Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 41 , Issue 12
Showing 1-50 articles out of 56 articles from the selected issue
  • Masao Hashimoto
    1968 Volume 41 Issue 12 Pages 2823-2828
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The electric and mechanical properties of lipid membranes between two electrolyte solutions were observed. The electric resistance was 107–108 Ω·cm2; the capacity, 0.2–1 μF/cm2, and the surface tension, 2.2–4.9 dyn/cm. The electric conductivity increased with an increase in the surface area of the lipid membranes. Furthermore, the electric resistance and the capacity decreased when an ionic surface-active agent was adsorbed to the lipid membranes. The effect may be caused by the structural change of the lipid membranes due to both the electric and the hydro-phobic interactions between the ionic surface-active agent and the lipid membranes.
  • Fumikatsu Tokiwa, Kenji Ohki
    1968 Volume 41 Issue 12 Pages 2828-2832
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Electrophoretic measurements have been made of the micelles of dimethyldodecylamine oxide (DDAO) and N-dodecyl-β-aminopropionic acid (DAPA), while changing the pH values of the solutions in the presence of 0.10 M sodium chloride. A picture of the structure of the electrical double layer around the micelle at different pH’s was then constructed, according to Stern’s theory, by a combination of the zeta potential, ζ, calculated from the electrophoretic mobility and the surface potential, ψ0, obtained previously from the potentiometric titration. With the micelle of DDAO, the thickness of the immobile part of the double layer depends slightly on the pH of the solution and is estimated to be about 5 Å. With the micelle of DAPA, the estimated thickness of the immobile part seems rather high, especially on the alkaline side of the solution. The ζ⁄ψ0 ratio for the micelles of DDAO and DAPA depends on the pH of the solution; in the case of DDAO the value of ζ⁄ψ0 increases with a decrease in the surface potential.
  • R. Allan Stewart, L. W. Reeves, Shizuo Fujiwara
    1968 Volume 41 Issue 12 Pages 2832-2834
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Contrary to previous reports, the linewidth of the electron spin resonance spectrum of cupric ion as measured in gauss between points of maximum slope is a sensitive function of ionic strength, chloride ion concentration and cuprous ion concentration. Assuming that electron spin relaxation rates do not change greatly on the addition of cuprous ion, it is possible to derive an electron exchange rate for the reaction:
    Cu^++Cu^2+↔Cu^2++Cu^+
    of k=1.53×109 l/mol/sec. This value is in good agreement with a previous determination of the same rate constant by McConnell and Weaver using the 63Cu nuclear magnetic resonance (0.5×108). The results for the linewidth changes can be rationalized in all cases by assuming that bridge chloride ions between two cupric ions or one cupric and one cuprous ion change drastically in concentration as such factors as ionic strength or chloride ion concentration changes. The g value of the electron (free) decreases as chloride ion is added, indicating delocalization of the unpaired electron onto chloride ligands.
  • Hiroshi Yokoi, Taro Isobe
    1968 Volume 41 Issue 12 Pages 2835-2839
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The ESR spectra of the copper(II) complexes of ethylenediamine, 1,2-diaminopropane, meso-2,3-diaminobutane, 1,3-diaminopropane, and ammonia were measured in methanolic and aqueous solutions at room temperature and in frozen solutions at the temperature of liquid nitrogen. The covalency of the bonding of the copper atom to the ligand atoms in these complexes was evaluated from the g values, the copper hyperfine constants, and the nitrogen super-hyperfine constants. Even in the case of amino groups which were coordinating groups, the π bonding seemed to be as important in determining the properties of the complexes as the σ bonding.
  • Kimio Tarama, Satohiro Yoshida, Shingo Ishida, Hideo Kakioka
    1968 Volume 41 Issue 12 Pages 2840-2845
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The role of the V=O bond in V2O5 in the adsorption of several gases was studied by measuring the electron spin resonance (ESR) and the infrared (IR) spectra. The ESR spectra of V2O5 supported on γ-Al2O3 were similar to those of VOSO4 on γ-Al2O3. When such electron-donating gases as CO, SO2 and C2H4 were adsorbed on this V2O5-γ-Al2O3, the signal intensity of ESR increased and the splitting of the h.f.s. became clear. Upon treatment with an electron-accepting gas such as O2, a reverse change was observed. In the case of V2O5 supported on SiO2, similar ESR spectra were observed by the adsorption of CO after a mild reduction. The IR spectra of V2O5 have a sharp absorption peak at 1023 cm−1 due to the stretching vibration of the (V=O)3+ bond; this peak became broader by adsorption of such gases as CO and SO2. Simultaneously, the center of the peak shifted to the red region and a weak hump appeared at 980–990 cm−1, probably due to (V=O)2+. These results of the ESR and IR measurements reveal that these electron-donating gases are adsorbed on the (V=O)3+ bonds on the surface of V2O5, and that the increase in electron densities in the adsorption sites results from adsorption of these gases. Furthermore, the role of this (V=O)3+ bond in oxidation reaction was also discussed.
