Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 45 , Issue 1
Showing 1-50 articles out of 81 articles from the selected issue
  • Noriyuki Watanabe, Eiji Niki
    1972 Volume 45 Issue 1 Pages 1-4
    Published: 1972
    Released: March 27, 2006
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    The Mössbauer spectra for ethyltin halides and related compounds (Et4Sn, SnX4 (X=Cl,Br, I), Et3SnX, Et2SnX2 (X=Cl, Br, I), EtSnI3) were obtained. The replacement of ethyl groups by halogen atoms made the isomer shifts more positive relative to the tetraethyltin precursor. These results may be explained in terms of the rehybridization theory that the s-character of a central atom tends to concentrate in orbitals directed toward electropositive substituents. A suggestion that the compounds of RSnX3 type show smaller quadrupole splittings than the R3SnX compounds is made and discussed in terms of the rehybridization in the orbitals of the tin atom and in terms of bond ionicity.
  • Yoshihito Takahashi
    1972 Volume 45 Issue 1 Pages 4-7
    Published: 1972
    Released: March 27, 2006
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    On sixteen compounds of phosphorus, the wavelength shifts of the Kα1,2 lines and the fine structures of the Kβ band of the phosphorus emission spectra were measured. For the oxygen compounds, the relationship between the intensity ratio of the Kβ′ line and the energy shift of the Kα1,2 lines was found to be expressed by a straight line similar to that found for sulfur and chlorine compounds. In the spectra of the oxyacids and their salts, the intensity ratio of the satellite line which is observed between the Kβ1 and Kβ′ lines is proportional to the number of the hydroxyl groups in a molecule. The appearance of this line seems to be attributable to the covalent bond between a third-period atom and a non-ionized atom. In the Kβ spectrum of triphenyl phosphite, the strong satellite line at the highest energy site seems to have a nature similar to those found in sulfite, chlorate, and phosphorus trichloride.
  • Kazuhiko Ichikawa, Mitsuo Shimoji
    1972 Volume 45 Issue 1 Pages 8-10
    Published: 1972
    Released: March 27, 2006
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    The absorption spectra in the ultraviolet and visible region were measured as a function of the temperature for pure molten I2 and for I2+Te solutions. The two peaks found at about 305 and 370 mμ can be attributed to the I3 ion. These peaks increase with the addition of Te indicating an increase in the concentration of the I3 ion. This result is consistent with the previous interpretation of the conductivity of molten I2 containing Te. The ionization potential of I3 can be estimated to be about 3.1 eV on the basis of a cyclic analysis using the model of Stein and Treinin which was developed for anion spectra in aqueous solutions. The temperature shift of the absorption energy can also be interpreted in terms of the same model. The heat change for the I2(g)+I(g)=I3(g) reaction is estimated as −48.0 kcal·mol−1.
  • Katsutoshi Ohkubo, Hirokazu Kanaeda
    1972 Volume 45 Issue 1 Pages 11-15
    Published: 1972
    Released: March 27, 2006
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    A theoretical study with the extended Hückel method augmented by d-orbitals was undertaken in order to elucidate the relation between the electronic structures of various onium compounds and their catalytic activities in the liquid-phase oxidation of hydrocarbons. There were several findings. Firstly, the differences in the catalytic activities of the carbonium, ammonium, and oxonium compounds are ascribed to those in the AO populations of the pz-orbitals on their central atoms. Secondly, the distinguished activities of sulfonium and phosphonium compounds were well explained by the partially-occupied sulfur or phosphorus 3d-orbitals, in which the dxz (or dyz) orbital is utilized most effectively for the interaction with the (1πg)z orbital of O2. Finally, the relatively low activities of arsonium and telluronium compounds are ascribed to the vacant and diffused 4d or 5d orbitals, while the appreciable activity of the selenonium compound is caused by the partial electron-occupancy of the 4dxz (or 4dyz) orbital of the central selenium.
  • Tetsuo Kosugi
    1972 Volume 45 Issue 1 Pages 15-19
    Published: 1972
    Released: March 27, 2006
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    The dissociation reactions of potassium sulfate and potassium carbonate were determined using a quadrupoletype mass spectrometer with a Knudsen-cell-type ion source. The vapor and dissociation pressures of potassium sulfate and the dissociation pressure of potassium carbonate were obtained, by the use of the Knudsen effusion method at temperatures from 900 to 1700°K, as follows:
    logP=−1.253×104\left(\frac1T\ ight)+7.724(K2SO4)
    logPd=−3.275×104\left(\frac1T\ ight)+20.83(K2SO4)
    logPd=−1.135×104\left(\frac1T\ ight)+9.257(K2CO3)
    The equilibrium constants of the dissociation reaction were estimated from the above data and from those of Kröger and Stratmann:
    logKp=−6.94×104\left(\frac1T\ ight)+38.8(K2SO4)
    logKp=−1.38×104\left(\frac1T\ ight)+9.80(K2CO3)
  • Koichi Niihara, Seishi Yajima
    1972 Volume 45 Issue 1 Pages 20-23
    Published: 1972
    Released: March 27, 2006
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    The behavior of the rhombohedral LnOF and the tetragonal Ln4O3F6 at high temperatures was investigated by differential thermal analysis and the high-temperature X-ray diffraction technique. In the case of the rare earth oxyfluorides, LnOF (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y), the high-temperature transition rhombohedral\ ightleftarrowscubic was observed by means of DTA and a high-temperature X-ray camera. The heat of transformation from rhombohedral to cubic was obtained by means of DTA. The transition temperatures and the heat of transformation, ΔH, shift to higher temperatures and to greater values respectively as the atomic numbers of the rare earth elements increase, although there are some anomalies. One endothermic peak was observed for the rare earth oxyfluorides, Ln4O3F6, from Sm to Lu. On the other hand, no peak was observed up to 1300°C for La, Pr, Nd, and Y. The behavior of the peak temperature of DTA against the atomic number for Ln4O3F6 is similar to that for LnF3; this indicates a transformation from an orthorhombic to a hexagonal structure.
