Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 42 , Issue 11
Showing 1-50 articles out of 73 articles from the selected issue
  • Yoichiro Sato, Minoru Kinoshita, Mizuka Sano, Hideo Akamatu
    1969 Volume 42 Issue 11 Pages 3051-3055
    Published: 1969
    Released: March 27, 2006
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    Stable cation radical salts were prepared by oxidation of perylene, 9,10-diphenylanthracene, 9,10-dimethylanthracene, and 9,10-dichloranthracene with antimony pentachloride. Perylene perchlorate was also obtained in a stable form. From the temperature variations of their paramagnetic susceptibilities, the exchange coupling constants for these salts were found to increase in the sequence of above listing ranging from ∼0 to 8.5×10−2 eV. The absorption spectra of these solid compounds were compared with those observed with solutions. While the absorption bands of each salt in the visible region were found to correspond to those of the solution spectrum of the respective compound, an extra absorption band was observed in the near-infrared region for compounds with larger exchange coupling constants. The appearance of the new absorption band was reasonably ascribed to charge-transfer interaction between the radicals. These observations are considered to support further our previous suggestion that the magnitude of the exchange coupling constant obtained through magnetic measurements is basically determined by the stabilization energy due to the charger-transfer configurational interaction.
  • Hiroshi Hotta, Nobutake Suzuki, Kazuo Isoda
    1969 Volume 42 Issue 11 Pages 3056-3064
    Published: 1969
    Released: March 27, 2006
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    The effect of organic additives on the autoxidations of benzene and toluene was studied at 180°C in a ferrous sulfate aqueous solution. The additives were benzene, toluene, ethylbenzene, cumene, cyclohexene, cyclohexane, n-hexane, t-butyl alcohol, isopropyl alcohol, and ethyl alcohol. The yields of the phenol and benzaldehyde produced were measured as functions of the initial volume fraction of the additive. The yields decreased with the addition of a trace of the additive, and the yields increased still more with further addition. In order to interpret these results, the general expression for the yield of the main product was derived by the Gale-Wagner method and was analyzed numerically by using the IBM 7044. The mole fraction of the additive, corresponding to the maximum yield, can give information regarding the relative reactivity of the additive as compared with the results of the above numerical analysis. It is concluded from the present study that the experiment of the flow system for the autoxidation of toluene containing various additives is necessary to get exact kinetic information concerning these additives by using the present numerical analysis, because the equation is derived on the assumption that the concentration of the additive is constant.
  • Yoshihito Takahashi, Katsumasa Yabe
    1969 Volume 42 Issue 11 Pages 3064-3072
    Published: 1969
    Released: March 27, 2006
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    The profile of the SKβ band in various sulfur compounds, including many organic compounds, was separated into peaks, and the wavelength values and the intensities of the separated peaks were discussed in relation to the chemical bonding. The band of sulfone and sulfoxide consists of three or four peaks. We named the peaks A, B, C (the strongest), and D, beginning from the longer-wavelength side. The relative intensity of the peak A (generally named Kβ′) increases as the number of valence electrons of the sulfur atom decreases. The peak B may be attributed to the non-polar single bond of sulfur in sulfone and sulfoxide. The clear peak, D, appears only in the band of sulfite and sulfoxide. The band of the compounds of thiourea type consists of two peaks. Using the results of the above study, the chemical structures of aldehyde-bisulfite adducts and 2-mercaptobenzimidazole, etc., were discussed.
  • Akihiko Nakahara, Motohiko Koyanagi, Yoshio Murakami, Takao Edamura, Y ...
    1969 Volume 42 Issue 11 Pages 3073-3075
    Published: 1969
    Released: March 27, 2006
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    The fluorescence spectrum of toluene in benzene has been photographed at 90°K and analyzed accurately. Systematic studies of concentrations made it possible to estimate the efficiency of energy transfer from the singlet state of the host molecule to that of the guest molecule. The fluorescence spectrum of pure benzene has also been studied at 4.2°K and 90°K for comparison, and the effect of toluene as an impurity in the benzene spectra has been discussed.
  • Kayoko Ozeki, Masaji Inagaki, Jiro Tanaka
    1969 Volume 42 Issue 11 Pages 3076-3083
    Published: 1969
    Released: March 27, 2006
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    The mechanism of the intensity gain of the n–π* transition has been investigated in several carbonyl compounds; (1) cyclohexane-1,4-dione, (2) d-α-bromocamphor, (3) bromonoranisatinone, (4) d-α-cyanocamphor, and (5) spiradine A methiodide. The results on the polarized absorption spectra of single crystals at room temperature have revealed that several mechanisms are involved in the appearance of the carbonyl n–π* band. These mechanisms, (1) the vibronic coupling, (2) the lowering of the symmetry properties of the n and π orbitals by the substituent perturbations, and (3) the charge transfer from the substituents, are discussed theoretically and compared with the experimental results. It is shown that the in-plane components, either parallel or perpendicular to the carbonyl axis, are predominant as the source of the band intensity. The ratio of intensities parallel and perpendicular to the carbonyl axis is estimated by the use of the polarization results.
  • Takefumi Oka, Yoshikazu Suda, Shin Sato
    1969 Volume 42 Issue 11 Pages 3083-3087
    Published: 1969
    Released: March 27, 2006
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    The γ-radiolysis of liquid nitrogen containing ethylene and propylene has been investigated. As the nitrogenous products, hydrogen cyanide (0.18) and acetonitrile (0.04) were observed in the case of ethylene, and acetonitrile (0.12), in the case of propylene. The values in the parentheses are the G-values estimated on the basis of the energy absorbed by liquid nitrogen. In order to elucidate the mechanism of the reaction between nitrogen atoms and propylene, the mixture of C3H6 and C3D6 and the CD3CH=CHD compound have also been used as solutes. The acetonitrile obtained was mainly CH3CN and CD3CN in the former case, and CD3CN in the latter. These results suggest that a nitrogen atom produced in the system attacks the carbon atom in the middle of propylene and produces acetonitrile, leaving a methyl radical, the carbon atom in which was originally attached to the double bond.
