Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 44 , Issue 7
Showing 1-50 articles out of 81 articles from the selected issue
  • Tatsuo Higashiyama, Shigeo Hasegawa
    1971 Volume 44 Issue 7 Pages 1727-1730
    Published: 1971
    Released: March 27, 2006
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    From the differential thermal and thermogravimetric analyses of potassium oxalate together with the X-ray diffraction studies, three crystallographic modifications of the anhydrous salt were found. When potassium oxalate monohydrate crystals were dehydrated at, e.g., 140°C, phase II, which is stable below 381°C, appears. The crystal in phase II has an orthorhombic unit cell (a=10.9, b=6.11, and c=3.44 Å at 17°C) and transforms at 381°C into phase I, which is stable above 381°C up to the temperature where the decomposition begins. The crystals in phase I belong to the tetragonal system (a=7.01 and c=7.53 Å at 404°C). The transition between phases II and I is not reversible in an exact sense, and when cooled phase I endures down to 215°C, where it transforms(reversibly) into phase III. Phase III can exist at room temperature. When heated, phase III transforms into phase I at 215°C (often accompanied by a partial transformation to phase II). The resulting phase then transforms into phase II. At all temperatures below 381°C phases I and III are metastable with respect to phase II, and they transform into phase II. The decomposition of potassium oxalate in an oxygen-free atmosphere seems to proceed in two stages.
  • Masao Sekizaki, Fumiyuki Marumo, Kazuo Yamasaki, Yoshihiko Saito
    1971 Volume 44 Issue 7 Pages 1731-1734
    Published: 1971
    Released: March 27, 2006
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    The crystal structure of bis(pyridine-2-acetamide)copper(II) perchlorate, Cu(paaH)2(ClO4)2, was determined from three-dimensional X-ray photographic data and refined by block-diagonal least-squares methods, using 1698 independent reflections to give R=0.12. The crystals are monoclinic with a space group of C2/c. There are four formula units in a unit cell with dimensions of: a=10.957, b=12.178, c=15.566 Å, and β=108.7°. The complex is centrosymmetric and square-planar, with two ligand molecules coordinating to the copper atom in trans positions through the amide-oxygen and the ring-nitrogen atoms. Two perchlorate ions coordinate weakly to the central copper atom through one of the four oxygen atoms from the top and bottom of the plane containing copper, amide-oxygen, and ring-nitrogen atoms.
  • Hajime Katô, Hiroshi Kato
    1971 Volume 44 Issue 7 Pages 1734-1739
    Published: 1971
    Released: March 27, 2006
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    The magnitude of the contact shift for hydrogen nuclei is directly related to the unpaired electron density, ρH, on the proton. The mechanism by which the unpaired electrons transfer from the transition metal d-orbitals to the ligand orbitals is studied on the basis of the method of intergroup (ligand and metal) configuration interaction. The ρH is given as a sum of two terms, ρHP and ρHD, due to the spin-polarization mechanism and the spin-delocalization mechanism respectively. When the interaction between metal and ligand is restricted to a localized bond N–M, such as nickel(II)-benzylamine, ρHP\simeq−(CMm)2H(0)|2πHN<NM|NM>⁄3\simeq0.001–0.0001 (Here πHN is the mutual atom(H)-atom(N) polarizability.). When the interaction between metal and ligand is not restricted to a special localized bond, as in metalocene, ρHP\simeq−(CMm)2H(0)|2πHH<HM|HM>⁄3\simeq0.01–0.001. The spin delocalization term has the order of magnitude of: ρHP\simeq−(CMm)2MN)2H(0)|2(PHN)2⁄2(δE)2 (Here PHN is the bond order between the H and N atomic orbitals.). If the proton H is not directly bonded to the atom N, ρHD\simeq0.0001. If the proton H is directly bonded to the atom N, ρHD\simeq0.001. By disregarding the contributions smaller than the order of magnitude O(S2), the formulation of the contact nuclear spin-spin coupling constant is derived. The most dominant term is identical with the formula which was derived by Pople and Santry for singlet free-ligand molecules.
  • Hiroo Niiyama, Etsuro Echigoya
    1971 Volume 44 Issue 7 Pages 1739-1742
    Published: 1971
    Released: March 27, 2006
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    Alkaline earth silicates having both acidic and basic sites can be considered as acid-base bifunctional catalysts. Dehydration and dehydrogenation of alcohols over these catalysts were carried out. Correlation between the selectivity and acid-base properties of alcohols and the catalysts was studied. It was found that acid-base properties of both the catalysts and the alcohols were cooperative in determining the selectivity of reaction.
