Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 51 , Issue 5
Showing 1-50 articles out of 75 articles from the selected issue
  • Keiichi Nagai, Mikio Katayama
    1978 Volume 51 Issue 5 Pages 1269-1272
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    TEA CO2 laser induced chemical reactions of ethylene, chloroethylenes and chloroethanes have been investigated. Since these compounds have absorptions at wavelengths of 10.6 or 9.6 μm band of the CO2 laser, strong excitation of the molecular vibration gives rise to an infrared photochemical reaction. In chlorine derivatives, the cleavage of the C–Cl bond by the laser irradiation appears to initiate decompositions of these materials. The final products were mainly brought about by molecular elimination of HCl, H2, or Cl2. The present results demonstrate that the CO2 laser induced reactions differ form their thermal reactions.
  • Tsutomu Okuda, Hideta Ishihara, Koji Yamada, Hisao Negita
    1978 Volume 51 Issue 5 Pages 1273-1277
    Published: 1978
    Released: April 19, 2006
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    The Zeeman effect on 81Br NQR and the quadrupole effect on 27Al NMR in L·AlBr3 complexes (L=KBr, POBr3, and H2S) were studied at room temperature. It was found that the 27Al quadrupole-coupling constant for these complexes decreases with decreasing coupling constant of the 81Br atom in –AlBr3 and that the atomic arrangement about the Al atom has C3V symmetry in POBr3·AlBr3 and H2S·AlBr3. In the latter complex, H2S molecule is reorientated at room temperature. The amount of charge transfer in these complexes was estimated on the basis of the Townes-Dailey theory and the bond angle ∠Br–Al–Br was found to depend on the amount of the charge transfer. The temperature dependence of the 81Br NQR frequencies was observed in order to obtain information about molecular motion in H2S·AlBr3 and POBr3·AlBr3.
  • Kojiro Takahashi, Zengo Horiuchi, Tatsuya Yasunaga
    1978 Volume 51 Issue 5 Pages 1278-1283
    Published: 1978
    Released: April 19, 2006
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    The binding of Toluidine Blue to chondroitin-4-sulfate was investigated by absorption spectra, titration curves, and temperature-jump relaxation spectra. The results were well interpreted by a basic model of binding to a linear lattice, where the cooperative interaction is restricted to the nearest-neighbor binding sites. The parameters g (number of binding sites per disaccharide repeating unit), K (cooperative binding constant), and q (strength factor of cooperativity) in 0.015 M phosphate buffer (pH 7.0) were determined to be 2, 1.02×105 M−1, and 270±60, respectively. The fastest process of the three relaxations observed in the system of Toluidine Blue-chondroitin-4-sulfate, could be interpreted as the aggregation process for cooperative binding. The rate constant \ ildekR was determined to be 1.6×108 M−1 s−1 at 28 °C.
  • Kenjiro Kondo, Masuo Yagi
    1978 Volume 51 Issue 5 Pages 1284-1290
    Published: 1978
    Released: April 19, 2006
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    The reactions of isomeric-transition activated 82Br were studied in the gaseous H82mBr–CH4(HBr/CH4=0.1±0.01) system. CH382Br and CH282BrBr were identified as the reaction products; their absolute yields were 0.8% for CH382Br and 3.7% for CH282BrBr respectively. The results were compared with those obtained in the H80mBr–CH4 and 80mBr2 (or 82mBr2)–CH4 systems. The effect of Krand Xe additives showed that these products were formed only through kinetic energy-independent (thermal-ionic) reactions, as opposed to the results obtained in the 80mBr2 (or 82mBr2)–CH4 system. This difference was explained on the basis of the kinetic energies initially acquired by the bromine atoms in the molecular-explosion process. In addition, an outstanding isotope effect resulting from the difference in the decay schemes of 80mBr and 82mBr was observed between the I. T.-activated 80Br and 82Br reactions in the H80mBr–CH4 and H82mBr–CH4 systems, and it was pointed out from the analysis of the 80mBr-data that the two successive internal conversions in the 80mBr decay were responsible for this isotope effect. It was considered that the second internal conversion started in a liquid-like condition such as ion-clusters containing the 80Br in the intermediate state; this idea is supported by the experimental results obtained in the condensed phase.
  • Megumu Nagasawa, Kiyoshi Kikukawa, Makoto Takagi, Tsutomu Matsuda
    1978 Volume 51 Issue 5 Pages 1291-1293
    Published: 1978
    Released: April 19, 2006
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    Irradiation of a solution of W(CO)6 and group IVa metal halides in benzene by UV light gave the olefin metathesis catalysts, of which the combination W(CO)6–TiCl4 was the most effective. Association of the coordinatively unsaturated W(CO)5 and TiCl4 was suggested to be a key step in the formation of a catalytically active complex. A survery was also made for other W(CO)6–MXn combinations for photo-generation of metathesis catalyst.
  • Shozo Yanagida, Kazutomo Takahashi, Mitsuo Okahara
    1978 Volume 51 Issue 5 Pages 1294-1299
    Published: 1978
    Released: April 19, 2006
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    The complexation of homogeneous polyethylene glycols and their dimethyl ethers(glymes) with alkali and alkaline-earth metal cations was studied by PMR spectroscopy on the basis of a comparison with crown ethers. The ethylene proton signal of octaethylene glycol in methanol-d4 was split into three lines by the addition of a potassium, rubidium, caesium, strontium, or barium cation. The latter two cations also caused large downfield shifts of the signals, which are quite comparable with those of 15-crown-5 and 18-crown-6 caused by the same metal cations. As for heptaethylene glycol, a splitting was observed in the presence of a strontium ion or an alkali metal cation except for a lithium ion. A large downfield shift was also observed in the presence of a strontium or barium ion. As for hexaethylene glycol, the signal was split only by a sodium ion, and the optimal interaction with a calcium ion was confirmed on the basis of the downfield shift. In methanol-d4, lithium and magnesium ions did not cause any change in the PMR spectra of either the crown ethers or the glycols. The PMR downfield-shift method also disclosed the metal-ion complexation of the glycols in water. The terminal hydroxyl groups play an important role in the complexation.