  • Toyoaki Kimura, Kenji Fueki, Zen-ichiro Kuri
    1969 Volume 42 Issue 11 Pages 3088-3092
    Published: 1969
    Released: March 27, 2006
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    The effect of cumene on the hydrogen yields from methylcyclohexane γ-irradiated at 100, 20, −72, −120 and −196°C has been investigated. Cumene did not compete with N2O for capturing electrons in methylcyclohexane and the yield of thermal H atoms in methylcyclohexane, determined by use of ethylene as an H atom scavenger, was smaller than the decrease in hydrogen yield in methylcyclohexane-cumene systems. Therefore, the decrease in hydrogen yield in methylcyclo-hexane-cumene systems can be ascribed mainly to positive charge transfer from methylcyclohexane to cumene. Further, the evidence of charge transfer from methylcyclohexane to cumene was found by the optical absorption method. The effect of cumene on the hydrogen yield from methylcyclohexane was similar in the temperature range from 100 to −196°C, especially at high cumene concentration. The effect of an electron scavenger at high concentrations was also examined with n-butyl chloride. In the present work, we have found that although the effect of a positive ion scavenger on the hydrogen yield from methylcyclohexane in the liquid state differs little from that in the glassy state, the effect of electron scavengers on the former differs considerably from that on the latter.
  • Akira Kotera, Hideomi Matsuda, Yuji Miyazawa, Etsuo Joko
    1969 Volume 42 Issue 11 Pages 3093-3099
    Published: 1969
    Released: March 27, 2006
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    A modification of the Archibald method for determining the molecular weight of a polydisperse sample in ideal and non-ideal solutions is developed in this paper. A reliable value of the weight average molecular weight is obtained from the plot of an apparent weight average molecular weight against the centrifugal time rather than against the amount of the solute sedimented from the meniscus. This fact is explained on the assumption of a fractionation effect of the solute caused by the centrifugal potential.
  • Hiroshi Mizuno, Takaji Fujiwara, Ken-ichi Tomita
    1969 Volume 42 Issue 11 Pages 3099-3105
    Published: 1969
    Released: March 27, 2006
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    The crystals of sodium salt of xanthine, C5H3N4O2Na·4H2O, are monoclinic with four molecules in a unit cell of dimensions; a=7.31, b=19.52, c=7.17 Å, β=100.0°, space group P21c. The structure has been determined by application of the sign relationship S(hkl)S(hkl′)∼S(h+h′,k+k′,l+l′) from (hk0) intensity data and refined by three-dimensional least-squares methods. The positions of the hydrogen atoms were determined by a three-dimensional difference Fourier analysis, and it was confirmed that deprotonation took place at the position of the imino N(3)H of the xanthine molecule. Each Na+ cation is surrounded by six water molecules and each xanthine anion participates in ten hydrogen bonds, forming a close-packed system.
  • Tadashi Okuyama, Takayuki Fueno, Junji Furukawa
    1969 Volume 42 Issue 11 Pages 3106-3108
    Published: 1969
    Released: March 27, 2006
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    The silver-ion complexation equilibria of a few cis-stable olefins have been investigated in an aqueous phase at 25°C. The trans isomers of β-chlorovinyl ethyl ether and 1,2-dichloroethylene were found to have greater equilibrium constants than the corresponding cis isomers. It was concluded that the relative stabilities of parent olefin isomers play an exclusive role determining their relative complexation abilities.
  • Hiroshi Kawabe, Masaya Yanagita
    1969 Volume 42 Issue 11 Pages 3109-3115
    Published: 1969
    Released: March 27, 2006
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    The second-order rate constant of the alkaline hydrolysis of polymethyl acrylate in an aqueous acetone solution decreases as the reaction proceeds. The plot of the logarithmic term of the second-order rate equation against the reaction time is divided into four lines; this suggests that the reaction proceeds in four steps. The rate equation of the reaction can be derived by assuming that the reactivity of ester groups is electrically affected mainly by a few neighboring hydrolyzed groups. The kinetic behavior is compared with the titration data of polyacrylic acid; the sets of data can be correlated through a simple equation containg two constants, k0, the intrinsic rate constant, and pK0, the intrinsic ionization constant.
  • Satoru Tsuda, Akira Yokohata, Michihiro Kawai
    1969 Volume 42 Issue 11 Pages 3115-3118
    Published: 1969
    Released: March 27, 2006
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    The negative ion mass spectra of tetrahydrofuran, with an emphasis on their relative abundances to the positive ions under 80 eV and 40 eV electron energies, and the ionization efficiency (IE) curves of me 16(O),me 25(C2H) and me 41(C2HO) ions to the extent of 40 eV electron energies were measured. The electron impacts of 80 eV and 40 eV gave almost the same distribution of me for negative ion mass spectra. The relatively strong peaks were observed at me 24(C2) ions for 80 eV and me 14(CH2) ions for 40 eV, besides the commonly strong peaks of me 25(C2H), me 16(O) and me 41(C2HO) ions. The comparison of the yield of C2H ions with that of C3H6+ gave the values 9.4×103 and 2.7×104 for C3H6+/C2H at 80 eV and 40 eV electron energies, respectively. The reaction schemes expected to occur at each onset observed in the IE curves were also discussed. It is of interest to note that C2H ions are not obtained in the range of low energy of electrons, but become observable at ∼23.5 eV.
  • Akira Imamura, Hiroko Fujita, Chikayoshi Nagata
    1969 Volume 42 Issue 11 Pages 3118-3123
    Published: 1969
    Released: March 27, 2006
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    The electronic structures of glycine have been calculated for the dipolar-ion form and the neutral form by means of the CNDO method. The relative stability of both the dipolar-ion form and the neutral form in the gas state was reproduced by our calculation. The geometry of the glycine was also reproduced by the CNDO method, indicating the validity of our calculation. In addition, the relative stability of the two tautomeric forms of glycine was proved to be independent of its geometrical modifications. The experimental fact that the dipolar-ion form is more stable than the neutral form in an aqueous solution was well explained by the calculation of the interaction energy between the solute and the solvent.
  • Kumasaburo Kodera, Yoshifumi Kita, Isao Kusunoki, Hiroshi Kishi, Atsuh ...