  • Toshihiko Hoshi, Hiroyasu Inoue, Junko Shiraishi, Yoshie Tanizaki
    1971 Volume 44 Issue 7 Pages 1743-1745
    Published: 1971
    Released: March 27, 2006
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    The ultraviolet absorption spectrum of diprotonated-2,7-diaminofluorene has been divided into two components polarized along the long and the short axes of the molecule by using the results of the dichroic spectra in the stretched PVA sheet. By a comparison of the experimental results with those calculated by means of a semiempirical LCAO-ASMO-SCF-CI approximation including a variable β method the assignment of the absorption bands has been made. It has been found that the compound has five absorption bands above 210 mμ. The existence of the additional 300 mμ band of fluorene has been explained theoretically by increasing the ionization potentials of the 9- and 10-carbon atoms by 3 eV from the usual value (11.42 eV).
  • Takanobu Shiokawa, Toshiro Sato, Kenjiro Kondo
    1971 Volume 44 Issue 7 Pages 1746-1750
    Published: 1971
    Released: March 27, 2006
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    An attempt was made to estimate the effect of benzene on the recombination reactions of the recoil bromine atoms activated by the 81Br(n,γ)82mBr\oversetI.T→82Br and 81Br(n,2n)80mBr reactions in ethyl bromide and benzene mixtures. It seems to be reasonable to conclude, from the consideration of the parent yield, that the reactions leading to the formation of parent molecules in the thermal and high-energy regions can be classified into two reaction types. Judging from the results of the 81Br(n,γ)82mBr\oversetI.T→82Br reaction, approximately 53% of the parent yield from the high energy reactions in the pure ethyl bromide system is formed through the de-excitation process of the excited ethyl bromide labelled by the direct substitution reaction of the energetic recoil atom, while 47% is formed by the reaction of the recoil atom with ethyl radicals in the cage. The reaction of ethylene with hydrogen bromide, which is produced by the decomposition of the labelled excited ethyl bromide, contributes about 51% of the parent yield from the thermal energy reaction; the rest is formed by the other thermal reactions. Furthermore, no essential difference was observed between the recombination reactions of the recoil 82Br and 80mBr atoms produced by the 81Br(n,γ)82mBr\oversetI.T→82Br and 81Br(n,2n)80mBr reactions respectively.
  • Iwao Fujita, Motoyoshi Hatada, Teiichiro Ogawa, Kozo Hirota
    1971 Volume 44 Issue 7 Pages 1751-1754
    Published: 1971
    Released: March 27, 2006
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    The emission spectra of several fragmental species, especially of hydrogen atoms, produced by the electron impact (energy:240 eV) of gaseous methanol and deuteromethanols have been investigated. The intensity ratios of the Balmer-β lines of the H and D atoms are ca. 2.9:1 for CH3OD and ca. 1:1.8 for CD3OH, indicating that the excited hydrogen atoms result from the O–H bond scission, as well as from the C–H bond scission, of the parent methanol molecules. The ratio of the scission probability of a C–H bond to that of the O–H bond is calculated to be 0.8, taking into account the correction of the isotope effect. It was concluded that the excited hydrogen atoms are produced by the primary process of fragmentation via a superexcited species.
  • Toru Iwaki, Masaji Miura
    1971 Volume 44 Issue 7 Pages 1754-1758
    Published: 1971
    Released: March 27, 2006
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    The reduced state of the surface of titanium dioxide was studied by the measurement of the heat of immersion in water. When the titanium dioxide was reduced by hydrogen at 500°C, the heat value decreased appreciably with an increase in the pressure of hydrogen, in contrast to the increase in the heat value due to the reduction by an organic contaminant. The heat value was not restored to the original state even after oxygen had been introduced at 500°C to the reduced sample, while the color of the sample returned to white from bluish gray. These phenomena were interpreted by examining the adsorption of water, the reduced amount, and the reflectance spectrum.
  • Takako Amano, Haruo Kuroda, Hideo Akamatu
    1971 Volume 44 Issue 7 Pages 1758-1763
    Published: 1971
    Released: March 27, 2006
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    Polarized absorption spectra were observed on the single crystals of molecular compounds which involve 1,6-diaminopyrene as electron donor and p-chloranil, p-bromanil, p-iodanil, and tetracyano-p-quinodimethane as electron acceptor. It is shown that, in spite of the low ionization potential of diaminopyrene 6.56 eV, its solid molecular compounds with chloranil, bromanil, and iodanil are of non-ionic type, and their crystal spectra exhibit the general features characteristic of a typical charge-transfer molecular compound composed of neutral molecules. The diaminopyrene-TCNQ, compound was found to be of ionic type. Although the bromanil and iodanil compounds of diaminopyrene exhibit two charge-transfer bands, in the region below 10 kK and at about 20 kK respectively, the chloranil compound does not show the near-infrared charge-transfer band corresponding to the charge transfer from the highest occupied orbital of the donor to the lowest vacant orbital of the acceptor. A discussion is given for this phenomenon from the overlap between the donor and acceptor orbitals.