  • Haruo Shizuka, Yasuyoshi Sawaguri, Toshifumi Morita
    1972 Volume 45 Issue 1 Pages 24-31
    Published: 1972
    Released: March 27, 2006
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    The photo-oxidation of N,N′-diphenyl-p-phenylenediarnine (DPPD) has been studied spectrophotometrically. The quantum yield for the diimine formation, Φ, in aerated cyclohexane at 2537 Å and 20°C did not change with variations of the irradiation time, the concentration of DPPD, or the light intensity. However, the Φ values increased, as did the decrease in the fluorescence quantum yields, as the excitation energies increased. The dissolved oxygen had the optimum concentration (1.2×10−4M), giving the maximum value of Φ in aerated cyclohexane at 2537 Å, and none of the product, the diimine, was obtained in the degassed system. When about 0.13M of ethanol or methanol was added to aerated cyclohexane, the maximum value of Φ was measured, and the addition of a highlypolar solvent, acetonitrile or H2O, decreased regularly in Φ. On the basis of these results, it can be said that the photo-oxidation of DPPD originates from the Franck-Condon state of the upper excited singlet state, 1(RH2)n. It seems that, in the primary processes of the reaction, the electron transfers take place from the Franck-Condon state of 1(RH2)n directly to the oxygen molecule (3Σg) and to the solvent, resulting in a trapped electron which immediately jumps into the oxygen molecule. Then, the (RH2)+O2 ion pair may be formed, and subsequently the intermediate, (RH2)+O2, may be converted to the product or the starting materials. The dissolved oxygen and the polar solvents are responsible for the electron-transfer processes, but they deactivate the ion pair, resulting in the decrease in Φ.
  • Kazutoshi Tanabe, Shinnosuke Saëki
    1972 Volume 45 Issue 1 Pages 32-38
    Published: 1972
    Released: March 27, 2006
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    Infrared absorption intensities of fundamental bands of three molecular species, CH3CCl3, CD3CCl3 in the vapor phase, and C2Cl6 in dilute solution in carbon disulfide have been measured. From the intensity data of four kinds of chlorinated ethanes C2H6, C2D6, CH3CCl3, CD3CCl3, the least number of common intensity parameters has been determined using the least squares method. Intensities of C2Cl6 calculated using the determined values of intensity parameters have been compared with the observed intensities in solution. It has proved that for almost all electro-optical parameters, it is possible to determine values commonly applicable to various chlorinated ethanes, while for μCH and δμCH⁄δrCH, it is not possible to find commonly applicable values, as in the case of chlorinated methanes.
  • Muneyuki Motoyama, Genzo Hashizume
    1972 Volume 45 Issue 1 Pages 38-42
    Published: 1972
    Released: March 27, 2006
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    Usefulness of X-ray emission spectrometry was demonstrated in a study of the grinding reaction of the system of fine particle silica and basic zinc carbonate. SiKα bands of the ground mixtures shifted toward the lower energy side relative to that of the fine particle silica, whearas SiKβ bands toward the opposite side. These band shifts were regarded as a measure of the reaction progress. The SiKβ band shift was shown more distinctly than the Kα band shift and explained as come from a decrease in the s-character of the bond caused by the chemical bonding of the zinc atom with the fine particle silica. The Kβ band shift was also correlated with the destabilization energy relative to the fine particle silica after C. G. Dodd and G. L. Glen. The band shifts indicated that the final product of this grinding reaction was amorphous zinc silicate-like compound. The correspondence of the X-ray band shifts with the infrared spectral shifts was also shown.
  • Hiroshi Masuhara, Noboru Mataga
    1972 Volume 45 Issue 1 Pages 43-47
    Published: 1972
    Released: March 27, 2006
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    It has been shown that excited electron donor-acceptor (EDA) complexes of s-tetracyanobenzene (TCNB) with benzene or toluene can be produced quite densely when excited with a giant pulse laser and that there arises a remarkable re-absorption of the charge-transfer (CT) fluorescence by the excited EDA complexes. We have investigated in detail the re-absorption effect by examining the dependence of the CT fluorescence spectra on the direction of observation, the decay function of the fluorescence, the effect of the concentration of solution as well as the effect of the exciting light intensity on it. The excited singlet-singlet (Sn←S1) absorption spectra have been obtained by analyzing the re-absorption effect. Since the CT fluorescence spectra are broad and have no structure, the fluorescence can work as a good light source for the absorption spectral measurement.
  • Kozo Tanabe, Chijiko Ishiya, Isao Matsuzaki, Ichiro Ichikawa, Hideshi ...
    1972 Volume 45 Issue 1 Pages 47-51
    Published: 1972
    Released: March 27, 2006
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    A new type of mixed metal oxide TiO2·ZnO was prepared by either heterogeneous or homogeneous co-precipitation and the acidic property was measured by n-butylamine titration and by observation of infrared spectra of adsorbed pyridine. It was found that TiO2·ZnO containing about 7 or 57% of ZnO shows a very large acid amount of 0.5–0.9 mmol/g and a fairly high acid strength of H0≤−3, the acid sites being both Brönsted and Lewis type and the acid sites of high strength created by heterogeneous precipitation. The catalytic activity and selectivity of TiO2·ZnO were found very high for the hydration reaction of ethylene. The catalyst was active also for the alkylation of phenol by methanol and gave only monoalkylated products.
  • Takayuki Fueno, Yoshiro Yonezawa
    1972 Volume 45 Issue 1 Pages 52-55
    Published: 1972
    Released: March 27, 2006
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    Charge-transfer complexations of carbonyl cyanide with furan, tetrahydrofuran, diethyl ether, and their sulfur homologs have been investigated in gaseous phase at temperatures 22–82°C. Thermodynamic data showed that the complexations are enthalpy-controlled in the temperature range studied and that the complexes formed from n-donors are fairly strongly bound. Both the transition and bonding energies could be interpreted in terms of the usual two-state resonance model. It has been deduced that the spatial arrangements of the components do not greatly differ for the various donors studied, despite the difference in precise nature of the bondings involved.