  • Fumikatsu Tokiwa, Kenji Ohki, Isao Kokubo
    1968 Volume 41 Issue 12 Pages 2845-2848
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The gel filtrations of mixtures of sodium dodecyl sulfate (SDS) and sodium tetradecyl sulfate (STS) have been studied for different mole ratios of STS/SDS with varying total concentrations. Above the critical micelle concentration (CMC) of the mixture, two retention volumes V1obs and V2obs were obtained from the elution curve, and the difference between V1obs and V2obs depends on the total concentrations of the mixture. The initial part of the effluent contains only STS, which means that the separation of STS from the mixture occurs after passing through the column. These results have been discussed by taking into consideration the equilibrium between monomers and micelles for the mixtures of the two surfactants. It is shown that the separation factor is determined by the CMC values of the two surfactants—the greater the ratio CMCA/CMCB (CMCA>CMCB), the greater the degree of separation.
  • Taku Matsuo, Hideto Shosenji, Reiji Miyamoto
    1968 Volume 41 Issue 12 Pages 2849-2852
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The longest wavelength electronic absorption band of 1-(p-substituted phenyl)pyrrole has been found to show a regular bathochromic shift as the electronegativity of the substituent on the phenyl group increases. The substituent effect is closely related to that for the intramolecular charge-transfer bands of p-substituted anilines. Therefore, the longest wavelength absorption band of 1-(p-substituted phenyl)pyrroles have been suggested to be originated from an electron transfer from the pyrryl group to the phenyl group. Only one exception is the spectra of 1-(N,N-dimethyl-p-aminophenyl)pyrrole. In this case, the longest wavelength electronic absorption band is suggested to be due to an electron-transfer from the N,N-dimethylamino group to the phenyl group.
  • Kunihiro Abe, Yoshio Matsunaga, Gunzi Saito
    1968 Volume 41 Issue 12 Pages 2852-2854
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The 4,4′-dinitrobiphenyl complexes with benzidine and tetramethylbenzidine, in which the long axes of the component molecules are known to be perpendicular to each other, were examined for the diffuse reflection spectra. The deep coloration in these complexes was found to be due to the appearance of broad, weak charge-transfer absorptions.
  • Haruo Kuroda, Shoji Hiroma, Hideo Akamatu
    1968 Volume 41 Issue 12 Pages 2855-2858
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Polarized absorption spectra in the 10–40 kK region were observed on single crystals of the molecular compounds of tetracyano-p-quinodimethane(TCNQ) with tetramethyl-p-phenylenediamine (TMPD) and with dimethyl-p-phenylenediamine (DMPD). These molecular compounds possess an ionic structure in the ground state. A strong, broad absorption band appears in the near-infrared region of the crystal spectra with a polarization parallel to the crystal axis along which the component ions are alternately stacked making their molecular planes parallel to each other. The absorption maximum of this band is located at 7.7 kK in TMPD·TCNQ and at 8.5 kK in DMPD·TCNQ. These bands are assigned as a one associated with the charge transfer from TCNQ ion to the positive ion of the donor. Other absorption bands found in the spectra can be assigned as local excitation bands associated with the intramolecular transitions of the component ions. However, they are found to be considerably broadened and appreciably shifted to higher energy as compared with the solution spectrum of each component ion.
  • Toshio Ikeda, Hidefusa Ohe, Saburo Kawamura
    1968 Volume 41 Issue 12 Pages 2858-2860
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The Soret coefficients of aqueous solution of alkaline earth chlorides were determined indirectly using combined thermocells. “Combined thermocell” refers to a cell system of a back to back combination of two thermocells made of common electrodes and different electrolytes without liquid junction. The values are −2.79 for MgCl2, −3.43 for CaCl2, −4.09 for SrCl2, and −4.73 for BaCl2, respectively (in the unit of 10−3 deg−1) at 0.005 M and 25°C. These agree with reported values found by the direct method.