  • Yasuo Ito, Kouji Okuda, Yoneho Tabata
    1971 Volume 44 Issue 7 Pages 1764-1767
    Published: 1971
    Released: March 27, 2006
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    The measurement of the e+ lifetime in solid monomers during polymerization has been carried out. The mechanism of solid-state polymerization can be analyzed by the measurement of the lifetime of positrons and the amounts of positronium formed. This method was applied to the solid-state polylmerization of acrylamide. It was found from the experiments that the lifetime spectrum changes remarkably in the induction period of polymerization. The decrease in the annihilation rate λ2 was interpreted in terms of the formation of a larger free volume during polymerization. The intensity of the slow component was also observed to decrease in the induction period of polymerization. The accumulation of active species which capture positrons and the decrease in the number of free volumes were suggested as explanations of the phenomena.
  • Kazuo Tajima
    1971 Volume 44 Issue 7 Pages 1767-1771
    Published: 1971
    Released: March 27, 2006
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    The adsorbed amounts were measured on the surface of aqueous solutions containing tritiated sodium dodecylsulfate (TSDS) and varying amounts of NaCl by the direct radiotracer method. The surface tensions were also measured for the same solutions by the drop-volume method. The Gibbs adsorption isotherm, derived without assuming the adsorption of the chloride ion, was applied, and the amounts of adsorption were calculated for both dodecylsulfate and chloride ions. The observed amounts of dodecylsulfate adsorption were confirmed to be in good agreement with those calculated, and the calculated amounts of chloride adsorption turned out to be nearly zero or slightly negative, which is usually theoretically assumed because of the ionic repulsion due to the adsorbed dodecylsulfate. Further, the adsorption of the dodecylsulfate ion attained a constant and saturate value beyond a certain concentration (SAC) below the critical micelle concentration (CMC). The logarithms of SAC were found to vary linearly with the logarithms of CMC for the range of salt concentration studied. The value of SAC being in a close relation with the surface phenomena is considered to be another measure of the surface activity of surfactants.
  • Takeshi Kawakami, Akihiro Konno, Yoshisada Ogino
    1971 Volume 44 Issue 7 Pages 1772-1777
    Published: 1971
    Released: March 27, 2006
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    In order to clarify the mechanism of the acidity change due to compression, aluminum sulfate was compressed under various pressures ranging from 0 to 4200 kg/cm2 and at a temperature of 20, 65, or 80°C, and the surface acidity and the structure of these samples were measured. It was found that the acidity change due to compression was proportionate to the protonic acid. Lewis acid was made to appear only by heating the sample at temperatures higher than 90°C. Further, for the purpose of increasing the surface acidity, the compression of the sample at lower temperatures was found to be more effective than the compression at higher temperatures. In addition to the spectroscopic data, the results of DTA and TGA experiments supported the idea that the observed acidity change resulted from the distortion of the structural unit of aluminum sulfate.
  • Yôichi Iida
    1971 Volume 44 Issue 7 Pages 1777-1780
    Published: 1971
    Released: March 27, 2006
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    The anion radical salts derived from 2,3-dicyano-1,4-benzoquinone and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone were prepared. The absorption spectra in an acetonitrile solution and the solid-state spectra were examined for these anion radical salts. Unlike the absorption spectra in solution, in the solid-state spectra strong charge-transfer bands appeared and there were blue-shifts of the high-energy bands. These spectroscopic features were discussed on the basis of the charge-transfer interaction between the anion radicals. The solid-state properties of these salts were compared with those previously investigated for the anion radical salts of the halogen-substituted p-benzoquinones.
  • Tsuguo Yamaoka, Saburo Nagakura
    1971 Volume 44 Issue 7 Pages 1780-1783
    Published: 1971
    Released: March 27, 2006
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    The interactions of alkylamines with p-benzoquinone and its chloro-derivatives in ethanol and ethyl ether were studied by the rapid scan spectrophotometric method. The formation of anion radicals was found spectroscopically for the n-butylamine-p-benzoquinone, n-butylamine-chloranil, dimethylamine-p-benzoquinone, and tri-n-butylamine-chloranil systems. The rates of ionization reactions were determined to be 0.30 sec−1 mol−1 (at 253.7°K), 0.89 sec−1mol−1 (at 222.7°K), and 1.39 sec−1mol−1 (223.2°K) for the tri-n-butylamine-chloranil, n-butylamine-chloranil, and n-butylamine-p-benzoquinone systems, respectively. The activation energy for ionization of the tri-n-butylamine-chloranil system in ethanol was estimated to be 0.57 kcal/mol.