  • Kayoko Umezawa, Takeo Yamabe
    1972 Volume 45 Issue 1 Pages 56-60
    Published: 1972
    Released: March 27, 2006
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    Copper ions on several kinds of cation exchange resins were investigated by means of ESR spectroscopy. It was found that the motion of copper ions is restricted in the network of the ion exchange resin, and that the mobility of copper ions is closely connected with the chemical interaction of the copper ions with the fixed ionic groups of the resins. The mobility of copper ions is in the order of; on the sulfonic group>on the phosphonic group>on the carboxylic group>on the iminodiacetate group. This sequence is the reverse of the selectivity for the copper ion. The effect of the water molecules involved in ion exchange resins is also considered, and the copper species on each ion exchange resin are assumed.
  • Yoshio Yamada
    1972 Volume 45 Issue 1 Pages 60-63
    Published: 1972
    Released: March 27, 2006
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    The interaction of bis(acetylacetonato)copper(II) (Cu(acac)2) adsorbed on X-type zeolite of the sodium form and on silica gel with ammonia and aniline was investigated by ESR. The magnetic and bonding parameters for Cu(acac)2 on the surfaces indicate that the axial-ligand field about the copper on the surfaces is similar to that in a toluene solution. This finding implies that the copper in Cu(acac)2 does not interact strongly with these surfaces. However, it was deduced from the change in the spectrum at higher temperatures that the quasi-π-electrons in Cu(acac)2 interact with the electrostatic field arising from the cations on the zeolite. When ammonia or aniline was introduced, the bonding characters of the complex altered significantly. It was found, from the variation in the parameters, that the axial-ligand field about the complex strengthens and that an adduct is formed. Furthermore, a spectral line at g=2.004, which was observed only for Cu(acac)2 on the zeolite in the presence of aniline, was considered to be due to a cation radical formed by an electron transfer from the aniline to the complex.
  • Yoshio Yamada
    1972 Volume 45 Issue 1 Pages 64-68
    Published: 1972
    Released: March 27, 2006
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    The interaction of bis(acetylacetonato)copper(II) (Cu(acac)2) adsorbed on X-type zeolite of the sodium form with pyridine was investigated by means of ESR. When a pyridine vapor was introduced to Cu(acac)2 on the zeolite, the spectral lines of the perpendicular g component for Cu(acac)2 were replaced by those consisting of a superhyperfine structure, which arises from the ligand nitrogen atoms. The observed spectrum was assigned to [Cu(pyridine)4]2+. Such a characteristic substitution reaction of Cu(acac)2 with pyridine was not, however, observed on silica gel nor in ordinary solvents. It is pointed out, on the basis of these results and of the considerations described in a preceding paper, that the reaction involves the following mechanism: the interaction of quasi-π-electrons in Cu(acac)2 with an electrostatic field originating from the cation on the zeolite lowers the stability of Cu(acac)2, and the complex is attacked by two adsorbed pyridine molecules and two pyridinium ions which are formed by the combination with protons on acid sites, resulting in the substitution reaction. In addition, [Cu-(pyridine)4]2+ was produced on other cation-exchanged zeolites and silica-alumina. The substitution reaction was also found when α-, β-, or γ-picoline was used instead of pyridine.
  • Kiyohisa Okano, Yasuo Saito, Yoshisada Ogino
    1972 Volume 45 Issue 1 Pages 69-73
    Published: 1972
    Released: March 27, 2006
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    In order to investigate the catalytic activity of molten metal, experiments were carried out using the dehydrogenation of n-butylamine, benzylamine, and cyclohexylamine as test reactions. The molten zinc catalyst was thus found to show specially high activities and selectivities in all test reactions. The activity of the molten gallium catalyst for the dehydrogenation of n-butylamine was also considerable. However, the selectivity of this catalyst was somewhat lower than that of the molten zinc catalyst, and considerable amounts of dibutylamine were produced at lower reaction temperatures. The other molten metals were found to be almost inactive. That is, Pb, Cd, Sn, and Bi were inactive, while Tl and In were only slightly active.
  • Teiki Iwaoka, Hiroshi Kokubun, Masao Koizumi
    1972 Volume 45 Issue 1 Pages 73-77
    Published: 1972
    Released: March 27, 2006
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    As an extension of the previous paper (This Bulletin, 44, 341 (1971)) which proposed the formation of a certain charge transfer complex between triplet phenothiazine (PTHT) and oxygen or dimethylisophthalate, the similar donor-acceptor interaction has been studied between PTHT and several other acceptors such as dimethylterephthalate (DMTP), nitrobenzene, dinitrobenzene, and terephthalonitrile in deaerated ethanol solutions. In case of DMTP, studies have been made also in cyclohexane. It has been established that all the acceptors except nitrobenzene attack PTHT with the diffusion controlled rate constant and that in ethanol they give rise to free radical ions and/or solvent shared ion-pair. In cyclohexane, however, no transient species other than triplet has been detected.
  • Kiyoshi Kawai, Yasuhiko Shirota, Hiroshi Tsubomura, Hiroshi Mikawa
    1972 Volume 45 Issue 1 Pages 77-81
    Published: 1972
    Released: March 27, 2006
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    Transient absorption spectra have been obtained by the flash photolysis of chloranil in various organic solvents. In trichlorotrifluoroethane, two T-T′ absorption systems of chloranil were obtained with well-resolved vibrational structures. In tetrahydrofuran, on the other hand, absorption spectra mostly consist of semiquinone radical formed by the hydrogen abstraction from solvent. In benzene and in acetone, the first T-T′ absorption system was much more diffuse and was accompanied by a weak, broad absorption at longer wavelength (λ>550 nm) which might be assigned to a charge transfer absorption from triplet chloranil as acceptor and the solvent molecule as donor. In acetone and in methanol, it has also been found that there is an equilibrium between semiquinone radical and semiquinone anion.
  • Mitsuru Asano, Yutaka Yamamoto, Noriaki Sasaki, Kenji Kubo
    1972 Volume 45 Issue 1 Pages 82-87
    Published: 1972
    Released: March 27, 2006
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    A quadrupole mass filter was used to determine the partial pressures of Sr(g) and SrO(g) over strontium oxide heated on a platinum-ribbon filament. The ion currents of 88Sr+ and 88Sr16O+ were measured while the filament temperature was continuously increasing at a heating rate of about 14°C/min; the calculations of the partial pressures were carried out by the integral method for Sr(g) and by the sensitivity-calibration method for SrO(g). The data are represented by:
    logPSr(g)(atm)=6.633−\frac2.536×104T
    in the temperature range of 1643–1851°K, and by:
    logPSrO(g)(atm)=6.707−\frac2.793×104T
    in the 1747–1850°K range. From the values of the partial pressures, the dissociation energy of strontium oxide was determined to be D0°(SrO)=96.2±0.9 kcal/mol by the third-law treatment and D0°(SrO)=102±5 kcal/mol by the second-law treatment.