    1969 Volume 42 Issue 11 Pages 3124-3130
    Published: 1969
    Released: March 27, 2006
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    The effect of chlorine, bromine, and oxygen on the emission of thermal positive ions from tungsten filaments has been studied. When a tungsten filament is heated in a vacuum, positive ion emission is always observed, and it cannot be removed completely by flashing the filament at high temperatures. This background ion emission increases greatly in halogen or oxygen. Main positive ions are K+ and Na+. The increase cannot be explained by the increase of the work function of tungsten by the formation of adsorbed layer of halogen or oxygen atoms. It is ascertained that the tungsten surface reacts with these gases and the reaction products evaporate as neutral particles. As the reaction proceeds, tungsten surface is removed successively and alkali metal atoms in the bulk are exposed to the surface and contribute to the positive ion emission.
  • Naosato Yoshida, Shuichi Hamada, Toshiaki Shirai
    1969 Volume 42 Issue 11 Pages 3131-3134
    Published: 1969
    Released: March 27, 2006
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    The viscosities and densities of liquid oligotrifluorochloroethylene were measured over a molecular-weight range from 820 to 1090 at temperatures from 40°C to 100°C. The temperature dependences of the viscosities did not show an Arrhenius-type variation, but were extremely adaptable in the WLF equation; i. e., a viscoelastic behavior was shown under the present experimental conditions. The apparent activation energies, ΔHa, for the viscous flow of the liquid samples were comparatively large and increased with an increase in the number-average molecular weight. The logarithm of the viscosity, logη, varied linearly with the logarithm of the number-average molecular weight, logη=AlogMn+B. The slopes, A, of the linear relationships were estimated to be 11.0, 10.4, 9.3, and 8.4 at 50, 60, 70, and 80°C respectively. The values of the slopes, A, were very much larger than unity in the case of usual organic polymers below the critical values of the molecular weight, and they decreased with an increase in the temperature.
  • Kazuyoshi Iimura
    1969 Volume 42 Issue 11 Pages 3135-3140
    Published: 1969
    Released: March 27, 2006
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    The infrared spectra of meso- and racemic-2,3-dibromobutanes in solution and in gaseous states were obtained in the study of the rotational isomers. The occurrence of three rotational isomers was confirmed for both meso- and racemic-isomers. The quantitative estimation of the equilibrium concentrations of the rotational isomers was also made in various solvents. The energy difference between the rotational isomers was determined by measuring the temperature-dependence of the absorption intensities of v(C–Br) vibrations.
  • P. K. Sundaram, M. M. Sharma
    1969 Volume 42 Issue 11 Pages 3141-3147
    Published: 1969
    Released: March 27, 2006
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    A variety of amines such as piperazine, pyrrolidine, morpholine, dialkyl amines, alkanolamines etc. were reacted with ethylene-, propylene-, and 1,2-butylene oxides in aqueous medium. Most of the experiments were made at 20°C. For some typical amines kinetic runs were made over a wide temperature range to obtain values of activation energy. Theoretical aspects of the reaction are discussed. It is shown that the method suggested by Swain and Scott could be used to correlate the rate constants. A close relationship exists between the relative rates of reaction of amines with CO2, COS, CS2 and alkene oxides.
  • Krishna Kumar, L. K. Saxena
    1969 Volume 42 Issue 11 Pages 3148-3154
    Published: 1969
    Released: March 27, 2006
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    The S2O82− induced reduction of mercuric chloride by malic acid has been studied by estimating the precipitated calomel. Kinetic measurements reveal the reduction rate to be independent of the acid concentration and first order in peroxodisulphate, but only to up an optimum concentration, whereafter further increase in inductor concentration decreases the reduction rate. A fractional order dependence in mercuric chloride concentration is encountered. The reaction is characterized by an initial of period induction. The initial rapid consumption of the acid results in lowering of the rate beyond a particular stage of the reaction. Increase of temperature and concentration of reactants is found to effect the period of induction. H+ ions and oxygen inhibit the reduction rate. Products identified are mainly calomel, carbon dioxide and malonic acid. A chain mechanism in which radical ion chain carriers participate, has been suggested.
  • Akio Iwase, Chieko Yokoyama
    1969 Volume 42 Issue 11 Pages 3155-3158
    Published: 1969
    Released: March 27, 2006
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    The oscillopolarographic depolarization effect of lanthanide ions in KI solutions was investigated using dropping (DME) and hanging-drop (HME) mercury electrodes. The lanthanide-ion incision depth in the dEdt=f(E) curve, measured in a 1M KI solution (pH 3.65) with a DME, was found to be much deeper than that in a 1M KCl solution. The temperature coefficient was negative for the La and Sm incision depths in the temperature range from 25° to 50°C. The incision depths of the La (pH 4.0) and Sm (pH 4.5) ions in a solution with an ionic strength of 0.7 (KCl added) were found to depend on the I concentration. These facts seem to show that I is adsorbed on DME, and that the adsorbed I (at −1.4 V) promotes the electrode reaction of lanthanide ions.
  • Nobufumi Maki, Kouei Yamamoto, Hiroshi Sunahara, Shukichi Sakuraba
    1969 Volume 42 Issue 11 Pages 3159-3165
    Published: 1969
    Released: March 27, 2006
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    In an aqueous solution containing an excess of ethylenediamine, i. e., under the conditions where the aquation is prevented, the dicyano-cobalt(III) complex, cis-[Co(CN)2en2]NO3, has been found to be reduced in three steps at the dropping mercury electrode (DME). The first step, corresponding to the acceptance of one electron, represents the reduction from the cobalt(III) to the cobalt(II) state, while the second and the third step were interpreted as being due to the reduction of two kinds of the cobalt(II) species formed by the overall rearrangement of ligands in solution. One such kind of cobalt species is the binuclear tetracyanocobaltate(II) complex, [Co(CN)4-en-Co(CN)4]4−, which is reduced to the metal through the cobaltate(I) complex, while the other is the cobalt(II) complexes with ethylenediamines in an equilibrium state, which are reduced directly to the metal at the DME. Namely, the second step represents the reduction from the cobalt(II) complex of the former to the cobalt(I) state, while the third step, denoting the reduction to the metal, was observed only on the dEdt-E curve of the oscillopolarogram, but not on the current-potential curve due to the maximum wave. In the non-aqueous solution of dimethyl sulfoxide, the dicyano-cobalt(III) complex, cis-[Co(CN)2en2]ClO4, undergoes the step-by-step reduction of Co(III)→Co(II)→Co(I)→Co(0), as it were, at the DME. Neither aquation nor rearrangements of ligands take place throughout reductions under these experimental conditions, that is, even in lower oxidation states of the cobalt.