  • Toyoaki Kimura, Tetsuo Miyazaki, Kenji Fueki, Zen-ichiro Kuri
    1968 Volume 41 Issue 12 Pages 2861-2866
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The effects of temperature and electron scavengers on the hydrogen yield in the radiolysis of methylcyclohexane have been investigated by conventional kinetic techniques. The I value for hydrogen formation from pure methylcyclohexane varied from 4.9 to 4.4 in the range from room temperature to liquid nitrogen temperature. In the iodobenzene-methylcyclohexane system, the decrease in hydrogen yield was equal to the yield of benzene produced within experimental error. It is concluded that the benzene is formed through H atom abstraction from the solvent molecules by phenyl radicals which are formed by dissociative electron attachment to iodobenzene and that the benzene yield indicates the scavenged electron yield. Furthermore, a kinetic treatment for electron scavenging in the glassy state was presented. In the N2O-methylcyclohexane system, it was found that the ratio of the nitrogen yield, G(N2), to the decrease in hydrogen yield, ΔG(H2), is 2 in the temperature range from room temperature to −140°C, 1 at −160°C, and increases from 1 to 4 with increasing N2O concentration at −196°C, respectively.
  • Hideo Ueda, Noriyoshi Sakabe, Jiro Tanaka, Akio Furusaki
    1968 Volume 41 Issue 12 Pages 2866-2871
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The structure of the Meisenheimer complex has been determined by the X-ray method. The complex is characterized by a symmetrical structure, in which the two methoxyl groups are nearly equivalent to each other. The results showed a peculiar shape of the reaction intermediate, the substituted carbon atom is transformed into a tetrahedral shape, while the planarity of the whole molecule is kept with an increased conjugation between the nitro group and the ring system.
  • Hajime Ogura
    1968 Volume 41 Issue 12 Pages 2871-2876
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The 60Co γ-irradiation of dilute aqueous solutions of hydrogen cyanide (6 mM) in the absence of oxygen yielded mainly ammonia with G=1.9, formaldehyde with G=1.1, and carbon dioxide with G=0.8, while G(–HCN)=5.8 molecules per 100 eV. Polymeric hydrogen cyanide was also observed with the G(–HCN(polymer))\simeq4, which showed an intense broad absorption band in the UV region upon γ-irradiation. The following material balances were observed with the main products:
    G(-HCN)\simeqG(NH_3)+G(-HCN(polymer))\simeqG(CO_2)+G(HCHO)+G(-HCN(polymer))
    The results can be interpreted in terms of a mechanism involving HCN, H2CN, and H(OH)CN radicals. The ratio of the rate constants for the reactions of eaq and H atoms with hydrogen cyanide to those with several scavengers have been determined as k(eaq + HCN)/k(eaq + NO3)=0.019 and k(H + HCN)/k(H + 2-propanol)=1.4, all at 17°C.
  • Hiroshi Seki, Reiko Nagai, Masashi Imamura
    1968 Volume 41 Issue 12 Pages 2877-2881
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The γ radiolysis of a binary mixture of methanol and water over a wide concentration range has been investigated. The observed yields of products are expressed as a linear function of the electron fraction of methanol in the mixture. The yields of molecular hydrogen were also determined. Analyzing the results on reasonable assumptions, one could obtain for neutral water, Ge\barsw=2.3–2.5 and GOHw≥2.6. It was concluded that, in the radiolysis of methanol, formaldehyde may be produced through the decomposition of CH2OH radicals in the spur region, not by the disproportionation of these radicals.
  • Syozi Noda, Kenji Fueki, Zen-ichiro Kuri
    1968 Volume 41 Issue 12 Pages 2882-2886
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    ESR and optical studies have been made of dissociative electron attachment by phenyl halides and reaction intermediates produced in γ-irradiated glassy solid matrices at 77°K. Dissociative electron attachment by phenyl halides is an efficient process and the ratio of cross sections C6H5I/C6H5Br/C6H5Cl for this process in MTHF glass is 1.5/1.0/1.0. The phenyl radical produced abstracts a hydrogen atom from solvents (MTHF, 3MP) at 77°K and is stable in aqueous alkali-metal hydroxide glass. A part of 3MP radicals in a γ-irradiated solution of phenyl bromide in 3MP at 77°K disappear by a first-order process for which k=4.3×10−2 min−1. γ-Irradiated 3MP glasses containing phenyl halides exhibit the optical absorption spectra having characteristic absorption bands in the visible and UV region which are assigned to solute cations and hydrogen-adducts respectively.