  • Naosato Yoshida, Shuichi Hamada
    1972 Volume 45 Issue 1 Pages 88-91
    Published: 1972
    Released: March 27, 2006
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    The viscosities of fractionated liquid oligotrifluorochloroethylene were measured in the molecular-weight range from 820 to 2100 at temperatures ranging from 40 to 120°C. While the relationships between logη and logMn were regarded as being approximately linear in the molecular-weight range smaller than 1090, and their slopes were much larger than unity, a considerable deviation from the approximately linear relationship was observed in the molecular-weight range larger than 1090. The temperature dependence of the viscosities was well explained in terms of the WLF equation under the present experimental conditions. The large slope in the range of the linear relationship may be caused because the reciprocals of the free-volume fractions, 1/f, increase remarkably with an increase in the molecular-weight. The free-volume per cubic centimeter, F, contributed by chain-ends increased abruptly with an increase in the molecular-weight in the range smaller than about 1200.
  • Shuji Saito, Fumio Makino
    1972 Volume 45 Issue 1 Pages 92-94
    Published: 1972
    Released: March 27, 2006
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    The microwave spectra of normal and 13C-isotopic species of dimethyl sulfone have been investigated, and the rotational constants of both species have been determined. The following r0-structural parameters have been determined: r(C–S)=1.777±0.006Å, r(S–O)=1.431±0.004Å, ∠CSC=103°17′±10′, and ∠OSO=121°1′±15′, assuming that r(C–H)=1.091Å and ∠HCH=109°34′. The variations in the structural parameters among the related alkyl sulfides, alkyl sulfoxides, and alkyl sulfones have been discussed. The dipole moment has been determined to be μ=4.432±0.041 D along the b axis. This value is consistent with the results of a bond-moment calculation based on the dipole moment of dimethyl sulfoxide.
  • Akira Ozora, Tsugito Nakagawa, Mitsuo Ito
    1972 Volume 45 Issue 1 Pages 95-98
    Published: 1972
    Released: March 27, 2006
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    In order to study the phase transition of 1,2-dichloroethane crystal at 177°K, the low-frequency Raman spectra were measured at various temperatures, and normal coordinate analysis was carried out. It was found that the phase transition is of rotational type in which the librational motion of the molecule about the axis passing through two chlorine atoms of the molecule changes into a nearly free rotation about the same axis.
  • Okitsugu Kajimoto, Takayuki Fueno
    1972 Volume 45 Issue 1 Pages 99-105
    Published: 1972
    Released: March 27, 2006
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    The exact classical-mechanical calculation of the translational-vibrational energy transfer of diatomic molecules was extended to collisions between inert gas and anharmonic oscillator of varying initial vibrational energy. The systems investigated were H2–He, N2–Ar, and I2–Ar. It was found that, at lower vibrational levels, the transitions in both upward and downward directions become more efficient with an increase in the initial vibrational energy of molecules. In a high vibrational energy region, however, vibrational deactivation reaches a maximum and then diminishes as the initial vibrational energy approaches the dissociation threshold. The results illuminate the essence of a “bottleneck” to vibrational energy flow involved in the activation process of bimolecular dissociation of diatomic molecules.
  • Yôichi Iida
    1972 Volume 45 Issue 1 Pages 105-109
    Published: 1972
    Released: March 27, 2006
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    The anion radical salts derived from 3,5,3′,5′-tetrachloro-4,4′-diphenoquinone and 3,5,3′,5′-tetrabromo-4,4′-diphenoquinone were prepared. The absorption spectra in solution and the solid-state spectra were examined in order to study the solid-state properties characteristic of the anion radical salts. The measurements of the static magnetic susceptibilities and the electrical resistivities were also useful for this purpose. These physical properties were found to be based on the charge-transfer interaction between the anion radical molecules. It was suggested that, in these solid anion radical salts, the anion radical molecules might be stacked by a unique face-to-face arrangement in groups of two or an infinite number of molecular systems.
  • Yashige Kotake, Mitsuo Ono, Keiji Kuwata
    1972 Volume 45 Issue 1 Pages 110-112
    Published: 1972
    Released: March 27, 2006
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    The photochemical decomposition of ethylamine at low temperatures was studied using ultra-violet light of various wavelengths (120–400 nm), and the photochemical reactions were examined. The initial stage of the decomposition is the release of the hydrogen atom by far ultra-violet light. As the decomposition proceeds, the effective wavelengths for the succeeding reactions become longer. The final products of the decomposition are the methyl radical and other diamagnetic species. The effects of the matrix and the counter ion on the reaction are also discussed.
  • Masaru Ohsaku, Yuji Shiro, Hiromu Murata
    1972 Volume 45 Issue 1 Pages 113-121
    Published: 1972
    Released: March 27, 2006
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    Infrared spectra recorded in the liquid and solid states of dimethyl sulfide, CH3SCH3, bis(methylthio)methane, CH3SCH2SCH3, bis(methylthiomethyl) sulfide, CH3SCH2SCH2SCH3, and bis[(methylthio)methylthio]methane, CH3SCH2SCH2SCH2SCH3, are reported. For the CH3SCH2SCH3 species, the gaseous spectra were also recorded. For these molecules, the observed bands were assigned to the fundamental modes of the vibrations with reference to those of reported analogous-structure molecules. The existence of the rotational isomers of the last three compounds was postulated. The regularity of the wave number of the fundamentals obtained and the intensity change in some of the bands for this series of compounds were discussed. The frequency shift in the liquid-solid phase transition was also described for a few bands.