  • Nobufumi Maki, Yukio Ishiuchi, Shukichi Sakuraba
    1969 Volume 42 Issue 11 Pages 3166-3171
    Published: 1969
    Released: March 27, 2006
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    The halogeno- and aquo-bis(dimethylglyoximato)amminecobalt(III) complexes of the trans-[CoIIIX dg2(NH3)]-type have been found to be reduced to the metal through the cobalt(I) state in a 0.5M Na2SO4 aqueous solution at the dropping mercury electrode (DME), where the ligand, X, denotes the ion, Cl, Br, or I, or the molecule, OH2. The aquation of the halogeno complexes is found to take place more rapidly in solution in this order: Cl<Br<I. The diaquobis(dimethyl-glyoximato) cobalt(III) ion, [Co(OH2)2dg2]+, has also been ascertained to undergo a step-by-step reduction to the metal through the cobalt(I) state at the DME.
  • Yuki Fujii, Mutsuo Kodama
    1969 Volume 42 Issue 11 Pages 3172-3177
    Published: 1969
    Released: March 27, 2006
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    In the present paper, the solution equilibria between the copper(II) ion and ethylenediaminemonoacetic acid (EDMA) were determined polarographically and, then copper(II)-EDMA complexes were prepared and characterized using ion-exchange chromatography and the visible and infrared absorption spectra. Since copper(II) ions in an EDMA solution behave reversibly in a polarographic electrolysis, the composition and the stability constants of copper(II)-EDMA complexes were determined from the dependence of the half-wave potential on the concentration of uncomplexed EDMA by employing a modification of the Deford-Hume method. The copper (II) ion was found to form complexes of 1-to-1 and 1-to-2 compositions with EDMA. Their successive formation constants, K1 and K2, were 2.52×1013 and 1.10×108 respectively. The copper(II)-EDMA complex with a 1-to-1 composition was easily isolated from an aqueous solution of pH 3.0–4.0. On the other hand, the complex with a 1-to-2 composition could be isolated in a low yield by adding ethanol from a solution containing an excess amount of EDMA in the pH range from 10.0 to 11.0. From the infrared spectra and the ion-exchange chromatographic behavior, the ethylenediaminemonoacetate ion in the complexes was concluded to function as a tridentate ligand.
  • Zenzi Hagiwara, Hideo Oki
    1969 Volume 42 Issue 11 Pages 3177-3184
    Published: 1969
    Released: March 27, 2006
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    Under experimental conditions similar to those in the elution system of the rare earth with a dilute HEDTA eluant, the Er-Tm separation factor has been found in the system of HEDTA and Dowex 50W, X-8, 50–100 mesh. The values for this pair, 1.57 at 25°C and 1.63 at 60°C were in agreement with the values calculated from the stability constants of the rare earth-HEDTA chelates. Further, an equimolar mixture of Er and Tm has been eluted with a 0.015M HEDTA solution buffered with ammonium hydroxide. Under the present experimental conditions, the adsorption band of each rare earth reached a steady state after it had moved down through the hydrogen-retaining bed to a distance several times the initial band length. Several series of experimental data were used for analyses of the adsorption band from the point of view of rate theory. It was concluded that the present ion-exchange process with a HEDTA eluant was controlled by film diffusion as the rate-determining step. The plate-height values were also found to be functions of the flow rate.
  • Shigenobu Yano, Haruko Ito, Yoshio Koike, Junnosuke Fujita, Kazuo Sait ...
    1969 Volume 42 Issue 11 Pages 3184-3189
    Published: 1969
    Released: March 27, 2006
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    Proton magnetic resonance (PMR) spectra of tetracyano-l-propylenediamine cobalt(III) ion and bis(l-propylenediamine) platinum(II) and palladium(II) ion have been measured in deuterated water and analyzed according to Castellano and Waugh’s exact analysis. The values of coupling constants clearly indicate that the l-propylenediamine chelate rings in these diamagnetic complexes have fixed λ-gauche form in aqueous solutions at room temperature.
  • Minoru Tanaka, Toshiyuki Shono, Koichiro Shinra
    1969 Volume 42 Issue 11 Pages 3190-3194
    Published: 1969
    Released: March 27, 2006
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    Seventeen 3-substituted-2,4-pentanediones were synthesized. The effect of substituents in the position 3 on the tautomeric equilibria, i.e., keto-, cis-enol- and trans-enol-forms, has been investigated by nuclear magnetic resonance spectroscopy. It has been found that the percentage of each tautomer depends upon the electronic and steric effects of the substituents. The relative intensity of intramolecular hydrogen bonds in these compounds was evaluated from both the NMR and IR data. It has been found from the half-wave potential data of polarographic reduction and the Cu–O stretching frequencies of 16 copper chelates of 3-substituted-2,4-pentanediones that the relative stability of the chelate decreases with an increase in the electron-withdrawing effect of the substituents.
  • Masahiro Yoshimura, Toshiyuki Sata
    1969 Volume 42 Issue 11 Pages 3195-3198
    Published: 1969
    Released: March 27, 2006
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    A new monoclinic phase of cerium orthovanadate, CeVO4(H), was found during the course of oxidation of pseudo-perovskite CeVO3 below 400°C. It has been confirmed to crystallize in the huttonite-type structure (C2h5P21n), that of LaVO4. The lattice parameters were determined to be:
    a0=6.98Å, b0=7.22Å, c0=6.76Å, β=105°02′, V=328Å3 and Z=4.
    This phase was metastable, and exothermally transformed into a known stable CeVO4 (tetragonal zircon-type, D4h19I41amd) above 400°C, releasing a small amount of oxygen. From magnetic, chemical and thermogravimetric analyses, the valences of cerium ion and vanadium ion in CeVO4-(H) seem to be tripositive and pentapositive respectively, but V4+ ion is mixed in zircon-type CeVO4; CeVO4(Z).