  • Takeshi Sawai, Naoki Ohara, Toshinari Shimokawa
    1978 Volume 51 Issue 5 Pages 1300-1306
    Published: 1978
    Released: April 19, 2006
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    The kinetics of the radiation-induced dechlorination of hexachloroethane was investigated in deoxygenated alcohol solutions. The major products were hydrogen chloride, pentachloroethane, 1,1,2,2-tetrachloroethane, tetrachloroethylene, and aldehydes or acetone. No 1,1,1,2-tetrachloroethane was observed. The radiationchemical yields of these products and the disappearance of hexachloroethane were quite high; these facts indicate that a chain reaction is involved in these processes. After the hexachloroethane had effectively dechlorinated down to tetrachloro compounds, there were no marked changes in the lower chlorinated compound upon continuous irradiation. Tetrachloroethane was formed via pentachloroethane, but tetrachloroethylene was produced by means of C2Cl5→C2Cl4+Cl reaction and the yield was paticularly high in methanol compared with the other alcohols. The chain length of the dechlorination from hexachloroethane to pentachloroethane and from pentachloroethane to tetrachloroethane increased in the order of 2-propanol>ethanol>methanol. The G(−C2Cl6) and G(products) were proportional to (dose rate)−1⁄2, and the ratio of G(C2HCl5) to G(C2Cl4) was a constant in each alcohol solution, regardless of the dose rate. The α-hydroxy alkyl radical is the chain carrier for the dechlorination reaction of hexachloroethane in alcohol solutions. The relative rates of the dechlorination were found to be 1, 3, and 14 for \dotCH2OH, CH3\dotCHOH, and (CH3)2\dotCOH, respectively. The order in the rate is in agreement with that of the redox potential of these radicals. The effect of the irradiation temperature on the products yields was also examined.
  • Tatsuo Takahashi, Takefumi Koiso
    1978 Volume 51 Issue 5 Pages 1307-1310
    Published: 1978
    Released: April 19, 2006
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    The thermodynamic ion-association constants (K) of [Cr(NH3)6]3+, [Co(NH3)6]3+, [Cr(en)3]3+, and [Co-(en)3]3+ with several anions in aqueous solutions were determined using the conductometric method. The logK values obtained at 25.0 °C are 1.17 for [Cr(NH3)6]3+–SCN, 1.34 for [Cr(en)3]3+SCN, 1.30 for [Co(NH3)6]3+–SCN, 1.34 for [Co(en)3]3+–SCN, 1.68 for [Co(en)3]3+–Br, 1.46 for [Co(en)3]3+–I, 1.37 for [Co(en)3]3+–ClO4, 3.20 for [Cr(NH3)6]3+–C2O42−, and 2.97 for [Cr(en)3]3+–C2O42−. The results indicate that the SCN ion has less of a tendency to associate with the complex cations than do other univalent anions, the K values of SCN being of the same order of magnitude as those of ClO4, and that the K values of chromium(III) complex cations with several anions are slightly smaller than those of the corresponding cobalt(III) complex cations.
  • Shingo Araki, Toshio Tanaka
    1978 Volume 51 Issue 5 Pages 1311-1314
    Published: 1978
    Released: April 19, 2006
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    Following 10 simple and complex salts of TCNQ\ ewdot with N,N-disubstituted 1,3-dithiolan-2-iminium cations; (Remark: Graphics omitted.) (n=1 when R1=R2=n-Pr, n-C6H13, n-C8H17, Ph, and R1=Me and R2=Ph; n=2 when R1= R2=n-Pr, n-Bu, Ph, and R1=Me and R2=Ph), and (Remark: Graphics omitted.) were prepared. Of these, simple salt (Remark: Graphics omitted.) was obtained in two different crystalline forms; unstable violet needles and green plates. All the salts as compacted samples displayed semi-conducting behaviors in the 20–90 °C range. Electrical resistivities of the 1:2 complex salts fell in the range of 5–90 ohm cm at 25 °C, while the simple and 2:3 complex salts showed much large resistivities (the order of 103–109 ohm cm). The measurements of electronic absorption spectra and magnetic susceptibilities indicated that the simple salts in the solid state involve dimeric (TCNQ)22−, except for the green salt of (Remark: Graphics omitted.) which consists of the iminium cation and discrete TCNQ\ ewdot radical anion. Electronic spectra of the 1 : 2 and 2 : 3 complex salts also are discussed in comparison with analogous TCNQ\ ewdot salts reported so far.
  • Hiroshi Nakatsuji, Kazuo Matsuda, Teijiro Yonezawa
    1978 Volume 51 Issue 5 Pages 1315-1323
    Published: 1978
    Released: April 19, 2006
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    The force and density origins of the molecular shapes of CH3+ and NH3 are studied comparatively on the basis of the floating wave functions which satisfy the Hellmann-Feynman theorem for the forces acting on the terminal protons. It is confirmed quantitatively that the previous concepts of the electrostatic force (ESF) theory correctly grasp the origins of the molecular shapes. Namely, the density-guiding rule which states that the nuclei are pulled in the direction of the electron-cloud reorganization i.e., the electron-cloud preceding and incomplete following), is verified as the density origin. The force origin which is the AD and EC forces reflects and quantifies the density origin. The roles of the other forces are also easily predicted by the ESF theory.
  • Yukiko Tanaka, Yoshimasa Tanaka, Yutaka Saito, Katsunosuke Machida
    1978 Volume 51 Issue 5 Pages 1324-1327
    Published: 1978
    Released: April 19, 2006
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    The infrared and Raman spectra of dimethylaminosulfonyl chloride and its C-deuterated derivative have been recorded in the liquid state. The fundamental frequencies have been assigned by referring to the band intensities, Raman depolarization ratios and isotopic frequency shifts. A normal coordinate analysis based on a planar Cs molecular model has been carried out by using a simple Urey-Bradley force field for stretching and bending coordinates and a valence force field for torsional coordinates. The calculated frequencies based on a refined set of force constants agree well with the observed ones.