  • Akio Furusaki
    1968 Volume 41 Issue 12 Pages 2886-2894
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The isomerization of several dimers of perchloro-(3,4-dimethylenecyclobutene) (I) has recently been reported by Fujino et al. Of these dimers, one (II) is transformed to other isomers (IIIa) and (IIIb) by means of pyrolysis at ca. 200°C. When heated to ca. 250°C, IIIa and IIIb are further converted into a fourth isomer (IV). The present X-ray study has revealed that II corresponds to perchloro-(3,4,7,8-tetramethylene-tricyclo[4.2.0.02.5]octane), as supposed from the chemical evidence, and IV, to perchloro-(4,8-dimethylene-tricyclo[3.3.2.01.5]deca-2,6-diene). It has been further established, from the results of the X-ray analysis of the dichloride of IIIa with the help of the chemical information, that IIIa and IIIb have the same two-dimensional chemical structure, perchloro-(3,4,7,8-tetramethylene-cycloocta-1,5-diene), rather than perchloro-(2,3,7,8-tetramethylene-bicyclo[4.2.0]octa-4-ene) which was speculated by Fujino et al., and that IIIa and IIIb are different from each other in the conformation of the cyclooctadiene ring. These structures for II, IIIa, IIIb, and IV give a reasonable explanation of the mechanism of the successive isomerization reactions mentioned above.
  • Tetsuo Noguchi, Masao Mizuno
    1968 Volume 41 Issue 12 Pages 2895-2899
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The liquidus curve in the ZrO2-TiO2 system previously reported by the present authors was again examined with a heliostat-type solar furnace in order to determine the peritectic point in the ZrO2-rich side region. Quenched specimens from the melt of the ZrO2-rich side region were analysed by the X-ray technique. The cooling curves from the melt suggested the existence of a new phase stable at higher temperatures, and a tentative phase diagram at high temperatures is presented.
  • Terumichi Nakagawa, Koichiro Miyajima, Toyozo Uno
    1968 Volume 41 Issue 12 Pages 2899-2903
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The alkali fusion of alkyl sulfates was investigated by pyrolyzing a mixture of alkyl sulfates and alkali metal hydroxide between 200–500°C. The pyrolyzates were isolated and identified to be 1-olefins, internal olefins, alcohols, and dialkyl ethers by gas chromatography and IR spectroscopy. The mechanism of this reaction was proposed from these results and an attempt was carried out to estimate the alkyl chain carbon number distribution of the commercially available sodium alkyl sulfates.
  • Tsai-Teh Lai, Mon-Chao Chen
    1968 Volume 41 Issue 12 Pages 2903-2908
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The complexation of lead ion with arginine hydrochloride has been studied polarographically at 30°C. Four kinds of complex species, PbCl+, Pb(H2Arg)Cl2+, Pb(H2Arg)(OH)2+ and Pb(H2Arg)2(OH)3+ (where H2Arg denotes the arginine univalent cation) were confirmed in various pH range, respectively. The logarithmic dissociation constant of Pb(H2Arg)2(OH)3+ was found to be 10.33±0.03 at ionic strength 0.9.
  • Nobuyuki Tanaka, Masahiro Kagawa, Minoru Kamada
    1968 Volume 41 Issue 12 Pages 2908-2913
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    From the thermogravimetric analysis, hexamminenickel(II) complexes were confirmed to decompose in two or three steps through lower ammine intermediates NiXm·nNH3: n=2, 1 and m=2 for X=Cl; n=2 and m=2 for X=I, Br; n=4 and m=2 for X=NO3 and n=2, 1/2 and m=1 for X=SO4. The diffuse reflectance spectra of these intermediates have been measured in a range between 5000 to 27000 cm−1, and they suggested that these intermediates may be polymers in which nickel ions were octahedrally coordinated with ammonia molecules and bridging halogen atoms. The infrared absorption spectra of these intermediates obtained in a range between 5000 and 60 cm−1 are also reported.
  • Yoshihisa Matsui, Ryuji Kawakado, Yoshio Date
    1968 Volume 41 Issue 12 Pages 2913-2918
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The complex formation between tetraethylammonium bromide (TEB) and mercuric bromide in dimethylformamide was observed conductometrically, and a complex, tetraethylammonium tribromomercurate (TETM), was isolated. Voltammetric studies of TEB, TETM, and mercuric bromide were made, using the dropping mercury electrode in dimethylformamide containing 0.1 M tetraethylammonium perchlorate. It was found that TEB gives two reversible anodic waves, of which the more negative one is due to the oxidation of mercury to TETM, and the more positive, to the oxidation of mercury to mercuric bromide. The electrode reaction mechanism was also investigated by means of large-scale electrolysis with a controlled potential.