  • R. K. Thakkar, S. R. Patel
    1969 Volume 42 Issue 11 Pages 3198-3203
    Published: 1969
    Released: March 27, 2006
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    6- and 7-Nitro-2-benzyl-3H-4-ketoquinazolines and their 3-Me and 3-Ph derivatives were prepared by condensing the 6-nitro (III) and 7-nitro (XII) derivatives of -4H-3,1-benzoxazin-4-one with ammonia, methylamine and aniline, respectively. The compounds III and XII were formed on refluxing 5- and 4-nitro-N-phenylacetylanthranilic acids with acetic anhydride. 6- and 7-Nitro-2-benzyl-3H-4-ketoquinazolines (IV and XIII) were also prepared by condensing 5- and 4-nitro-N-phenylacetylanthranilic acids with formamide, respectively, in very low yields. The compounds IV and XIII yielded the corresponding 2-benzoyl derivatives on oxidation and the corresponding 2-(1-phenylstyryl) derivatives on reaction with benzaldehyde. 6- and 7-Nitro-2-styryl and 2-(1-phenylstyryl)-3H-4-ketoquinazolines were not oxidized by alkaline permanganate. UV spectra of these compounds have been studied.
  • Katsuo Akagane, F. J. Allan, G. G. Allan, T. Friberg, S. Ó Muir ...
    1969 Volume 42 Issue 11 Pages 3204-3207
    Published: 1969
    Released: March 27, 2006
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    The reaction of α-dione monoximes with aldehydes and ammonia affords a general and facile synthetic route to 1-hydroxyimidazoles. By selection of the starting materials substituents can be readily introduced into the 2,4 and/or 5 positions of the imidazole ring which is formed via the intermediacy of a gem-aminoalcohol. The reactions of the N-hydroxyl function are discussed.
  • Takayuki Otsu, Bunichiro Yamada, Hiroshi Yoneno
    1969 Volume 42 Issue 11 Pages 3207-3210
    Published: 1969
    Released: March 27, 2006
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    A study of the polymerizations and copolymerizations of α-methoxyacrylonitrile(MeOAN) and methyl α-methoxyacrylate(MeOA) has been made. These monomers were homopolymerized with a radical initiator at 60°C, but did not give any polymer with such ionic catalysts as BF3O-(C2H5)2 and C6H5MgBr at 0°C. From the radical copolymerizasions of these monomers with styrene at 60°C, their Q, and e values were determined to be as follows:
    Q=0.72, e=0.40 for MeOAN
    Q=0.47, e=0.04 for MeOA
    These monomers were also copolymerized with acrylonitrile, and the copolymerization parameters were determined.
  • Tsutomu Kagiya, K\={o}z\={o} Narita, Masatsune Kondo
    1969 Volume 42 Issue 11 Pages 3211-3215
    Published: 1969
    Released: March 27, 2006
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    Formaldehyde, carbon dioxide, and N-phenylethylenimine were allowed to terpolymerize by means of dimethyl ether acetate to give a crystalline solid terpolymer, melting at 178–265°C, with the composition of: CH2O: 70–95, CO2: 0.5–5, C8H9N: 5–25 mol%. The content of N-phenylethylenimine in the terpolymer thus obtained increased with the content of the imine in the feed, and that of carbon dioxide in the terpolymer, with the content of the imine in the feed, the lowering of the polymerization temperature, and the polymerization time. The infrared spectrum of the terpolymer showed the characteristic peaks of –(–CH2OCH2O–)–, (Remark: Graphics omitted.) and (Remark: Graphics omitted.). The mechanism of the terpolymerization was proposed on the basis of these results.
  • Teruo Hiraki
    1969 Volume 42 Issue 11 Pages 3216-3220
    Published: 1969
    Released: March 27, 2006
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    The present study was undertaken in order to ascertain the difference, if any, in the chemical behavior of methyl acetate and acetic anhydride submitted to a silent discharge between that in the presence and that in the absence of ethylene. (1) In the reaction of methyl acetate without ethylene, the main products were methanol, diacetyl, liquid hydrocarbons, formaldehyde, methane, carbon dioxide, carbon monoxide, and hydrogen. Although the methanol yield was almost the same, regardless of the presence or absence of ethylene, the yields of the hydrocarbons, all the carbonyl compounds, and of n-butyl acetate increased in the presence of ethylene. The great quantity of methanol produced might indicate that C–OCH3-bond breaking in the methyl acetate occurs preferably upon the discharge. (2) With acetic anhydride, on the other hand, acetaldehyde, acetone, ethyl acetate, ethyl methyl ketone, diacetyl, hydrocarbons, carbon monoxide, carbon dioxide, and hydrogen were obtained as the main products. The yields of acetone and diacetyl decreased remarkably in the presence of ethylene, while the yields of hydrocarbons, ethyl methyl ketone, n-butyl methyl ketone, and of n-butyl acetate increased. The CH3COO· and CH3CO· radicals are thought to be the main intermediates in this reaction. The formation of n-butyl acetate and of n-butyl methyl ketone in the presence of ethylene can be explained on the basis of the telomerization of ethylene initiated by these radicals.
  • Etsuo Niki, Yoshio Kamiya, Nobuto Ohta
    1969 Volume 42 Issue 11 Pages 3220-3223
    Published: 1969
    Released: March 27, 2006
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    The effects of solvents on the rate of decomposition and the efficiency of radical production by AIBN were studied by measuring the rate of evolution of nitrogen from AIBN and the inhibition time in the oxidation of tetralin. The rates of decomposition of AIBN were larger in aromatic solvents than in aliphatic solvents. The efficiency of AIBN was found to depend more on the viscosity of the medium than on the polarity of the solvents. The requirements for the determination of the inhibition time are discussed.
  • Etsuo Niki, Yoshio Kamiya, Nobuto Ohta
    1969 Volume 42 Issue 11 Pages 3224-3229
    Published: 1969
    Released: March 27, 2006
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    The rates of oxidation of 1.47M tetralin in a variety of solvents at 70°C in the presence of 1.00×10−2M AIBN varied by a factor of 2.9, ranging from 6.39×10−6 mol/l/sec in n-decane to 1.84×10−5 mol/l/sec in nitromethane. The rate of oxidation was dependent on the composition of the solution as well as the kinds of solvents. It was found that the solvents affected the initiation step approximately as much as they affected the propagation and/or temination step. The rate of initiation by AIBN was mainly dependent on the viscosity of the medium, while that of propagation and termination was mainly determined by the dielectric constant of the medium. The correlation between log(kp⁄(2kt)1⁄2) and (D–1)/(2D+1) was discussed, where kp and kt are the rate constants for propagation and termination steps, respectively, and D is the dielectric constant of the medium, under conditions where the complication caused by the selective solvation could be excluded.