  • Tadashi Kato, Tsunetake Fujiyama
    1978 Volume 51 Issue 5 Pages 1328-1331
    Published: 1978
    Released: April 19, 2006
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    Light scattering spectra have been observed for binary solutions of chloroform–tetrabutylammonium chloride (TBACl) and chloroform–hexadecyltrimethylammonium chloride (HTACl) at various concentrations. The Rayleigh intensities have been reduced to concentration fluctuations. The observed concentration dependence of the concentration fluctuation was explained in terms of the existence of aggregates which were composed of a few surfactant molecules and several decades of chloroform molecules. Using the infrared data, the structures of the aggregates were demonstrated to be double-layered. In HTACl solution, a singular concentration dependence of concentration fluctuation was observed in the concentration range below 0.004 mole fraction.
  • Hiromi Motomura, Zenzo Morita
    1978 Volume 51 Issue 5 Pages 1332-1336
    Published: 1978
    Released: April 19, 2006
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    The diffusion coefficients and rate constants of the reactions of C. I. Reactive Yellow 4, Orange 1, and Red 1 were measured at 30 °C by means of a cylindrical cellophane film roll. The diffusion coefficients of the three hydrolyzed dyes were nearly constant at all the pH values examined. The apparent diffusion coefficients of all the active species of Orange 1 and Red 1 except Yellow 4 were gradually decreased with an increase in the pH of the dyebath; this decrease was due to the hydrolysis of the active species in the cellulose substrate. The rate constants of the reactions with cellulose were of a pseudo-first-order; i.e., the second-order rate constants of reactions with cellulose were constant up to a certain pH, and thereafter they decreased with an increase in the pH of the dyebath. The pH dependence of the reactivity with cellulose was similar to that of the hydrolysis reported previously. The concentration profiles of the removed and immobilized species in cellulose dyed from a weakly alkaline dyebath agreed with the theoretical profiles of active and reacted species respectively. From a highly alkaline dyebath, those of the immobilized species agreed with the theoretical profiles of reacted species, while those of the removed ones did not agree with theoretical profiles of active species because of hydrolysis.
  • Nobutake Suzuki, Okihiro Tokunaga, Masamitsu Washino
    1978 Volume 51 Issue 5 Pages 1337-1340
    Published: 1978
    Released: April 19, 2006
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    The radiation-induced decoloration of azo and anthraquinone dyes was studied in N2O-saturated aqueous solutions containing halide ions. In the N2O-saturated solutions, the decoloration yield, G(–Dye), increased markedly upon the addition of Br and I, which are efficient scavengers of the OH radical. In the nitrogensaturated solutions, however, the G(–Dye) decreased upon the addition of Br and I. Such an increase in the G(–Dye) upon the addition of Br and I in the N2O-saturated solutions is mainly attributable to the attacks of the halide radical anions, Br2 and I2, on the ring structure of the dyes. On the other hand, the G(–Dye) was not changed upon the addition of Cl in the N2O-saturated solution. This may be attributable to the very slow rate of the formation of Cl2 in a neutral solution.
  • Hirotoshi Ito, Yasumasa J. I’Haya, Toshiyuki Eri
    1978 Volume 51 Issue 5 Pages 1341-1349
    Published: 1978
    Released: April 19, 2006
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    The UV, ORD, and CD spectral bandshapes of polyadenylic acid (poly A) have been investigated theoretically in order to challenge the problems of whether discrimination of the single- and double-stranded poly A’s is computationally possible and of what structure poly A holds in a neutral solution. A linear response polarizability theory is applied to the derivation of UV, ORD, and CD bandshape functions of a polymer composed of N identical monomers. Using the observed and/or assumed values for the spectral bandshape of the adenine monomer, the UV, ORD, and CD spectra of both single- and double-stranded poly A’s are calculated by changing geometrical parameters. The single-stranded poly A at neutral pH is assumed to have a regular helical structure which is regarded as a counterpart of the double helix form of the double-stranded poly A. This model leads to the chainlength (N) effect which in turn suggests that the structure of poly A in a neutral solution is very flexible and is such that it can be approximated as a random assembly of adenine dirners and/or trimers, when the theoretical spectra of both the single- and double-stranded poly A’s are compared.
  • Henryk Kozlowski, Jun-ichi Isoya, Shizuo Fujiwara
    1978 Volume 51 Issue 5 Pages 1350-1353
    Published: 1978
    Released: April 19, 2006
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    The ESR spectra of Cd(I) hot ions produced in solid solutions of K2[(Zn, Cd, Hg)(CN)4] indicate that there are paramagnetic species of hot-ion molecules characteristic of the single phase of K2[Zn(CN)4] and of the solid solution. The total contribution from the s and p orbitals to the spin density of the Cd(I) hot ions is constant, although the relative contributions from these two orbitals vary. It is shown that the mother lattice surrounding the hot ions determines the electronic structure and stability of the hot ions. These results suggest that the investigation of hot ions in a solid solution is useful for the study of microstructure of the solid solution.
  • Masatoshi Watabe, Masayuki Zama, Sadao Yoshikawa
    1978 Volume 51 Issue 5 Pages 1354-1357
    Published: 1978
    Released: April 19, 2006
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    Three isomers of L-histidinatoiminodiacetatocobalt(III) complex have been prepared and characterized on the basis of their absorption, circular dichroism and proton magnetic resonance spectra. These isomers isomerized mutually in water at 80 °C. The equilibrium mole fractions of these isomers in water were found for cisN, transN and fac to be 0.91, 0.04, and 0.05, respectively.
  • Kenzo Kitayama, Takashi Katsura
    1978 Volume 51 Issue 5 Pages 1358-1362
    Published: 1978
    Released: April 19, 2006
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    The phase equilibria in the Lu2O3–V2O3–V2O5 system were established at 1200 °C. In this system, Lu2O3, LuVO3 LuVO4, V2O3, V3O5, V4O7, V5O9, V6O11, V7O13, and three new compounds Lu7V3O16, Lu2V2O7, and LuV4O8 are stable. LuVO4, V2O3, VO2, Lu7V3O16, Lu2V2O7, and LuV4O8 have non-stoichiometric compositions. The relationships between the composition and the −logPO2 values of the solid solutions were obtained from the thermogravimetric results. On the basis of the phase equilibria, the standard Gibbs free energies of several reactions were determined. The spacings, relative intensities, and densities of new compounds were also determined.
