acylation, the driving force for the incorporation and the geometry of the intra-complex have been discussed.
  • Fumikatsu Takeuchi, Tom Sugiyama, Takako Fujimori, Kazuhiko Seki, Yosh ...
    1974 Volume 47 Issue 5 Pages 1245-1250
    Published: 1974
    Released: March 27, 2006
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    Nicotinic acid and its derivatives show manifold photoreactivity depending on the solvent and the acidity of the solution. The cationic form of these compounds in general undergoes photo-hydroxylation in aqueous solutions, and photo-ethylation in ethanol solutions. The anionic form of nicotinic acid is resistant to UV-irradiation in strongly alkaline aqueous solution, but undergoes photo-decarboxylation in alkaline ethanol solution. Nicotinic acid yielded 2-(3-pyridyl)-5-pyridinecarboxylic acid in aqueous solutions at pH=4–6. Photo-substitution by 1-hydroxyethyl group occurs in the neutral forms of 3-cyanopyridine and ethyl nicotinate in ethanol solution. The photoreactivity of nicotinic acid is considered on the basis of CNDO/2 calculation.
  • Shigeo Wake, Yoshio Otsuji, Eiji Imoto
    1974 Volume 47 Issue 5 Pages 1251-1256
    Published: 1974
    Released: March 27, 2006
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    The photochemical behavior of phenazine in acidified hydroxylic solvents varied with the concentration of acids present in the solutions. Irradiation of phenazine in an aqueous phosphoric acid afforded a 1 : 1 mixture of phenazinium and 1-hydroxyphenazinium cation radicals which were converted to a mixture of phenazine and 1-hydroxyphenazine. Irradiation in moderately strongly acidified alcohols (0.1–1.0 M HCl in alcohols) or in acetic acid containing 0.1 M p-toluenesulfonic acid yielded a 1 : 1 mixture of phenazine and the corresponding 1-alkoxyphenazines or 1-acetoxyphenazine after work-up of the reaction mixture. On the other hand, irradiation in a very strongly acidified methanol (5.6–9.6 M HCl in methanol) gave only the phenazinium cation radical. Mechanistic studies revealed that in the moderately strongly acidified media the reaction proceeds through a solvent-addition to the excited singlet phenazinium monocation, and in the very strongly acidified methanol the reaction proceeds through an electron transfer from the solvent to the excited singlet phenazinium dication.
  • Shigeo Wake, Yuichi Takayama, Yoshio Otsuji, Eiji Imoto
    1974 Volume 47 Issue 5 Pages 1257-1262
    Published: 1974
    Released: March 27, 2006
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    Irradiation of phthalazine (1) and quinoxaline (2) in acidified methanol yielded 1-methylphthalazine (3a) and 2-methylquinoxaline (4), respectively. The quantum yields for the formation of 1-alkylphthalazines, which were obtained upon irradiation of 1 in acidified alcohols, varied with the sort of alcohols used and decreased in the order of methanol>ethanol>>2-propanol. When a mixture of 1 and 2,6-di-t-butylphenol (6) was irradiated in benzene containing trifluoroacetic acid under evacuated conditions, the oxidation of 6 occurred to form 3,5,3′,5′-tetra-t-butyldiphenoquinone (7) without destruction of 1. Detailed mechanistic studies suggest that the photoalkylations of 1 and 2 in acidified alcohols proceed through an electron-transfer from solvents to an excited state of the protonated diazines.
  • Tadashi Okuyama, Takayuki Fueno
    1974 Volume 47 Issue 5 Pages 1263-1266
    Published: 1974
    Released: March 27, 2006
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    PMR and CMR spectra of benzofuran and its derivatives (2-CH3, 3-CH3, 5-CH3, 6-CH3, 5-CH3O, 6-CH3O, and 5-Cl) have been measured. The chemical shifts of 2-H and 2-C of 5- and 6-substituted derivatives obeyed a modified Hammett equation, δ=ρ1σ12σ20. Electronic effects were found to be transmitted mainly through the bond 8–3. It was concluded that the ground-state electronic structure is similar to that of styrene rather than phenyl vinyl ether.
  • Tadashi Okuyama, Kiyomitsu Kunugiza, Takayuki Fueno
    1974 Volume 47 Issue 5 Pages 1267-1270
    Published: 1974
    Released: March 27, 2006
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    Bromination of benzofuran (BF) and its derivatives (5-CH3, 6-CH3, 5-CH3O, and 5-Cl) has been studied kinetically in acetic acid and by product analysis under various conditions. Product analysis revealed that bromine adds to BF in trans fashion, electrophilic bromine attacking at the 2-position. Analysis of substituent effects on the rate of bromination showed that the electronic effects are transmitted through both the bond 8–3 and the bonds 9–1–2 by a comparable magnitude. The transition state of the reaction was concluded to closely resemble a cyclic bromonium ion intermediate.
  • Tadashi Okuyama, Kiyomitsu Kunugiza, Takayuki Fueno
    1974 Volume 47 Issue 5 Pages 1271-1273
    Published: 1974
    Released: March 27, 2006
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    Cationic copolymerizations of various pairs of benzofuran derivatives have been carried out in CH2Cl2 using SnCl4–CCl3CO2H (2: 1) as catalyst at 0 °C. Effects of 2- and 3-methyl substitutions on the monomer reactivity ratio suggested that the polymeric cation adds at the 2-carbon of benzofuran. Analysis of the effects of 5- and 6-substituents on the reactivity revealed that the transmission efficiency of electronic effects through the two paths, the bonds 8–3 and 9–1–2, is comparable in magnitude. It was concluded that the transition state of the propagation step closely resembles a bridged carbonium ion intermediate.
  • A. M. Islam, A. M. Khalil, A. A. El-Maghraby
    1974 Volume 47 Issue 5 Pages 1274-1276
    Published: 1974
    Released: March 27, 2006
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    The isomeric 5-bromo- and 6-bromo-3-benzalphthalides were prepared by condensation of 4-bromophthalic anhydride with phenylacetic acids. The reaction of such isomeric bromobenzalphthalides with primary aromatic amines give the corresponding bromobenzalphthalimidines. Bromophthalazinone derivatives were obtained in good yields by the reatcion of bromobenzalphthalides with hydrazine hydrate.
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