  • Kazuko Kohara
    1969 Volume 42 Issue 11 Pages 3229-3233
    Published: 1969
    Released: March 27, 2006
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    Guaiazulene was oxidized with potassium permanganate and with selenium dioxide according to the Treibs procedure. An acidic and a neutral crystalline compounds obtained from the permanganate oxidation in acetone were identified by means of UV, IR, and NMR spectrum measurements as 4-methyl-7-isopropylazulene-1-carboxylic acid and 1-formyl-4-methyl-7-isopropylazulene respectively. It was also confirmed that the selenium dioxide oxidation of guaiazulene in acetone gave 3-formylguaiazulene and 3,3′-diguaiazulenylacetone, the chemical structure of which had already been established by Treibs.
  • Akira Omori, Noboru Sonoda, Yuzo Uchida, Shigeru Tsutsumi
    1969 Volume 42 Issue 11 Pages 3233-3237
    Published: 1969
    Released: March 27, 2006
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    The reactions of carbon suboxide with alicyclic diketones and with phenols were found to give various pyrone derivatives. From the reaction of 5,5-dimethyl-1,3-cyclohexanedione, 4-hydroxy-7,7-dimethyl-5,6,7,8-tetrahydro-2H-benzo[b]pyran-2,5-dione (II) was produced in the presence of a sulfuric acid catalyst. However, the reaction with 1,2-cyclohexanedione gave the malonic acid diester (III), and the formation of corresponding pyrone was not observed. The reaction of phenols with carbon suboxide gave only esters of malonic acid in the presence of the sulfuric acid catalyst, whereas cyclization to coumarin derivatives occurred on the presence of aluminum trichloride, in addition to the formation of the esters. The structure of the pyrone derivatives and the possible reaction mechanism were discussed.
  • Ryo Yoshizawa, Takashi Inukai
    1969 Volume 42 Issue 11 Pages 3238-3242
    Published: 1969
    Released: March 27, 2006
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    Peroxy-trans-crotonic acid was prepared from dicrotonyl peroxide by alkaline cleavage and isolated for the first time in a crystalline state, mp 41–42°C. It was characterized by NMR and IR spectra, and its stability briefly tested. Reaction with dimethyl sulfide gave a quantitative yield of crotonic acid. Its pKa in water at 25°C was 8.2. Second order rate constants of reaction with crotonaldehyde in benzene (Table 4) were measured: Ea, 13.3 kcal/mol; log A(l/mol sec), 5.3; ΔS\ eweq, −36 eu/mol. Detection of a possible intermediate, a peracid-aldehyde complex X, was attempted by means of NMR but evidence for it was not obtained.
  • Masanori Kosugi, Kohji Takeuchi, Toshihiko Migita
    1969 Volume 42 Issue 11 Pages 3242-3244
    Published: 1969
    Released: March 27, 2006
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    Acetonitrile, propionitrile, n-butyronitrile and pivalonitrile were photochlorinated competitively at 40°C in the presence of an appropriate chlorinated ethane, and relative amounts of the chlorinated products were determined by v.p.c. From the results the relative reactivities of C-H bonds toward hydrogen abstraction by chlorine atom were estimated. A linear free energy relationship was observed between σ* value of X and the reactivity of CH3–X toward chlorination (X: –CN, –CH2CN, –CH2CH2CN, –CMe2CN). This indicates that cyano group will affect the reactivities of these C-H bond through its inductive effect.
  • Kazuo Kumamoto, Hiroshi Yoshida, Tsuyoshi Ogata, Saburo Inokawa
    1969 Volume 42 Issue 11 Pages 3245-3248
    Published: 1969
    Released: March 27, 2006
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    Sugars containing a carbon-phosphorus bond were synthesized by the photochemical addition of diethyl thiophosphonate to unsaturated sugars. By UV illumination from a high-pressure mercury lamp in the presence of diethyl thiophosphonate, -D-glucal gave 1,5-anhydro-2-deoxy-2-(diethyl thiophosphonate)-D-glucit; 3-deoxy-1,2;5,6-di-O-isopropylidene-α-D-erythro-hex-3-enose gave 1,2;5,6-di-O-isopropylidene-3-deoxy-3-(diethyl thiophosphonate)-α-D-glucofuranose and 1,2;5,6-di-O-isopropylidene-3-deoxy-3-(diethyl thiophosphonate)-α-D-galactofuranose (4:1 mol ratio); 6-O-benzyl-5-deoxy-1,2-O-isopropylidene-α-D-xylo-hexofuran-5-enose gave 6-O-benzyl-5-deoxy-5-(diethyl thiophosphonate)-1,2-O-isopropylidene-α-D-glucofuranose and 6-O-benzyl-5-deoxy-5-(diethyl thiophosphonate)-1,2-O-isopropylidene-α-L-idofuranose (2:5 or 5:2 mol ratio), and 5-deoxy-l,2-O-isopropylidene-3-O-methyl-α-D-xylofuranose-4-ene gave 5-deoxy-5-(diethyl thiophosphonate)-1,2-O-isopropylidene-3-O-methyl-α-D-xylofuranose.