  • Takashi Nogami, Keitaro Yoshihara, Saburo Nagakura
    1972 Volume 45 Issue 1 Pages 122-128
    Published: 1972
    Released: March 27, 2006
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    Interactions of chloranil with p-phenyIenediamine, N,N-dimethyl-p-phenyIenediamine, and N,N,N′,N′-tetramethyl-p-phenylenediamine were studied by measuring visible and ultraviolet absorption spectra at various temperatures between 77°K and 300°K. In an ether-isopropyl alcohol (3:1) mixed solvent, the p-phenylenediamine- and N,N-dimethyl-p-phenylenediamine-chloranil systems were led to the substitution reaction through the outer complex and the ionic species as reaction intermediates. In ethyl ether, the p-phenylenediamine- and N,N-dimethyl-p-phenylenediamine-chloranil systems were found to yield the inner complex and the substituted species through the outer complex, respectively. In the N,N,N′,N′-tetramethyl-p-phenylenediamine-chloranil system, the inner complex was found to be formed via a clustering of the outer complexes.
    The interactions between aromatic amines and chloranil were found to be classified into the following three types: (a) the charge-transfer (outer or inner) complex is formed between an electron donor and an acceptor and no further reaction proceeds; (b) the substitution reaction occurs through the outer and inner complexes; (c) the substitution reaction occurs through the outer complex and ionic species. The difference in the reactivities between mtfta-substituted derivatives of aniline and ortho- and para-substituted ones was explained by taking the π-electron density on the amino group into account.
  • Jiro Hiraishi
    1972 Volume 45 Issue 1 Pages 128-132
    Published: 1972
    Released: March 27, 2006
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    The infrared spectra of copper formate tetrahydrate are measured in the frequency region from 4000 to 24 cm−1 at various temperatures. This compound is known to undergo an antiferroelectric phase transition at −37.7°C. The bands due to the librational and translational modes of the crystalline water molecules in the antiferroelectric phase are quite different from those in the paraelectric phase, while no appreciable differences between the spectra in the two phases are observed for other bands. Those facts agree with the results obtained by the crystallographic study, which show that the ordering of the orientation of the water molecules occurs at the phase transition. The similarity of the librational and the translational modes of the water molecules to those of ice is also discussed.
  • Hideaki Chihara, Minoru Nakamura
    1972 Volume 45 Issue 1 Pages 133-140
    Published: 1972
    Released: March 27, 2006
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    Heat capacity of NH4Cl was measured between 8 and 300 K with an adiabatic calorimeter. The low-temperature limit of the Debye temperature is 352 K and its high-temperature limit in the harmonic approximation is 285 K. The λ transition point Tλ is 242.502±0.004 K with the heat of transition 1168 J mol−1 and the entropy of transition 5.00 JK−1 mol−1. It is very close to the first-order transition. From the analysis of the heat capacity between 242 and 300 K, an extra contribution to the heat capacity that amounts to 11.5 JK−1 mol−1 at 300 K is extracted and explained by a simple model which assumes an additional type of order-disorder in the arrangment of NH4 ions above Tλ. The energy difference between the parallel and the antiparallel pairs of NH4 ions is estimated to be 1.46 kj mol−1 from the low-temperature tail of the heat capacity anomaly near Tλ.
  • Hiroko Kaneko, Takeo Ozawa
    1972 Volume 45 Issue 1 Pages 140-145
    Published: 1972
    Released: March 27, 2006
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    In the presence of the chlorate ion, the electrode reaction of the various titanium(IV)-chelates is followed by a cyclic process, i.e., an electrochemical reduction of electroactive species generated continuously by coupled chemical oxidation. The reaction rate constant of the regeneration is determined from the ratio of the limiting current observed by the DC polarographic method in the presence of the chlorate ion to that determined without it, and it is calculated using Koutecky’s equation. The complex-forming agent decreases the wave height of the catalytic waves of titanium(IV) chelates, and a clear dependency of the height of the catalytic waves on the dissociation constants of the titanium chelates is found. The catalytic wave heights of the titanium(IV) chelates decrease in the order of oxalic acid, NTA, EDTA-OH, EDTA, and CyDTA; the dependency on the stability seems to be the reverse. The logarithm of the dissociation constant is in a linear relation with the logarithm of the catalytic current. The mechanism is discussed on the basis of the above-mentioned facts.
  • Akitane Akiyama, Tsuyoshi Suzuki, Takashi Saji
    1972 Volume 45 Issue 1 Pages 146-149
    Published: 1972
    Released: March 27, 2006
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    The electrolytic conductivities and densities of condensed phosphoric acids have been measured in the P2O5 concentration range from 55% to 80% at 55.0, 70.0, and 90.0°C. Assuming the proton jump mechanism through the hydrogen bond network of H2O and H3PO4, the molar conductance was calculated and found to be constant in the P2O5 concentration range between 60% and 76%. The investigation has been extended to the mixtures of condensed phosphoric acids and concentrated sulfuric acid. The complex formation of [H4PO4+·HSO4] and [H3O+·HSO4] has been suggested in the mixture.
  • Yoshio Ishino, Tetsuya Ogura, Kenichiro Noda, Tsuneaki Hirashima, Osam ...
    1972 Volume 45 Issue 1 Pages 150-154
    Published: 1972
    Released: March 27, 2006
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    [Cu(allyl alcohol) (H2O)]ClO4 (abb. Cu(all)(H2O)ClO4), [Cu(allyl alcohol)2(H2O)]ClO4 (abb. Cu(all)2-(H2O)ClO4), [Cu(2-methylallylalcohol)(H2O)]ClO4 (abb. Cu(meth)(H2O)ClO4) and [Cu(cis- and trans-2-butenyl alcohol)2 (H2O)]ClO4 (abb. Cu(cis-and trans- but2 (H2O)ClO4) were synthesized. It was shown by means of equivalent conductance that Cu(all)(H2O)ClO4 is a strong electrolyte of uni-uni valent in acetone. The molecular weight of Cu(all)(H2O)ClO4 obtained from measurements of the direct vapor-pressure depression of acetone showed that the complex is monomeric. The C=C stretching band of the allylic alcohol shifts by about 100 cm−1 to the lower frequency side upon coordination. The chemical shifts of the vinyl protons in these complexes shift by about 0.5–1 ppm to the higher frequency side than those of free alcohols. It was concluded that the allylic alcohol coordinates to the copper atom through both the double bond and the oxygen atom. The equilibrium constant corresponding to Cu(trans-but)+2(H2O)ClO4+2cis-2-butenyl alcohol=Cu(cis-but)+2(H2O)ClO4+2trans-2-butenyl alcohol in 2-butenyl alcohol was estimated to be 9.82 at 25°C and the enthalpy change was estimated to be −3.13kcal/mol.