  • Mamoru Shibuya, Kazutoyo Endo, Hirotoshi Sano
    1978 Volume 51 Issue 5 Pages 1363-1367
    Published: 1978
    Released: April 19, 2006
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    Tin plates corroded by various acids were nondestructively analyzed by a 119Sn conversion electron Mössbauer spectroscopy, a transmission Mössbauer spectroscopy, and an X-ray diffractometry. The conversion electron method was shown to be useful for analysis of some corrosion products which could not be easily observed by the transmission method. By using both the Mössbauer spectroscopy and the X-ray diffractometry, the corrosion products formed by 6.7M-HNO3, 5.7M-HCl, and 9.0M-H2SO4 were determined to be SnO2·nH2O, Sn4(OH)6Cl2, and SnSO4, respectively.
  • Hiroaki Wada
    1978 Volume 51 Issue 5 Pages 1368-1373
    Published: 1978
    Released: April 19, 2006
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    An equilibrium study of the Fe–V–S system was carried out in the range of log(PS2/atm)=−4 to −0.8 at temperatures between 723 and 1093 K. The gravimetric method was employed by making use of a quartz spring balance. The partial pressure of sulfur was controlled in an N2-sulfur vapor system by temperature regulation. The partial pressure of S2 was calculated from the thermodynamic data, taking account of the existence of different molecular species: S2 through S8. Three kinds of ternary sulfides with different Fe/V ratios were used as starting material. The PS2-T-X relation was established through in situ measurements at high temperatures. It was found that the Fe–V–S system has an extensive ternary solid solution with the NiAs type of fundamental structure.
  • Takashi Shibahara, Masayasu Mori
    1978 Volume 51 Issue 5 Pages 1374-1379
    Published: 1978
    Released: April 19, 2006
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    Raman and infrared spectra of μ-hyperoxo and μ-peroxo ammine and cyano dicobalt(III) complexes have been studied and isotopic shifts of ν(OO) and ν(CoO) examined using 18O. A μ-hyperoxo complex, [(NH3)5Co(O2)Co(NH3)5]X5 shows peaks around 1110, 620, and 440 cm−1 assignable to ν(OO), sν(CoO), and asν(CoO), respectively, whereas a μ-peroxo complex, [(NH3)5Co(O2)Co(NH3)5]X4 shows peaks around 805, 645, and 545 cm−1 assignable to ν(OO), sν(CoO), asν(CoO), respectively. These observed values are best reproduced, when the following force constants are assumed in the UBFF calculation: K(OO)=5.6, K(CoO)=1.40 mdyn/Å for μ-hyperoxo complexes and K(OO)=2.7, K(CoO)=2.15 mdyn/Å for μ-peroxo complexes. The calculated isotopic shifts are in good agreement with the observed ones. Raman and infrared spectra of dibridged μ-amido-μ-O2 (both peroxo and hyperoxo) dicobalt(III) complex have also been characterized. A linear relationship has been found between ν(OO) and the bond order of the O2 moiety in O2-complexes in different oxidation states including alkali hyperoxide, alkali peroxide, hydrogen peroxide, oxygen, and O2+ species.
  • Hiroshi Ogino, Makoto Shimura, Nobuyuki Tanaka
    1978 Volume 51 Issue 5 Pages 1380-1385
    Published: 1978
    Released: April 19, 2006
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    The reduction of the cobalt(III) complexes, CoX(NH3)5(3–m)+ (Xm=Cl, Br, NCS, and H2O) and Co(en)33+, by Cr(II)–HEDTRA was studied by the stopped-flow method, where en and HEDTRA denote ethylenediamine and N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetatic acid respectively. From the kinetic behavior and the spectral properties of the immediate chromium(III) products, it is concluded that the Cr(II)–HEDTRA reductions of CoX(NH3)52+ (X=Cl, Br, and NCS) are of an inner-sphere type. The effect of the HEDTRA coordinated to chromium(II) on the rates of the electron-transfer reactions is discussed.
  • Hisayoshi Nakai, Yukinao Noda
    1978 Volume 51 Issue 5 Pages 1386-1390
    Published: 1978
    Released: April 19, 2006
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    The crystal of the title compound is monoclinic, with a=19.099(6), b=8.100(3), c=16.177(5) Å, β=100.54(5)°, the space group of C2/c, and Z=4. The structure was determined from the counter data and was refined to R=0.083 for 1736 non-zero reflections. The coordination geometry of the copper atom is best described as a distorted trigonal bipyramid, in which the equatorial plane is composed of Cu, two N, and water O atoms, and the axial positions are occupied by two N atoms. The complex has a crystallographically imposed twofold axis which passes through the copper and the water oxygen atoms at the equatorial plane. The two phenanthroline ligands are related with each other by this axis.
  • Shuhei Fujinami, Muraji Shibata, Hideo Yamatera
    1978 Volume 51 Issue 5 Pages 1391-1396
    Published: 1978
    Released: April 19, 2006
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    On the basis of a tetragonal (D4h) model, the procedures for calculating the vibronically induced transition moment have been described, and a correlation in the band intensity between two nondegenerate transition components (A2 and B2) has been shown. The correlation has then been applied to understanding the characteristic absorption spectra of the trans-[CrClF(NH3)4]+ and trans-[CrF2(NH3)4]+ complexes. Furthermore, an effect upon the band intensity caused by the configuration interactions among the E states has been proposed in order to explain the characteristic spectra of the trans-[Co(C2O4)2(py)2] and trans-[Co(CO3)2(py)2] complexes. This treatment has been applied also to the spectra of cobalt(III) complexes with C4V symmetry.
  • Hideo Kurosawa, Shigeaki Numata, Toshifumi Konishi, Rokuro Okawara
    1978 Volume 51 Issue 5 Pages 1397-1399
    Published: 1978
    Released: April 19, 2006
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    Synthesis of some new trimethylsilylmethyl, neopentyl, and isobutylthallium compounds is described. Dialkykhallium halides containing these bulky alkyl substituents were found to be dimeric, in marked contrast to the polymeric dimethylthallium halide analogs. Trimethylsilylmethylthallium diisobutyrate possesses much higher stability than the methyl and ethylthallium analogs. These facts were discussed in terms of the steric bulk of the alkyl groups attached to thallium.