  • Kunio Okamoto, Kôichi Komatsu, Haruo Shingu
    1969 Volume 42 Issue 11 Pages 3249-3254
    Published: 1969
    Released: March 27, 2006
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    The reaction of tropylium fluoroborate in an aqueous solution has been carried out at room temperature with powders of various metals (Mg, Al, Mn, Zn, Cr, Fe, Cd, Co, Ni, Sn, Pb, Sb, Cu, Hg, and Ag) under heterogeneous conditions and with several metallic ions (Cr(II), Ti(III), Sn(II), Cu(I), Fe(II), Fe(III), Hg(I), Hg(II), and Ag(I)) in a homogeneous solution. All these reagents, except Ag, Fe(III), Hg(I), Hg(II), and Ag(I), reduce with ease the tropylium ion to give the tropyl radical, which then rapidly couples to bitropyl; their reducing powers, estimated by comparing the yields of bitropyl under the same reaction conditions, correlate with their oxidation electrode potentials and oxidation-reduction potentials. The ferric ion, the mercurous ion, the mercuric ion, and the silver ion afforded no bitropyl, but only an oxidation product of the tropylium ion, i.e., benzaldehyde. Silver powder gives neither a reduction nor an oxidation product under these reaction conditions. The reduction has also been carried out in an acetonitrile solution, and the reducibility of tropylium fluoroborate with powders of Zn, Fe, Ni, Sb, Cu, and Ag has been compared with that of triphenylmethyl fluoroborate under heterogeneous conditions. Both the tropylium ion and the triphenylmethyl cation are smoothly reduced by Zn, Fe, Ni, Sb, and Cu in this solvent. The tropylium ion, however, is not reduced by silver powder, while the triphenylmethyl cation is reduced to the triphenylmethyl radical. This greater reducibility of the triphenylmethyl cation is consistent with what could be anticipated from the data of half-wave potentials, ionization potentials, and H.M.O. calculation reported with respect to these two carbonium ions.
  • Zen-ichi Yoshida, Nobuyuki Ishibe
    1969 Volume 42 Issue 11 Pages 3254-3258
    Published: 1969
    Released: March 27, 2006
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    Using a series of alkylphenols and naphthols as the proton donors, the hydrogen bond shifts and the association constants of hydrogen-bonded complexes involving methyl benzenes, naphthalene, and phenanthrene as the proton acceptors have been determined from the infrared spectra in carbon tetrachloride. The frequency shifts (Δv) of the hydroxyl stretching vibration and the free energy changes (−ΔF) for complex formation increase with decreasing pKa of the proton donors. Linear correlation between −ΔF and Δv are obtained for each proton donor interacting with methyl benzenes. The entropy anomaly discovered previously was confirmed. Chargetransfer arguments of Basila and co-workers are reconsidered for the hydrogen-bonded systems involving a π base as the proton acceptor.
  • Zen-ichi Yoshida, Nobuyuki Ishibe
    1969 Volume 42 Issue 11 Pages 3259-3262
    Published: 1969
    Released: March 27, 2006
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    Hydrogen bonding of 4-substituted-2,6-xylenols to mesitylene has been investigated by measurement of the hydroxyl stretching vibration. A linear relationship between the electronic effects of para substituents (Hammett σp constant) and the frequency shifts of the hydroxyl stretching vibration was obtained. A similar correlation was also observed with the free energy change associated with the formation of the hydrogen-bonded complex. The thermodynamic sutdies on the hydrogen bonding of 2,6-xylenol and phenol with both mesitylene and acetonitrile demonstrated the steric effect of 2- and 6-methyl groups on hydrogen bond formation. The free energy change for hydrogen bond formation with 2,6-xylenols as the proton donor was lower than with phenol. This is explained in terms of both entropy and enthalpy factors.
  • Zen-ichi Yoshida, Nobuyuki Ishibe
    1969 Volume 42 Issue 11 Pages 3263-3266
    Published: 1969
    Released: March 27, 2006
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    The π hydrogen bonding between phenol and monoolefins has been studied by examining the OH stretching vibration spectra of phenol in the presence of monoolefins. From comparison of the hydrogen bond shifts, it has been shown that the basicity of the aliphatic olefins toward phenol increases with the increasing alkylsubstitution on the double bond carbon. The endo-cyclic olefins are more basic than RCH=CH2 and RCH=CHR′ where R and R′ represent alkyl groups. The equilibrium constants for complex formation with olefins were smaller than those with aromatic hydrocarbons. The steric effects on the hydrogen bond complex with aliphatic and endocyclic olefins have been discussed.
  • Hiromichi Kono, Mikio Shiga, Izumi Motyoama, Kazuo Hata
    1969 Volume 42 Issue 11 Pages 3267-3269
    Published: 1969
    Released: March 27, 2006
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    Acetylferrocene reacted with nitromethane and morpholine in the presence of titanium(IV) chloride to give a Mannich base, 2-ferrocenyl-2-morpholino-1-nitropropane (7), whose sodium salt (8) was then converted to 2-ferrocenyl-1-nitropropene (9) by acidifying it with hydrochloric acid. In the presence of aluminum chloride in place of titanium (IV) chloride, acetylferrocene as well as 1,1′-diacetylferrocene dimerized to form α,β-unsaturated ketone, (10) or (11).
  • Hiromichi Kono, Mikio Shiga, Izumi Motoyama, Kazuo Hata
    1969 Volume 42 Issue 11 Pages 3270-3273
    Published: 1969
    Released: March 27, 2006
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    A new method of synthesizing 1-ferrocenyl-2-iodo-2-nitroethylene (6) was presented, whereas 1-ferrocenyl-2-halo-2-nitroethylene could not be prepared by the usual method, involving the direct halogenation of the nitroolefin. The iodonitroethylene (6) was prepared by the reaction of the sodium salt of 1-ferrocenyl-2-nitroethylene with iodine or with potassium iodide. This procedure proved to be useful for introducing various groups on the α-carbon of the nitroethylene. The stereochemistry of nitroalkenylferrocenes, including some previously reported ones, was discussed on the basis of their spectral data.
  • Hiromichi Kono, Mikio Shiga, Izumi Motoyama, Kazuo Hata
    1969 Volume 42 Issue 11 Pages 3273-3277
    Published: 1969
    Released: March 27, 2006
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    The condensation reaction of formylferrocene with simple aliphatic and alicyclic ketones, as acetone, ethyl methyl ketone, isobutyl methyl ketone, and cyclohexanone, in the presence of piperidine as a condensing agent afforded seven kinds of β-ferrocenyl-α,β-unsaturated ketones. The geometric configurations of the unsaturated ketones were discussed on the basis of their NMR spectra, and the influences of the ferrocenyl group on the π-π* transition bands in their UV spectra were also discussed.