  • Masayuki Muto, Tetsuo Baba, Hayami Yoneda
    1968 Volume 41 Issue 12 Pages 2918-2921
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    An isomeric form of the hitherto known cis-[Co(CN)2 en2]+ was prepared from cis- or trans-[CoCl2 en2]+ and potassium cyanide in dimethylsulfoxide solution. The new complex was characterized by UV, IR and NMR spectra, and its trans configuration was established.
  • Akira Misono, Tetsuo Osa, Takamichi Yamagishi
    1968 Volume 41 Issue 12 Pages 2921-2927
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The direct electro-reduction of naphthalene was investigated in various solvents, mainly in an acetonitrile-water solution using supporting electrolytes containing tetraethylammonium and tetra-n-butylammonium cations. The main reduction product was 1,4-dihydronaphthalene, though small amounts of 1,2-dihydronaphthalene and tetralin were also detected. Under optimum conditions, the selectivity and the current efficiency of the formation of 1,4-dihydronaphthalene were 98% and 86.4% respectively. It was found that the water concentration and the solvent had a significant influence on the reduction products and the current efficiency. 1,4-Dihydronaphthalene is mainly formed through the step-by-step addition of two electrons and protons. In addition, 1,4-dihydronaphthalene may be formed by the protonation of the dianion formed by the disproportionation of the anion radical. Further, it was proposed that the formation of the tetraethylammonium radical might partly occur by means of the electron transfer from the anion radical of naphthalene to the tetraethylammonium cation, besides the direct electron transfer to the cation from the electrode.
  • Yo Miyagi, Sadao Kimura, Ryozo Goto
    1968 Volume 41 Issue 12 Pages 2927-2931
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    In the presence of cyanide ions, an α-ketoaldehyde dimerizes to give an acylformoin. The tautomerism of this compound was studied. It was found that the tautomerism between I and II is affected by the solvents and by the substituents. In proton-accepting solvents (EtOH, THF), I predominates. In ethanol-free chloroform, II is dominant for almost all substituents. In ethanol-containing chloroform, some acylformoins exist as I, while the others exist as II. The former case is observed when R=t-Bu and p-X–C6H4 (X=H, t-Bu, Cl, and Br); the latter case, when R=Me, i-Pr, and p–Me-C6H4. In the former case, ethanol reacts slowly with I to give an O-ethyl derivative (III). When R=2,4,6-Me3–C6H2, II predominates in all states. When R=p-Cl–C6H4 and p-Br–C6H4, I and II were isolated as crylstals. The solvent effects are interpreted in terms of the hydrogen-bonding interactions of I with basic and hydroxylic solvents.
    (Remark: Graphics omitted.)
  • Takayuki Otsu, Masami Yamaguchi
    1968 Volume 41 Issue 12 Pages 2931-2935
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The polymerization of styrene with systems of various metals and organic halides was investigated at 60°C. It was found that the metals which could be used as hydrogenation catalysts were effective as initiators and that the organic halides with a weak carbon-halogen bond showed a high initiating activity for styrene polymerization. From the kinetic studies of the polymerization of styrene by reduced nickel and chloroform, the rate of polymerization was shown to be proportional to the monomer concentration and to the square-root concentration of both nickel and chloroform in the lower concentration range of chloroform. Some radical inhibitors were also found to inhibit this polymerization. These results indicated that this initiator system could induce the radical polymerization. The apparent overall activation energy for the polymerization by this system was estimated as 11 kcal/mol. The resulting polystyrene was found to be a relatively-low-molecular-weight atactic polymer.
  • Tetsuo Nozoe, Takashi Toda, Toyonobu Asao, Akira Yamanouchi
    1968 Volume 41 Issue 12 Pages 2935-2941
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The tropylation of azulene, oxaazulan-2-one, and their derivatives was investigated, and various 1 and/or 3-tropylazulenes and 3-tropyloxaazulan-2-ones were obtained. The NMR, UV, and visible spectra of these tropylazulenes were then discussed. Some electrophilic reactions, such as azo-coupling and the acid treatment of four kinds of tropylazulenes, were studied, and it was found that exchanges of the tropyl group and the attacking electrophilies occurred.
  • Seiji Ebine, Masamatsu Hoshino, Kazuko Takahashi
    1968 Volume 41 Issue 12 Pages 2942-2948
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Isomeric 5,7- and 4,7-dibromo-2,3-benzotropones were prepared, not via 2,3-benzotropone, but by the bromination and subsequent dehydrobromination of 2,3-benzocycloheptenone. The tropone structure of these compounds was based on spectral data and hydrogenation to 2,3-benzocycloheptenone. The dibromo-2,3-benzotropones, when treated with hydroxylamine, underwent cine-reaction to 5- and 4-bromo-6-hydroxylamino-2,3-benzotropone oximes, which were then hydrolyzed and debrominated to the same 6-hydroxy-2,3-benzotropone. 5,7,5′-Tribromo-2,3-benzotropone was obtained by the drastic bromination, followed by the dehydrobromination, of 2,3-benzocycloheptenone. The position of a hydroxyl group in 6-hydroxy-2,3-benzotropone was confirmed by oxidation to o-carboxycinnamic acid, while that of the 5′-bromo substituent in 5,7,5′-tribromo-2,3-benzotropone was confirmed by hydrogenation to 5′-bromo-2,3-benzocycloheptenone.