  • Motomichi Inoue
    1978 Volume 51 Issue 5 Pages 1400-1403
    Published: 1978
    Released: April 19, 2006
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    ESR spectra were recorded on the single crystal of di-μ-oxo-tetrakis(2,2′-bipyridine)dimanganese(III,IV) perchlorate trihydrate. ESR signals attributable to the excited quartet state were observed in addition to an ESR signal due to the ground doublet state. From the temperature dependence of the signal intensities, the exchange integral was determined as Jk=−207 K. The spectrum of the quartet state exhibits a fine structure: |D| and |E| were estimated to be equal to 0.39 and 0.12 cm−1, respectively. The constants are interpreted in terms of the dipole-dipole interaction and the crystal-field effect; the anisotropic part of the exchange interaction is negligibly small. The hyperfine structure in the spectrum of the doublet state indicates that odd electrons are distributed unequally on two manganese atoms in the dimer. This is due to an odd e electron (in the t23-t23e1system) localized mostly on one of the paired manganese atoms.
  • Fujio Mizukami, Juichi Imamura
    1978 Volume 51 Issue 5 Pages 1404-1412
    Published: 1978
    Released: April 19, 2006
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    Metal-ion catalyzed oxidation of tetralin and metal-ion catalyzed decomposition of α-tetralin hydroperoxide (THP) were carried out in acetic acid in both the presence and absence of an additive. It was found that the rate-determining step in the oxidation of tetralin is the decomposition of THP. The results also suggest that the decomposition of THP with cobalt catalysts proceeds by the inner-sphere mechanism. In the oxidation of tetralin catalyzed by first-transition-metal ions, excepting vanadium, cobalt showed the highest activity and the lowest selectivity of hydroperoxide, and chromium showed the highest ratio of α-tetralone to α-tetralol (On/Ol). The order of the activities of metal acetates in producing oxidation is in agreement with that of the activities of metal acetates in producing decomposition. Such agreement was also found for Co(acac)3, Cr(acac)3, Mn(acac)2, and Fe(acac)3 catalysts. For oxidation with Co(OAc)2·4H2O and Cr(OAc)3, the product distributions were examined for various conversions of tetralin. In the both cases, the On/Ol ratios increase with increasing tetralin conversion. However, the mechanisms responsible for the increase in the On/Ol ratio appear to be different.
  • Manabu Sen\={o}, Shinsaku Shiraishi, Yukio Suzuki, Teruz\={o} Asahara
    1978 Volume 51 Issue 5 Pages 1413-1417
    Published: 1978
    Released: April 19, 2006
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    N-Aryl-α-chloro-α,α-diphenylacetimidoyl chlorides were prepared from Schiff bases and dichlorocarbene generated by use of the phase transfer catalyst. Treatment in sulfuric acid gave 3,3-diphenyl-2-indolinone derivatives. The synthetic route to 2-indolinone was found to give a higher overall yield than that by other methods. 2,2-Dichloro-1,3-diphenylaziridine gives α-chloro, α-acetoxy or α-hydroxy-α,α-diphenylacetanilide on treatment with sulfuric acid. Comparison of 2,2-dichloro-1,3-diphenylaziridine, 2,2-dichloro-1,3,3-triphenylaziridine and N-aryl-α-chloro-α,α-diphenylacetimidoyl chloride in their reactivities with sulfuric acid shows that the pathway of the reaction is governed by the character and number of substituents at the reaction center where carbonium ions are developed.
  • Toshiro Chiba, Yoshiyuki Takata
    1978 Volume 51 Issue 5 Pages 1418-1421
    Published: 1978
    Released: April 19, 2006
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    The electrolytic recycle of Ti4+-Ti3+ has been employed for a redox-system consisting of hydroxylamine and Ti3+ which can produce amino radicals. From electroanalytical measurements, it was found that titanium(IV) chloride in hydrochloric methanol was reducible to Ti3+ with a sufficient current efficiency at the platinum electrode and the reduction was speeded up by an addition of hydroxylamine. On macro-scale electrolysis using a small amount of titanium(IV) chloride in the presence of 1,3-butadiene and hydroxylamine, the generated amino radical undergoes additive dimerization with butadiene and gives diaminooctadienes in reasonable yields.
  • Masatoshi Nagai, Noriyuki Sakikawa
    1978 Volume 51 Issue 5 Pages 1422-1426
    Published: 1978
    Released: April 19, 2006
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    Catalytic hydrogenolysis of phenothiazine, thianthrene, and phenoxathiin as appropriate model reactants in the competing reactions of sulfur, nitrogen, and oxygen removal over NH4Y zeolite, pre-sulfided Co–Mo–Al2O3, and Ni–W–SiO2Al2O3 catalysts has been carried out using the batch method. The cleavage patterns and the schemes in the hydrogenolysis of the three compounds and the active sites of an NH4Y zeolite for the hydrogenolysis are discussed. The C–S bond in phenoxathiin was more prone to cleavage than the C–O bond, and the C–N bond in phenothiazine was not broken in our experiments. Sulfur removal from the three compounds took place more than the removal of nitrogen or oxygen. The reactivity over the zeolite Y, pre-sulfided Co–Mo–Al2O3, and Ni–W–SiO2Al2O3 catalysts decreased in the order of phenothiazine>phenoxathiin>thianthrene, but in the absence of the catalyst the thermal stability was phenoxathiin>thianthrene>phenothiazine. In the hydrogenolysis of the three compounds over the NH4Y catalyst the desulfurization activity of the zeolite Y catalyst was maximized when calcined at 500 °C. The reaction of phenoxathiin was found to be accelerated by Brönsted acid, but this did not hold true in the case of phenothiazine and thianthrene.
  • Jyuzo Nakayama, Yukie Watabe, Masamatsu Hoshino
    1978 Volume 51 Issue 5 Pages 1427-1432
    Published: 1978
    Released: April 19, 2006
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    5-Aza, 2,3-benzo-5-aza-, 6-aza-, and 2,3-benzo-6-aza-1,4-dithiafulvalenes were synthesized and their spectroscopic properties are described. For example, the reaction of 2-methylthio-1,3-dithiolylium iodide with pyrrole gave 2-(2-pyrrolyl)-1,3-dithiolylium iodide in a 92% yield, which was treated with DBU, giving rise to 5-aza-1,4-dithiafulvalene as thermally-stable orange crystals in an 82% yield. Several reactions found during the course of these synthetic studies are also reported.