  • Tetsuo Nozoe, Kazuko Takahashi, Hiroshi Yamamoto
    1969 Volume 42 Issue 11 Pages 3277-3284
    Published: 1969
    Released: March 27, 2006
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    On the reaction with a base (e.g., aqueous sodium hydroxide), isopropyl- and methyl-tropylium ions afforded cycloheptatrienyl polymers with an alkylene bridge, such as IIIa and IIIb, while the t-butyltropylium ion gave a mixture of 3- and 4-t-butyltropone, which was then transformed to 4-and 5-t-butyltropolone (VIIIa and IX). The bromination of VIIIa with 3 mol of bromine in methanol gave 3,7-dibromo-4-t-butyl-2-methoxy-2,3-dihydrotropolone (XIIa). On the heating of the adduct (XIIa) at 130°C, 7-bromo-4-t-butyltropolone (XIa) was formed.
  • Tsuyoshi Shishibori, Takayuki Suga, Satoru Watanabe, Tamon Matsuura
    1969 Volume 42 Issue 11 Pages 3284-3288
    Published: 1969
    Released: March 27, 2006
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    The conformational analysis of a stereoisomeric pair of 4-hydroxymenthones, (1R:4R)-(−)-4-hydroxymenthone (1) and (1R:4S)-(+)-4-hydroxyisomenthone (2), was made by means of temperature-dependent circular dichroism. It was demonstrated that α-hydroxyketone (1) exists in the conformational equilibrium: 1a\leftrightarrows1b; the conformer 1a exists predominantly in a nonpolar medium, whereas the conformer 1b is more stable than 1a in a polar medium. On the other hand, the other isomer, (2), exists preferentially in the state of the conformer 2b in either a polar or a nonpolar solvent. The results were interpreted in terms of the competition of the steric factor and intramolecular hydrogen-bonding.
  • Kunio Okamoto, Seiki Saitô, Haruo Shingu
    1969 Volume 42 Issue 11 Pages 3288-3297
    Published: 1969
    Released: March 27, 2006
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    The rates of the phenolysis of cis- and trans-4-t-butylcyclohexyl p-toluenesulfonates have been measured in the presence of equimolar amounts of triethylamine in phenol, phenol-benzene (3 : 1 by wt), and phenol-benzene (1 : 1 by wt) solvents. At 75°C, the axial isomer, i.e., the cis tosylate, phenolyzes more rapidly in the phenol-benzene mixture (1 : 1 by wt) than the equatorial isomer, i.e., the trans tosylate, by a factor of 3.08; this factor is not far from the axial-equatorial rate ratios observed in other hydroxylic solvents, indicating that phenol is a typical solvolytic solvent. Under the same reaction conditions as the rate measurements, the equatorial tosylate yields t-butylcyclo-hexene (72.5%), t-butylcyclohexyl phenyl ether (9.4%), predominantly inverted (cis-4-t-butylcyclo-hexyl) phenyl ether, and t-butylcyclohexylphenol (4.4%), whereas the axial tosylate yields t-butyl-cyclohexene (87%) and the phenyl ether (8.7%), largely inverted (trans-4-t-butylcyclohexyl) phenyl ether, but containing increasing amounts of retained (cis-4-t-butylcyclohexyl) and and rearranged (trans-3-t-butylcyclohexyl) ethers; the rest is a mixture of t-butylcyclohexylphenols (1.6%). The composition percentages of the retained phenyl ether obtained from the two tosylates, i.e., 20.4% for the cis tosylate and 12.9% for the trans tosylate, indicate the highest extents of retention for phenol among those known for any other hydroxylic solvents. The initially added t-butylcyclohexenes exert no influence on the olefin or on the phenyl ether composition, whereas triethylammonium and diethylammonium p-toluenesulfonates, when added initially, enhance the phenolysis rate and exert a small but definite influence on the composition of the phenyl ether. The hypothesis of the hydrogen-bridged cation, proposed in order to explain the enhanced rate of the cis isomer and in order to elucidate the retained solvolysis product, has been questioned by a consideration of the mechanism on the basis of the results of this phenolysis.
  • Kunio Okamoto, Seiki Saitô, Haruo Shingu
    1969 Volume 42 Issue 11 Pages 3298-3305
    Published: 1969
    Released: March 27, 2006
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    As the first examples of solvolytic cis-trans isomerization and 1,2-rearrangement for the 4-t-butylcyclohexyl system, phenolytic cis-trans (or trans-cis) isomerization and 1,2-rearrangement have been found for cis- and trans-4-t-butylcyclohexyl p-toluenesulfonates in the phenol-benzene (1 : 1 by wt) solvent at 75.0°C. The tosylate, recovered after a 75% completion of the SN1 phenolysis of the cis-4-tosylate, was composed of small amounts of the trans-4-tosylate (1%) and the cis-3-tosylate (11%), besides 88% of the starting cis-4-tosylate, clearly indicating occurrence of both the cis-trans isomerization and the 1,2-rearrangement of the starting cis-4-tosylate. In a similar fashion, starting from the trans-4-tosylate, small amounts of the cis-4-tosylate (0.7%) and the trans-3-tosylate (2.6%) were recovered from the tosylate after the SN1 phenolysis was 75% complete. On the basis of the results of an examination into the influence of the added tosylate anion on the extent of isomerization and of rearrangement, it has been suggested that the cis-trans or trans-cis isomerization results largely from the external SN2-like attack of the tosylate anion on the SN1 ion-pair intermediate and partly as a consequence of the rotation of the t-butylcyclohexyl cation within the ion-pair intermediate, whereas the 1,2-rearrangement proceeds through an intramolecular 1,2-shift of hydrogen within the 4-t-butylcyclohexyl cation.
  • Kinko Koyano, Hiroshi Suzuki
    1969 Volume 42 Issue 11 Pages 3306-3309
    Published: 1969
    Released: March 27, 2006
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    The NMR and UV spectra of α,N-diphenylnitrone and its derivatives which have a substituent at the para position of the α-phenyl group and some of which have in addition a methyl substituent at the ortho position of the α-phenyl group were measured. Examination led to the following conclusions. The NMR signal of the ortho protons of the α-phenyl group appears at a very low field. This is mainly attributed to the direct effect of the negatively charged oxygen atom of the nitrone group. Increase in the electron-donating power of the para substituent enhances this effect.
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