  • Yoshinori Nishikawa, Yukio Nakamura, Shinichi Kawaguchi
    1972 Volume 45 Issue 1 Pages 155-160
    Published: 1972
    Released: March 27, 2006
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    Tris(acetylacetonato)manganese(III) reacts with ethylenediamine (L2) and other primary amines (L) in organic solvents at room temperature producing Mn(acac)2L2. The same Mn(II) complexes were also prepared quantitatively by reactions of Mn(acac)2(H2O)2 with amines. Besides the usual hexa-coordinate monomeric complex, allylamine gave a dimeric compound [Mn(acac)2(CH2=CHCH2NH2)]2, which is the first example of the binuclear manganese(II) complex of acetylacetone. The stoichiometry of the redox reaction between Mn(acac)3 and ethylenediamine was established and discussed in connection with the initiation mechanism of vinyl polymerization.
  • Kuwako Ohkawa, Junnosuke Fujita, Yoichi Shimura
    1972 Volume 45 Issue 1 Pages 161-166
    Published: 1972
    Released: March 27, 2006
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    A series of new kinds of mixed cobalt(III) complexes, trans (O,X)-[Co(X) (aminoacidato) (diethylenetriamine)]Y, have been prepared and characterized by visible and ultraviolet, circular dichroism, and proton magnetic resonance spectroscopy for X=CN, NO2, and Cl; aminoacid=glycine, α-aminoisobutyric acid, L-alanine, L-valine, L-threonine, and L-proline; and Y=Br, Cl, or ClO4. The proton magnetic resonance spectra of the cyano mixed complexes show the existence of new conformational isomers, endo and exo forms, which concern the ligand CN and the hydrogen atom attached to the central nitrogen atom of the meridionally coordinated diethylenetriamine ligand.
  • S. B. Akki, S. M. Khopkar
    1972 Volume 45 Issue 1 Pages 167-170
    Published: 1972
    Released: March 27, 2006
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    The thio derivative of 2-thenoyltrifluoroacetone 1,1,1-trifluoro-4-(2-thienyl)-4-mercaptobut-3-en-2-one (STTA) is used for the simultaneous extraction and direct colorimetric determination of lead. About 100 μg of lead is quantitatively extracted, at pH 6.5, with 10 ml of 0.0020M STTA-CCl4 as a bright orange colored complex, which can be measured spectrophotometrically at 480 nm. The system conforms to Beer’s law over the concentration range of 1–40 μ/ml of lead(II). The color of the complex is stable for 60 hr. Lead can be quantitatively extracted and determined in the presence of a number of ions. The method is made selective by using some sequestering agents and carrying out selective extractions with mesityl oxide. The procedure is found to be suitable for the analysis of lead in gun metal and solder.
  • Motonori Tamaki, Isao Masuda, Koichiro Shinra
    1972 Volume 45 Issue 1 Pages 171-174
    Published: 1972
    Released: March 27, 2006
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    The preparation of diamagnetic CoII(dmgH)2NO (dmgH=dimethylglyoximato monoanion) is reported. The complex shows the IR absorption band of NO at 1641 cm−1, indicating a neutral NO ligand in the complex. The IR and electronic spectra are consistent with the structure of the penta-coordinate, the square-pyramidal configuration of the complex. In the presence of oxygen and water, the complex is oxidized rapidly (NO→NO2, Co(II)→Co(III)) and converted into CoIII(dmgH)2NO2·OH2. During the reaction, a complex formulated as [CoII(dmgH)2NO·OH2] [CoIII(dmgH)2NO2]·2H2O is obtained. It is considered that, in the complex, the Co(II) is bound with the Co(III) through a NO bridge. The assignments of the IR spectra have been made using 15NO and 15NO2.
  • Isao Yoshida, Yoshitsugu Oono, Hiroshi Kobayashi, Keihei Ueno
    1972 Volume 45 Issue 1 Pages 174-178
    Published: 1972
    Released: March 27, 2006
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    Thermally stable and low melting copper(II) chelates of β-diketones have been synthesized as follows; bis-(heptane-2,4-dionato)copper(II), mp 172°C; bis(nonane-4,6-dionato)copper(II), mp 162°C; bis(5-ethylheptane-2,4-dionato)copper(II), mp 72°C; bis(3-ethylnonane-4,6-dionato)copper(II), mp 50°C; bis(3,7-diethylnonane-4,6-dionato)copper(II), mp 58°C. Their thermal characteristics including enthalpy and entropy of fusion, have been discussed in relation with the molecular structure of the copper chelates.
  • Yuzo Yoshikawa, Kazuo Yamasaki
    1972 Volume 45 Issue 1 Pages 179-184
    Published: 1972
    Released: March 27, 2006
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    Three possible isomers of bis(diethylenetriamine)cobalt(III) halide were isolated by column chromatography on ion-exchange cellulose and Sephadex, and the mer- and u-facial isomers were completely resolved by column chromatography on SE-Sephadex. These isomers were studied by electronic, infrared, and PMR spectroscopy, and the absolute configuration of the u-facial isomer was assigned on the basis of the circular dichroism spectrum.