  • Muneji Miyoshi, Ken-ichi Nunami, Hiroshi Sugano, Toshiyuki Fujii
    1978 Volume 51 Issue 5 Pages 1433-1440
    Published: 1978
    Released: April 19, 2006
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    A sweetness potency was found in novel α-L-aspartyl dipeptide analogs which were quite stable on heating in an aqueous solution. The insertion of a methylene group into the peptide chain of α-L-aspartyl dipeptide esters mostly decreased the potency of the sweetness. However, the further exchange of the carbonyl and oxygen functions with each other on the ester group of a C-terminal β-alkyl-β-aminopropionic acid was found to increase the sweetness. Thus, N-(α-L-aspartyl)-O-pivaroyl-D-alaninol, N-(α-L-aspartyl)-O-cyclobutylcarbonyl-D-alaninol and N-(α-L-aspartyl)-O-cyclopropylcarbonyl-D-alaninol were all more than 200 times as sucrose.
  • Toshiyuki Oyama, Toshio Hamano, Katsuyuki Nagumo, Ryohei Nakane
    1978 Volume 51 Issue 5 Pages 1441-1443
    Published: 1978
    Released: April 19, 2006
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    In the ethylation of benzene with ethyl-1-13C fluoride and ethyl-1-d2 fluoride in boron trifluoride hydrate, almost a 50% isotope position rearrangement in the ethyl group of ethylbenzene was found, whereas in the boron trifluoride-catalyzed ethylation in excess benzene no rearrangement was observed. Based on these results, it was suggested that an electrophile is an ethyl cation in the ethylation of benzene in excess boron trifluoride hydrate and a nonionized polar complex in the boron trifluoride-catalyzed ethylation in excess benzene.
  • Kunihiro Ichimura
    1978 Volume 51 Issue 5 Pages 1444-1449
    Published: 1978
    Released: April 19, 2006
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    Visible light irradiation of a solution of zinc octaethylporphin (ZnOEP) in the presence of acyl azide gives zinc complex of 5-acylamino-2,3,7,8,12,13,17,18-octaethylporphin together with a small amount of zinc complex of 21-acylamino-2,3,7,8,12,13,17,18-octaethylporphin. Zinc 5,10,15,20-tetraphenylporphin (ZnTPP) is coverted into zinc complex of 21-acylamino-5,10,15,20-tetraphenylporphin in a similar way. The pyrolysis of the N-acylaminated ZnOEP affords the rearrangement product in addition to ZnOEP, while N-acylaminated ZnTPP is converted into ZnTPP on heating. The spectroscopic properties of these photoproducts are given.
  • Masahiko Kato, Masakazu Tsuji, Toshio Miwa
    1978 Volume 51 Issue 5 Pages 1450-1455
    Published: 1978
    Released: April 19, 2006
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    The effect of 1-exo- and 1-endo-methoxycarbonylmethyl groups on the course of the photo-induced BersonWillcott rearrangement of methyl 1a,7b-dihydro-1H-cyclopropa[a]naphthalene-1-acetate have been studied. Different reaction rates with the same final products have been observed and are discussed from the view of the stereochemical course of the reaction, which strongly supports the 60°-mechanism, i.e., a slither motion of C-1 with inversion of configuration.
  • Minoru Imoto, Yoshiyuki Nishida, Toshiyuki Yoshikawa, Tatsuro Ouchi
    1978 Volume 51 Issue 5 Pages 1456-1458
    Published: 1978
    Released: April 19, 2006
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    The radical polymerization of methyl methacrylate (MMA) was carried out with the system of ribonucleic acid (RNA), Cu(II) ion and water. The generation of free radical was found to take place in the water layer where RNA and Cu(II) ion exist. Urea shows a promoting activity. The effects of pH of water medium and temperature on the conversion of MMA were investigated. A reaction mechanism was proposed.
  • Toyoshige Tanabe, Toshikazu Nagai
    1978 Volume 51 Issue 5 Pages 1459-1463
    Published: 1978
    Released: April 19, 2006
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    The reactions of several diazomethanes bearing a variety of substituents with sulfur dioxide were carried out in ethanol. The reaction of a diazomethane possessing an electron-releasing group gave the olefin as the major product. On the contrary, the ethyl ethers were predominantly afforded from the reactions of the diazomethanes containing an electron-withdrawing group. Moreover, the ethyl alkanesulfonates were obtained in the cases bearing the substituent of an intermediate electronic character. The observed product distribution is interpreted in terms of the nucleophilicity of the α-carbon atom of the diazomethane: the preference of the formation of sulfene by the electrophilic attack of SO2 on the diazomethane to the acid-catalyzed decomposition by ethyl hydrogen sulfite reflects the nucleophilicity of the α-carbon atom in the diazomethane.
  • Masahiko Sisido, Eiichi Yoshikawa, Yukio Imanishi, Toshinobu Higashimu ...
    1978 Volume 51 Issue 5 Pages 1464-1468
    Published: 1978
    Released: April 19, 2006
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    The intrachain aminolysis by a terminal 4-pyridyl group of a p-nitrophenyl ester group at the other terminal of a poly(oxyethylene) chain was investigated. The rate constants of the intrachain reaction were determined as a function of the degree of polymerization, n, of the poly(oxyethylene) chain over the range of 5–33 at 15, 25, and 35 °C. The rate constant was at its maximum at n=7 and decreased with an increase in the chain length. A comparison of the data with those obtained with polysarcosine chain showed that the intrachain reaction proceeded more effectively in the latter chain. Some thermodynamic considerations were made as to the cyclization process of a poly(oxyethylene) chain.
  • Masahiko Sisido, Yukio Imanishi, Toshinobu Higashimura
    1978 Volume 51 Issue 5 Pages 1469-1472
    Published: 1978
    Released: April 19, 2006
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    Monte Carlo calculation was performed to estimate the ring-closure probability of a poly(oxyethylene) chain. The calculation was made for various chain lengths on the basis of a rotational isomeric state model in which the intrachain atomic overlaps were excluded in terms of the hard-sphere model. The chain-length dependence of the ring-closure probability thus obtained was compared with that of the rate-constant ratio of the intrachain reaction vs. the intermolecular reaction previously reported. For longer chains, the calculation agreed well with the experimental data. For shorter chains, the agreement was less satisfactory; this discrepancy was attributed to the effect of the bulky terminal groups of the poly(oxyethylene) chain. The thermodynamic parameters for the cyclization were determined, and it was found that the chain-length dependence of the ring-closure probability is mainly governed by the conformational enthalpy.