  • Masamatsu Hoshino, Seiji Ebine
    1968 Volume 41 Issue 12 Pages 2949-2953
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    6-Hydroxy-2,3-benzotropone (or 3-hydroxy-4,5-benzotropone) (I) was brominated under various conditions, and the bromination products were subjected to debromination, substitution, and some other reactions. I reacted with a molar equivalent of bromine at 25°C to give 7-bromo-6-hydroxy-2,3-benzotropone (II), and with two molar equivalents of bromine at 25°C to give an adduct of II with bromine (V), which, on heating, was dehydrobrominated to 5,7-dibromo-6-hydroxy-2,3-benzotropone (IV). On the other hand, I reacted with bromine at 100°C to give 5-bromo-6-hydroxy-2,3-benzotropone (III), IV, and 2,2,7-tribromo-4,5-benzocyclohepta-4,6-diene-1,3-dione (VI), depending on the amount of bromine employed. All these bromination products could be debrominated with ease with hydrogen in the presence of catalyst to yield I. When II was heated with hydrobromic acid, the 7-bromo substituent was in part eliminated to give I and migrated in part to give III. When IV and 4,7-dibromo-6-hydroxy-2,3-benzotropone (X) were heated with hydrobromic acid, the 7-bromo substituents were eliminated and the 4- or 5-bromo substituent remained unreacted, producing III and 4-bromo-6-hydroxy-2,3-benzotropone (IX) respectively. When II and IV were heated with hydrochloric acid, the 7-bromo substituents were not eliminated but, rather, substituted with chlorine atoms to give 7-chloro-6-hydroxy-2,3-benzotropone (VII) and 5-bromo-7-chloro-6-hydroxy-2,3-benzotropone (VIII) respectively. These facts suggest that I and its bromo derivative sometimes behave as unsaturated β-diketones (I′).
  • Yoshio Iwakura, Keikichi Uno, Shinsaku Shiraishi, Tatsuhiko Hongu
    1968 Volume 41 Issue 12 Pages 2954-2959
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Thiophenc-2-carbonitrile N-oxide (I) and 5-chlorothiophene-2-carbonitrile N-oxide (II) were synthesized by the chlorination of corresponding aldoxime with nitrosyl chloride. These compounds gave Δ2-isoxazolines and isoxazoles through 1,3-dipolar cycloaddition reaction with compounds having double or triple bond as dipolarophiles. In the cycloaddition reaction, II was less reactive than I. This would be explained by stability of II owing to electron-withdrawing ability of chlorine atom at 5-position in the thiophene ring. Furoxans, the dimers of the nitrile N-oxide, were formed from these 1,3-dipoles in the absence of dipolarophile.
  • Tadashi Sasaki, Moriyasu Ando
    1968 Volume 41 Issue 12 Pages 2960-2963
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    N-Phenyl-C-(6-uracilyl)nitrone (II) was prepared in 80% yield from orotaldehyde (I) and phenylhydroxylamine. II underwent 1,3-dipolar cycloaddition reactions with several ethylenic and acetylenic compounds to afford the corresponding isoxazolidines (IIIa—f) and isoxazolines (IVg—i). Similar reactions of II with phenyl isocyanate, carbon disulfide and with enamine were carried out successfully. The structural elucidation of these products was done on the basis of their NMR spectra.
  • Tadashi Sasaki, Toshiyuki Yoshioka, Iwao Izure
    1968 Volume 41 Issue 12 Pages 2964-2969
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    C-(5-Nitro-2-furyl)-N-phenylnitrone (I) was prepared from 5-nitro-2-furfural and phenylhydroxylamine in an 80% yield. The 1,3-dipolar cycloaddition reactions of I with various olefins were carried out, and the corresponding 5-substituted isoxazolidine derivatives were obtained. The structual elucidation of these products was made on the basis of the nmr spectral data. Several observations support the theory that these reactions proceed via a concerted one-step process.