  • Takaharu Honjyo, Toshiyasu Kiba
    1972 Volume 45 Issue 1 Pages 185-191
    Published: 1972
    Released: March 27, 2006
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    The solvent extraction of cobalt(II) with 1,1,1-trifluoro-4-(2-thienyl)-4-mercaptobut-3-en-2-one (abbreviated as STTA) in cyclohexane has been investigated, and a new spectrophotometric method for the determination of minute amounts of cobalt has been developed on the basis of the results obtained in the extraction study. When a sample solution the pH of which had been adjusted to 6.0–6.5 with hydrochloric acid or sodium hydroxide solution was shaken with a 10−3M STTA organic solution, the extraction of cobalt(II) proceeded rapidly and quantitatively. The amount of cobalt up to 8 ppm in the final organic phase could be determined by measuring the absorbance at 480 or 490 nm against the reagent blank. All other interferring ions, such as Hg(II), Cu(II), Ni(II), Pb(II), Zn(II), and Fe(III), extractable together with cobalt(II) could be stripped out of the organic phase by shaking it with 1–12M hydrochloric acid, while cobalt remained in the organic phase as it was. After this treatment, the organic phase was shaken with an aqueous buffer solution of pH 9–11; thereby, the excess of the reagent was released to a great extent from the organic phase into the aqueous solution. The cobalt-STTA chelate was then the only one existing in the organic phase; therefore, the sensitivity and the selectivity of the method increased so much that a few ppb of cobalt(II) could be determined precisely by measuring the absorbance of the final organic phase at 360 nm against the reagent blank. In this work, the apparent mole ratio of STTA to cobalt in the complex formation was estimated to be 4:1, and the molar absorption coefficients of the chelate in cyclohexane were found to be 4970000 (at 360 nm), 13200 (at 450 nm), 6500 (at 480 nm), and 5500 (at 490 nm) respectively. Anions, such as oxalate and citrate, as well as EDTA interfered with this extraction. By the recommended procedure, cobalt of a few ppb in an analytical-grade reagent of nickel nitrate hexahydrate could be determined.
  • Yosio Iwakura, Keikichi Uno, Suck-Ju Hong, Tatsuhiko Hongu
    1972 Volume 45 Issue 1 Pages 192-195
    Published: 1972
    Released: March 27, 2006
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    The reactions of C-(p-substituted phenyl)-N-(p-substituted phenyl) nitrones with N-(p-substituted phenyl)maleimides were carried out in THF to give both trans- and cis-isoxazolidines. The formation ratios of trans- to cis-isoxazolidines (ITIc) were determined by the NMR spectra of the cycloadduct mixtures. Though the values of ITIc varied with the electronic characters of the substituents, R1, R2, and R3, they were always found to be larger than unity.
  • Tetsushi Yamashita
    1972 Volume 45 Issue 1 Pages 195-198
    Published: 1972
    Released: March 27, 2006
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    N-Prolyl-p-aminostyrene was synthesized by the reaction of N-carboxy-L-proline anhydride with p-aminostyrene phosphate. This optically-active basic monomer was then copolymerized wtih N,N′-bis(p-viny]phenyl)-adipamide to give a basic polymer. Similar basic polymers were also obtained, starting from other α-amino acids, through this procedure. Of these polymers, the polymer involving L-proline was used for the chromatographic resolution of the phthalamidic acid derivatives of DL-phenylalanine, DL-valine, and DL-phenylglycine. The polymer resolved partially DL-N-(o-carboxybenzoyl)phenylalanine.
  • Yosio Hayasi, Hitosi Nozaki
    1972 Volume 45 Issue 1 Pages 198-202
    Published: 1972
    Released: March 27, 2006
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    Unstable dimethylsulfonium (phenylthio)methylide (2) is prepared in a THF solution from the corresponding sulfonium salt by treating it with n-butyllithium. Sulfenyl-substituted stable phenacylides 6a and 6b are obtained in three ways. The ylide 6a decomposes at 120°C in benzene to give (E)-9, the dimer of benzoyl(phenylthio)carbene. In contrast, the heating of 6a in ethanol affords ethanolysis products (11, 12) and ethyl benzoate. The alkylation of 6a and 6b with trimethyl- and triethyloxonium fluoroborate gives the vinylsulfonium salt 13. The ylide 2 reacts with (Z)- and (E)-1,2-dibenzoylethylene and with diethyl fumarate to give cyclopropanes, 15 and 16 respectively.
  • Hiroteru Sayo, Hidenobu Ohomori, Tsuneji Umeda, Masaichiro Masui
    1972 Volume 45 Issue 1 Pages 203-208
    Published: 1972
    Released: March 27, 2006
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    Alkaline hydrolysis of substituted α-nitroisobutyranilides, trichloroacetanilide and trifluoroacetanilide was studied kinetically at various hydroxyl ion concentrations in 10% aqueous dioxane. The formation of phenylcarbamate ion as an intermediate was confirmed on hydrolysis of the α-nitroisobutyranilides and trichloroacetanilide but not trifluoroacetanilide. All the substituted α-nitroisobutyranilides except the p-nitro derivative were found to undergo C–C bond fission exclusively. Trichloroacetanilide and the p-nitro derivative of α-nitroisobutyranilide underwent both C–C and C–N bond fission. The mechanism of C–C bond fission in the hydrolysis of α-nitroisobutyranilides was explained on the basis of the solvent isotope effect as a fast reversible addition of a hydroxyl ion followed by a rate-determining decomposition of the tetrahedral addition intermediate to form a phenylcarbamate ion and a carbanion.
  • Ichiro Hirao, Yasuhiko Kato, Hiromichi Tateishi
    1972 Volume 45 Issue 1 Pages 208-213
    Published: 1972
    Released: March 27, 2006
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    Reactions between 5-nitro-2-furimidoylhydrazine (I) and acetic or propionic anhydride (or the corresponding acids) under various conditions afforded 5-methyl- (II) and 5-ethyl-2-(5-nitro-2-furyl)-1,3,4-oxadiazole (IV) and 5-methyl- (III), 5-ethyl- (IX), 1 -acetyl-5-methyl- (VII), 1-propionyl-5-ethyl- (VIII), 1-propionyl-5-methyl- (X), and 1-acetyl-5-ethyl-3-(5-nitro-2-furyl)-1,2,4-triazole (XI) respectively. The treatment of I with acetic and propionic anhydride in refluxing benzene or tetrahydrofuran gave 1-acetyl- (V) and 1-propionyl-2-(5-nitro-2-furimidoyl)-hydrazine (VI) respectively. Compounds, VII, VIII, X, and XI were also prepared by the cyclization of V with propionic anhydride and by that of VI with acetic anhydride in dioxane. The structures of the products were discussed on the basis of the spectral data.