  • Takao Ooya, Masahiro Minabe, Kazuo Suzuki
    1978 Volume 51 Issue 5 Pages 1473-1476
    Published: 1978
    Released: April 19, 2006
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    The Wagner-Meerwein rearrangement of 9′-methyl-9,9′-bifluoren-9-ol yielded 10-(2,2′-biphenylylene)-9-methylenephenanthrene. Ozonolysis of the phenanthrene afforded 10-(2,2′-biphenylylene)-9-phenanthrone. This pinacolone was converted into 2′-(9-fluorenyl)biphenyl-2-carboxylic acid. Oxidation of 4,9′-bifluoren-9-one, which was obtained by ring closure of the acid, gave 9′-hydroxy-, 9′-benzyl-, and 9′-benzyloxy-4,9′-bifluoren-9-one. Isomers of 2,2′-diethyl-9,9′-bifluorene-9,9′-diol were obtained by reduction of 2-ethyl-9-fluorenone. The pinacols were rearranged to the corresponding pinacolones, which were cleaved into carboxylic acids. The structural assignment of these isomers was made by spectral analyses.
  • Mitsuaki Narita
    1978 Volume 51 Issue 5 Pages 1477-1480
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The fragment condensation on the soluble polymer support using dicyclohexylcarbodiimide (DCCI) plus 1-hydroxy-1H-benzotriazole (HOBt), diethoxyphosphoryl cyanide (DEPC), and triphenylphosphine (Ph3P) plus di-2-pyridyl disulfide ((PyS)2) as coupling reagents gave rise to efficient coupling (86–99% yield) of the peptide fragment, t-butyloxycarbonyl-L-O-benzyl-tyrosylglycylglycyl-L-phenylalanine [Boc-L-Tyr(Bzl)–Gly–Gly–L-Phe–OH], to the amino free terminal of Leu anchored to the soluble polymer support, H–L-Leu–OCH2–resin. Relative reactivity ratios of Boc–amino acids and Boc–L-Tyr(Bzl)–Gly–Gly-L-Phe–OH with H–L-Leu–OCH2–resin in the coupling reaction using the three coupling reagent systems could be easily determined by use of amino acid ratios in the acid hydrolysates of the resulting peptide resins in which they were taken. The peptide chain length of Boc–L-Tyr(Bzl)–Gly–Gly–L-Phe–OH has no influence on the reactivity of C-terminal amino acid in the coupling reaction using DCCI plus HOBt or DEPC as a coupling reagent when Boc–L-Phe–OH was replaced with Boc–L-Tyr(Bzl)–Gly–Gly–L-Phe–OH. The coupling reagent, Ph3P plus (PyS)2, brought about a marked decrease in the reactivity of the fragment peptide acid.
  • Fumio Ando, Jugo Koketsu, Yoshio Ishii
    1978 Volume 51 Issue 5 Pages 1481-1483
    Published: 1978
    Released: April 19, 2006
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    Tris(dialkylamino)-arsines (I), -stibines (II), and -bismuthines (III) react with sulfur dioxide to give the corresponding tetraalkylsulfurous diamides and the corresponding metal oxides or polymers containing the metals. The reactivity of these metal amides in view of the fastness of the initial reactions follows the order III>II>I, however, the yields decrease in the order I>II>III. Tris(dialkylamino)phosphines, on the other hand, give hexaalkylphosphoric triamides and hexaalkylphosphorothioic triamides in a ratio of 2 : 1. The reactivity of the various phosphorus compounds toward sulfur dioxide increases with increasing nucleophilicity of the phosphorus atom; P(NEt2)3>Ph2PNEt2>Ph2POEt>PhP(OEt)2>P(OEt)3. The reaction mechanism of compounds (I), (II), and (III) with sulfur dioxide is different from that of the phosphorus amides.
  • Masahiro Kurabayashi, Christoph Grundmann
    1978 Volume 51 Issue 5 Pages 1484-1486
    Published: 1978
    Released: April 19, 2006
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    The cycloaddition of aromatic nitrile oxides(2a=benzo-; 2b=p-tolu-; 2c=mesitylenecarbo-) with 1,3,5-triazine(1) is reported. The corresponding 3-substituted 1,2,4-oxadiazoles(3a,b,c) are obtained in fair yields only when BF3 is added. It was stoichiometrically confirmed that one mol of 1 behaves so as to supply three mols of azomethine radicals. A reaction scheme initiated from a two-step cycloaddition of 2 to 1 activated by BF3 is suggested. The mixture, 1 : 2c : BF3=1 : 3 : 1, afforded a better yield of 3c(69%) than an equimolar mixture of 2c with ethyl formimidate or formamidine.
  • Toshiyuki Kodaira, Kohzoh Hashimoto, Yoshihiko Sakanaka, Sumio Tanihat ...
    1978 Volume 51 Issue 5 Pages 1487-1489
    Published: 1978
    Released: April 19, 2006
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    The effect of the wavelength of irradiated light on the photocopolymerizations of oxygen with styrene (1) and α-methylstyrene (2) was investigated in connection with the charge-transfer bands observed between these monomers and oxygen, with the latter as an electron acceptor. It appeared that the excitation of the charge-transfer bands is responsible for the copolymerizations and that the photoabsorptions due to 1 and 2 do not contribute to the reactions, although the excited singlet states of these compounds were quenched by oxygen according to a Stern-Volmer plot.