  • Itsutoshi Maeda, Ryonosuke Yoshida
    1968 Volume 41 Issue 12 Pages 2969-2974
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The hydroformylation reactions of acrolein acetals and acetates were carried out in order to discuss the side reactions and any subsequent reactions. Acrolein cyclic acetals reacted with carbon monoxide and hydrogen in the presence of a dicobalt octacarbonyl catalyst to give n- and iso-aldehydes in a 2:1 ratio; they gave no further reaction products. Acrolein diethylacetal underwent hydroformylation using a rhodium catalyst to give n- and iso-aldehydes in a 1:2 ratio. In the presence of a cobalt catalyst, however, various products were obtained. As a result of the acidity of cobalt hydrocarbonyl and a high reaction temperature, n-aldehyde, first formed in benzene, underwent change to 2,5-diethoxytetrahydrofuran and 1,1,4-triethoxybutane. In ethanol, n- and iso-aldehydes gave the corresponding acetals. In the hydroformylation of acrolein acetate, only n-aldehyde was obtained. Iso-aldehyde seemed to be converted into 2-methyl-3-acetoxyacrolein by deacetylation. In ethanol, besides n-acetal, iso-acetal and propionaldehyde acetate, 2,5-diethoxytetrahydrofuran and 2-methyl-3-ethoxyacrolein were recognized. The former seemed to be formed from n-aldehyde by ring closure and ethanolysis. The latter seemed to be formed by the ethanolysis of 2-methyl-3-acetoxyacrolein. In ethyl orthoformate, no side reaction was observed and the yield of the main product, 1,1-diacetoxy-4,4-diethoxybutane, amounted to 80%.
  • Itsutoshi Maeda, Ryonosuke Yoshida
    1968 Volume 41 Issue 12 Pages 2975-2978
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    DL-Tryptophan hydrantoin was obtained from phenylhydrazone of β-(hydanto-5-yl)-propionaldehyde acetal (5-(γ,γ-dialkoxypropyl)hydantoin) by Fischer’s indole synthesis. β-(Hydanto-5-yl)propionaldehyde acetal was prepared by Bucherer’s reaction from 1,1-diacetoxy-4,4-dialkoxybutane obtained by the hydroformylation of acrolein acetate. Attempts to crystallize β-(hydanto-5-yl)-propionaldehyde acetal from Bucherer’s reaction solution were unsuccessful, but 5-alkoxy-1,3-dioxoperhydropyrro[1,2-c]imidazole was obtained by treating the solution with ion exchange resins in alcohol. It could be also converted to tryptophan hydantoin.
  • Tetsuo Nozoe, Shoji Ryu, Takashi Toda
    1968 Volume 41 Issue 12 Pages 2978-2984
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The electrophilic substitution reactions of 2-aminotropone (I), 2-methylaminotropone (II), and 2-dimethylaminotropone (III) were investigated. The structure of the products was proved by hydrolysis to lead to known tropolone derivatives. By the nitrosation of II, N-nitroso-2-methylaminotropone was obtained in a good yield; this compound is a new type of active troponoid compound. The substitution reactions of III gave tropolone derivatives, accompanied by the hydrolysis of the dimethylamino group. The mechanism of the hydrolysis is then discussed.
  • Teruzo Asahara, Manabu Sen\={o}, Hideaki Kaneko
    1968 Volume 41 Issue 12 Pages 2985-2989
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The electrolytic reduction of naphthalene was carried out in various alcohol-hexamethylphosphoramide (HMPA) systems in the presence of lithium chloride. The reduction of naphthalene proceeds effectively at relatively low cathode potentials in the presence of HMPA; the composition of the products varies with the changes in the reduction potential, the kind of alcohols, and the concentration of HMPA. The dark blue color is observed at the cathode during the electrolysis in HMPA solutions in either the presence or the absence of ethanol. It is suggested that the color reflects the generation of solvated electrons, and that reduction of naphthalene is caused not through a direct electron-transfer from the cathode, but through a reaction with solvated electrons as the reductive agent.
  • Yoshinobu Takegami, Yoshihisa Watanabe, Isao Kanaya, Takeaki Mitsudo, ...
    1968 Volume 41 Issue 12 Pages 2990-2994
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The reaction between potassium iron carbonylates (KHFe(CO)4, K2Fe(CO)4 and K2Fe2(CO)8) and isoprene has been studied. Isoprene is reduced at room temperature to give three olefins (3-methyl-1-butene (I), 2-methyl-1-butene (II), and 2-methyl-2-butene (III)). The reaction conditions (solvents, atmospheres, additives such as water) have a great effect on the yield and distribution of the olefins. Under carbon monoxide in the presence of water, the reduction is highly promoted, giving 2 mol/mol-Fe(CO)42− of the olefins. The percentage of II is almost constant (about 15%) in any case, but the percentages of I and III, very dependent on the conditions, change in the 3–40 and 50–80% ranges respectively. The reaction is suggested to proceed via some kinds of σ- and π-allyl iron carbonyl complexes. Under carbon monoxide the carbonylation of isoprene also occurs.