  • Akiko Chinone, Kozo Inouye, Masaki Ohta
    1972 Volume 45 Issue 1 Pages 213-215
    Published: 1972
    Released: March 27, 2006
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    Sulfurization of 1,3-diarylpropanetrione (1) with hydrogen sulfide and hydrogen chloride afforded a mixture of 4-hydroxy-3,5-diaryl-1,2-dithiolium chlorides (3) and 3,5-diaryl-1,2-dithiolium chlorides (4). Treatment of a mixture of 3a and 4a with triethylamine in alcohol gave anhydro-4-hydroxy-3,5-diphenyl-1,2-dithiolium hydroxide (5a) and the 4-substituted product (6). Sulfurization of dibenzoyldibromomethane yielded 3,5-diphenyl-1,2-dithiolium bromide. Reactions of 5a with picric acid and acetic anhydride in the presence of perchloric acid were carried out.
  • Shigeo Nishimura, Masayoshi Uramoto, Tetsuo Watanabe
    1972 Volume 45 Issue 1 Pages 216-222
    Published: 1972
    Released: March 27, 2006
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    The hydrogenation of ethyl p-tolyl ether (1) in ethanol has been studied with five unsupported platinum metals as catalysts, mainly with the purpose of estimating the yields of ethyl 4-methyl-1-cyclohexenyl ether (2) formed as intermediate. Except for ruthenium catalyst, the hydrogenation of 1 in ethanol was accompanied by the formation of acetal 3, ketone 4 and alcohol 5 which seem to be related to the formation of 2. The amounts of 2 and the related compounds which were desorbed from the catalyst surface have been estimated to be 32–33% for Ru, 32–34% for Rh, 72–76% for Pd, 3.7% for Ir and 4.7% for Pt, by application of both kinetic and extrapolation methods. A good agreement was obtained between the results from the two methods. The proportion of hydrogenolysis increased for the catalyst metals in the order Pd<Ru<<Rh<Ir<Pt. With platinum catalyst a noticeable amount of toluene was formed along with methylcyclohexane. The hydrogenation of ethyl 4-methyl-3-cyclohexenyl ether (6), one of the other intermediates of the hydrogenation of 1, has also been studied in ethanol. Hydrogenolysis occurred extensively with palladium and rhodium catalysts, but much less with ruthenium, iridium and platinum catalysts. The hydrogenation route of 1 and its relation to hydrogenolysis and stereochemistry of hydrogenation of 1 are discussed with reference to the formation and hydrogenation of its intermediates.
  • Nobukatsu Katsui, Hajime Matsue, Tomohiko Hirata, Tadashi Masamune
    1972 Volume 45 Issue 1 Pages 223-226
    Published: 1972
    Released: March 27, 2006
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    In connection with the studies of hatching substances for soybean cyst nematodes, the neutral fraction of the roots of the “kidney bean” (Phaseolus vulgaris L.) has been examined. It was found that phytosterols and triterpenes exist in the roots of plants.
  • Takashi Toda, Hiroshi Horino, Tetsuo Nozoe
    1972 Volume 45 Issue 1 Pages 226-229
    Published: 1972
    Released: March 27, 2006
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    Several 5-azidotropolones were synthesized by the reaction of sodium azide with tropolone diazonium salts which has been prepared from the corresponding 5-aminotropolones. Most of the 5-azidotropolones thus obtained were stable except for the 4-alkyl derivatives. Their electrophilic substitution reactions took place at their 3- and 7-positions, and also their hydroxyl groups behaved like those of other tropolones. 5-Azidotropolone methyl ether did not react with aromatic amines, but it did with aliphatic amines and guanidine to give 2-aminotropone derivatives and 1,3-diazaazulene derivative. The thermolysis of 5-azidotropolone and its methyl ether afforded 5-aminotropolone and its methyl ether respectively; however, 5-azido-4-phenyltropolone gave indolo[3,2-d]tropolone.
  • Kuniyuki Takahashi, Akihisa Miyake, Go Hata
    1972 Volume 45 Issue 1 Pages 230-236
    Published: 1972
    Released: March 27, 2006
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    The allylic compounds (I), R1–O–R (R=allylic groups, R1=Ph, Me, PhCH2, MeCO), react with active-hydrogen compounds such as phenols, alcohols, carboxylic acids, primary and secondary amines and active methylene compounds, to give allylic derivatives of the active-hydrogen compounds by an intermolecular exchange of the allylic groups of I with the atom to which the active hydrogens are bonded in the presence of palladium catalysts. Allyl and substituted-allyl ethers are more reactive than the corresponding carboxylates. In the reactions of methyl and benzyl ethers, it is necessary to add phenol to obtain the exchange products in fairly good yields. Bis(triphenylphosphine) palladium chloride plus sodium phenoxide, palladium acetate plus triphenylphosphine, and zerovalent palladium complexes such as tetrakis (triphenylphosphine) palladium and (maleic anhydride)bis(triphenylphosphine)palladium are effective catalysts.
  • Otohiko Tsuge, Sumio Iwanami, Shigeru Hagio
    1972 Volume 45 Issue 1 Pages 237-240
    Published: 1972
    Released: March 27, 2006
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    The reaction of benzoylmethanesulfonyl chloride with enamines derived from cyclohexanone in the presence of triethylamine has been studied. The chloride reacted with 1-(1-morpholino)- and 1-(1-piperidino)cyclohexene in the presence of triethylamine, affording the corresponding acyclic sulfones. On the other hand, the reaction of the chloride with 1-(1-pyrrolidinyl)cyclohexene gave 2-benzoylmethanesuIfonylcyclohexanone and 2,3-dibenzoyl-2,3,4,5,6,7-hexahydrothianaphthene 1,1-dioxide. The latter compound, whose structure corresponded to the compound derived from the 2:1 adduct of benzoylsulfene and the enamine with the elimination of sulfur dioxide and pyrrolidine, reacted with hydrazine hydrate to give 1,4-diphenyl-5a,6,7,8,9,9a-hexahydrothianaphtheno[2,3-d]-pyridazine, which was then transformed into 3,4,6-triphenylpyridazine.
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