  • Ryoichi Hasegawa, Yoshio Kamiya
    1978 Volume 51 Issue 5 Pages 1490-1494
    Published: 1978
    Released: April 19, 2006
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    The liquid phase autoxidation of nitroalkylbenzenes catalyzed by transition metal and bromide ions in acetic acid was investigated at 55–85 °C. A remarkable synergistic effect was found on the mixtures of metal catalysts composed of cobalt and other transition metals, the maximum reaction rate being observed at the molar ratio of Co : Mn : Br=1 : 0.005–0.01 : 1–2. The rate of oxygen absorption of p- or m-nitroalkylbenzenes wasas affected by the partial pressure of oxygen, showing deviation from the first order dependency on the substrate concentration in contrast to the case of ordinary alkylbenzenes. The results can be explained by the retardation effect due to nitro compounds which might result from the reaction with alkyl radicals and the deactivation of metal catalysts. o-Nitroalkylbenzenes except nitroethylbenzene show a great resistivity against the oxidation. The retardation effect can be ascribed to the inhibiting effect due to inactive free radicals and also to the various reduced products resulting from the intramolecular reaction of nitro groups and active radicals. It was found that the autoxidation of p-nitrotoluene catalyzed by Co–Mn–Br catalyst proceeds very rapidly at temperatures as low as 85 °C, yeilding mostly p-nitrobenzoic acid along with a small amount of p-nitrobenzaldehyde.
  • Hisaji Taniguchi, Toshikazu Ikeda, Eiji Imoto
    1978 Volume 51 Issue 5 Pages 1495-1500
    Published: 1978
    Released: April 19, 2006
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    1,3-Dipoles, such as phenylglyoxylonitrile oxide (1), benzonitrile oxide, and phenyl azide, undergo cycloadditions to the more electron-rich double bond of 2,3-bis(methoxycarbonyl)bicyclo[2.2.2]octa-2,5-diene (5) to afford only endo adducts. The cycloadditions of these 1,3-dipoles to the more electron-rich double bond of 6,7-bis(methoxycarbonyl)bicyclo[3.2.2]nona-6,8-diene (6) give only exo adducts. Benzonitrile-N-phenylimine (4) undergoes cycloadditions to both the more electron-rich and the more electron-poor double bonds of 5 or 6. The reaction of 4 with 5 yields two endo adducts, and the reaction of 4 with 6 gives two exo adducts. However, the cycloaddition of 1 to 5,6-endo,endo-bis(methoxycarbonyl)bicyclo[2.2.2]oct-2-ene affords both the exo- and endo adducts. The reason for the predominant endo cycloadditions toward 5 and exo cycloadditions toward 6 is discussed.
  • Masaru Shin, Ken Inouye, Hideo Otsuka
    1978 Volume 51 Issue 5 Pages 1501-1506
    Published: 1978
    Released: April 19, 2006
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    The synthesis is described of four quinoxaline-2-carbonyl (Qxc) tetradepsipeptide derivatives, Qxc–D-Ser[Z–MeCys(Bzl)–MeVal]–Ala–OH, Qxc–D-Ser[Bpoc–MeCys(Bzl)–MeVal]–Ala–OBut (2), Qxc-D-Ser(Z–MeVal)–Ala–MeCys(Bzl)–OH, and Qxc–D-Ser(Bpoc–MeVal)–Ala–MeCys(Bzl)–OBut, corresponding to the partial structure of a quinoxaline antibiotic, triostiin A. The Qxc group was introduced at the dipeptide or tripeptide stage with Qxc–ONp as acylating agent. Qxc–D-Ser–Ala–OBut and Qxc–D-Ser–Ala–MeCys(Bzl)–OBut were acylated with Z–MeVal–OH by using p-toluenesulfonyl chloride as activating agent to give the desired depsipeptides in excellent yields, whereas the acylation with Bpoc–MeVal–OH by the same procedure was unsuccessful. The latter could be achieved by the N,N′-carbonyldiimidazole method, though the yields were relatively low. The treatment of compound 2 with an aqueous acetic acid–formic acid mixture for removal of the Bpoc group brought about concomitant formation of cyclo[–MeCys(Bzl)–MeVal–].
  • Hisao Imaizumi, Yoji Hashida, Kohji Matsui
    1978 Volume 51 Issue 5 Pages 1507-1510
    Published: 1978
    Released: April 19, 2006
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    Phenylhydrazine gave o-phenylenediamines as the major product upon heating in a molten mixture of AlCl3–NaCl–KCl. In the molten mixture, some aromatic compounds gave the corresponding aromatic amines in good yields in the presence of phenylhydrazine, suggesting that the method provides a novel direct process for the preparation of aromatic amines.
  • Mitsuhiro Sumitani, Kazuhiko Kanemitsuya, Hajime Yasuda, Hisaya Tani
    1978 Volume 51 Issue 5 Pages 1511-1515
    Published: 1978
    Released: April 19, 2006
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    Insertion of aluminum to the C–O–C bond of saturated cyclic ethers by the HgCl2–ZnCl2–MeI catalyst system led to the reductive cleavage of 5, 6, and 7 membered ring ethers to give polymeric alkoxyalkylaluminum compounds. The relative rate of the reaction was increased in the order of tetrahydrofuran, 3-methyltetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydropyran, oxepane, 7-oxabicyclo[2.2.1]-heptane, and 2-methyltetrahydropyran. The cleaved cyclic ethers are bonded with aluminum atoms bifunctionally and the resulting polymeric aluminum compound gave dideuterio alcohols upon deuterolysis. Addition reaction of allyl halides and reduction of chloral with the aluminum compound provided a novel route for the preparation of unsaturated alcohols.
  • Masaru Tada, Tetsuro Maeda, Hiroshi Saiki
    1978 Volume 51 Issue 5 Pages 1516-1520
    Published: 1978
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    UV irradiation of 1-(1-cycloalkenyl)-4-phenyl-1-butanones gives differing products depending on the reaction conditions, neutral or acidic. In benzene 1-(1-cyclopentenyl)-4-phenyl-1-butanone gives 4-phenylspiro[4,4]-nonan-1-one, formed by the intramolecular abstraction of hydrogen, and 4-cyclopentylidene-4-phenylbutanal, formed by Norrish type I fission of the spiro ketone. 1-(1-Cyclohexenyl)-4-phenyl-1-butanone does not exibit this behavior. Both ketones give the reduction products, 1-cyclopentyl-4-phenyl-1 -butanone and 1-cyclohexyl-4-phenyl-1-butanone, under the action of trifluoroacetic acid, and cyclized products, 7-phenylperhydro-4-indenone and 4-phenylperhydro-1-naphthelenone, under the action of boron trifluoride etherate. The reaction processes under acidic conditions have both an ionic and a free radical nature. The results have lead to the proposition of the mechanism involving electron transfer, proton transfer, and hydrogen abstraction.
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