  • Akira Misono, Yasuzo Uchida, Kunikazu Yamada, Tadashi Saeki
    1968 Volume 41 Issue 12 Pages 2995-3001
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The copolymerization of vinyl chloride with ethylene was carried out in n-heptane by using the catalyst systems consisting of VO(OEt)3 and AlEt3, AlEt2Cl, or AlEtCl2 at 50°C. It was found that each of the above catalyst systems produces a random copolymer at Al/V molar ratios below 1.5; however, polyethylene is mainly obtained above the ratio of 1.5. With the VO(OEt)3/AlEt3 catalyst system, its good catalyst activity being in contrast with the inactivity of the Ti(O-n-Bu)4/AlEt3 catalyst system, the maximum catalyst activity was observed at the Al/V molar ratio of 0.5. The copolymerization rate decreased with an increase in the ethylene fraction in the monomer mixture, reaching a minimum value at a 80 mol% ethylene feed; however, the rate increased above this feed ratio with a further increase in the ethylene feed. The contamination of a copolymer with polyethylene which has been observed in the copolymerization by the Ti(O-n-Bu)4/AlEt2Cl or AlEtCl2 catalyst system was not observed in the present case. The monomer reactivity ratios for the copolymerization by the VO(OEt)3/AlEt3 catalyst system were found to be r1(vinyl chloride)=2.48 and r2(ethylene)=0.02. The reaction between VO(OEt)3 and AlEt3 was investigated by means of infrared spectroscopy and gasometry, and it was found that the average valency states of the V of the catalyst system is higher than four at the Al/V molar ratio range where a random copolymer is exclusively obtained.
  • Keisuke Wada, Harukichi Hashimoto
    1968 Volume 41 Issue 12 Pages 3001-3007
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The reactions between benzyl chloride and cuprous chloride were studied. It was found that good yields of bibenzyl were obtained by the addition of ethylenediamine, diethylenetriamine, triethylenetetramine, acetylacetone and EDTA. Nothing of bibenzyl was observed in the cases of ethanolamine, pyridine, dipyridyl, phenanthroline and triphenylphosphine. These facts, together with the spectral studies of copper complexes can reasonably be explained by the formation of reactive species of the type CuI(en)nCl. The course of the reaction was discussed on the basis of the substituent and medium effects. Radical but not free type mechanisms which include the transient organocopper species were considered. Some additional comments were also made.
  • V. Kesavan, V. C. Devanathan, N. Arumugam
    1968 Volume 41 Issue 12 Pages 3008-3011
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Tadashi Sasaki, Toshio Ohishi
    1968 Volume 41 Issue 12 Pages 3012
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Tatsuya Sekine, Yoshimitsu Kawashima, Takaaki Unnai, Mitsuo Sakairi
    1968 Volume 41 Issue 12 Pages 3013-3015
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Norio Kunieda, Kazuo Sakai, Shigeru Oae
    1968 Volume 41 Issue 12 Pages 3015-3016
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Tadashi Sato, Sotaro Watanabe
    1968 Volume 41 Issue 12 Pages 3017-3018
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Tsutomu Fukuyama, Kozo Kuchitsu, Yonezo Morino
    1968 Volume 41 Issue 12 Pages 3019-3020
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Tsutomu Fukuyama, Kozo Kuchitsu, Yonezo Morino
    1968 Volume 41 Issue 12 Pages 3021-3022
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Tokiti Noda, Michio Inagaki, Shigehiko Yamada
    1968 Volume 41 Issue 12 Pages 3023-3024
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Shonosuke Zen, Seiko Tashima, Shinkichi Kot\={o}
    1968 Volume 41 Issue 12 Pages 3025
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Chiro Shinomiya, Toshiaki Kishikawa
    1968 Volume 41 Issue 12 Pages 3026
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Kahei Takase, Toyonobu Asao, Naonori Hirata
    1968 Volume 41 Issue 12 Pages 3027
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
  • Tadayoshi Higashiyama, Hideo Ueda, Akitsugu Nakahara
    1968 Volume 41 Issue 12 Pages 3028
    Published: 1968
    Released: March 27, 2006
    JOURNALS FREE ACCESS
feedback
Top