  • Akimichi Yokozeki, Kozo Kuchitsu
    1971 Volume 44 Issue 7 Pages 1783-1788
    Published: 1971
    Released: March 27, 2006
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    Bicyclo[2.2.2]oct-2-ene and bicyclo[2.2.2]octa-2,5-diene have been investigated by gas electron diffraction. They are found to have C2v symmetry in respect of the thermal-average nuclear positions. The structural parameters with estimated limits of error (the γg bond lengths and the angles difined in the γα structure) determined by a leastsquares analysis on the molecular intensities are as follows for octene and octadiene, respectively: C(sp3)–C(sp3) (weighted average of the C1–C7, and C7–C8 bonds)=1.549±0.008 and 1.553±0.017 Å, C(sp2)–C(sp3)=1.509±0.015 and 1.521±0.008 Å, C(sp2)–C(sp2)=1.341±0.008 and 1.339±0.005 Å, C(sp3)–H (average)=1.112±0.008 and 1.105±0.012 Å, ∠C–C=C=114.2±0.6° and 113.5±0.5°, The dihedral angle θ between the C1–C2–C3 C4 and C1–C6–C5–C4 planes=121.2±2.1° and 123.4±2.2°, ∠C=C–H=122.4±6.0° and 125.5±4.0°, ∠H–C–H=109.2±4.0° and 111.3±7.0°. A conformational analysis based on an empirical prescription of strain energies, similar to that of Jacob et al., and a molecular-orbital analysis (CNDO/2) have accounted for the observed bond angles given above to within 1.5°.
  • Gunzi Saito, Yoshio Matsunaga
    1971 Volume 44 Issue 7 Pages 1788-1791
    Published: 1971
    Released: March 27, 2006
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    The electron-acceptor strengths of the substituted naphthoquinones were compared with that of p-chloranil in terms of their complexing properties. The following electron affinities were estimated: 2.05 eV for 2,3-dichloro-1,4-naphthoquinone, 2.24 eV for 2,3-dichloro-5-nitro-1,4-naphthoquinone, 2.74 eV for 2,3-dicyano-1,4-naphthoquinone, and 2.78 eV for 2,3-dicyano-5-nitro-1,4-naphthoquinone.
  • Megumu Munakata
    1971 Volume 44 Issue 7 Pages 1791-1796
    Published: 1971
    Released: March 27, 2006
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    Cobalt(II) complexes with ornithine, 2,4-diaminobutyric acid and 2,3-diaminopropionic acid were studied as new oxygen complexes. The former complex was reversibly, while the latter two complexes were irreversibly oxygenated at room temperature. These oxygenated complexes were diamagnetic and showed electronic absorption spectra similar to that of oxygenated cobalt histidine complex, and they were assumed to be O2-bridged binuclear complexes, L2Co–O2–CoL2 (L: ligand). Cobalt and O2 of the binuclear complexes existed in the state of Co(III) and O22−, respectively. Thermodynamic measurements showed that oxygenation was an exothermal process, and deoxygenation an endothermal one. The reversibility correlated with the reduction potential of the central cobalt(III) ion and the enthalpy change of the oxygenation. Easier deoxygenation corresponded to more positive reduction potential and to smaller enthalpy change.
  • Yoshimi Kurimura, Kousaburo Ohashi
    1971 Volume 44 Issue 7 Pages 1797-1800
    Published: 1971
    Released: March 27, 2006
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    The specific rates for the Fe2+ reductions of cis-Co(en)2ACl2+ (A=methyl-, ethyl-, propyl-, butyl-, ethanol-, and propanolamine), Co(dien)(en)Cl2+ and Co(tetren)Cl2+ have been determined. The observed rates are relatively insensitive to the cis-ligand of the A. The rate constant for the cis-Co(en)2ACl2+ decreases with an increase in the size of the A ligand. In such cases as that of the aminoalcohol ligand, the rate is greater than that of the corresponding alkylamine ligand complex. The effect of chelation by nonbridging ligands has been discussed by comparing the relative effectiveness for Fe2+ reductions of CoN5Cl2+ (N5=(NH3)5, (en)2NH3, (dien)(en), and tetren) with that for Cr2+ reductions of some Co(III) complexes.
  • Tatsuya Saito
    1971 Volume 44 Issue 7 Pages 1800-1807
    Published: 1971
    Released: March 27, 2006
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    The photonuclear reaction yields of 24Na and 28Mg in magnesium, aluminum, silicon, phosphorus, and sulfur were obtained at energies between 20 MeV and 250 MeV by the induced radioactivity method. The 12C(γ,n)11C yield was used as a standard for the beam monitor. The excitation curves of the 27Al→24Na, 28Si→24Na, Si3028Mg, 31P→24Na, 31P→28Mg, 32S→24Na, and 32S→28Mg reactions were obtained from the yields by the photon-difference method. Each of these excitation functions indicates a peak in the 50–70 MeV energy range, except in the case of the sulfur target, in which the peak is due to the contribution from the compound-nucleus process. The interaction of photons with nuclei at photon energies exceeding the peak energy region probably does not lead to the formation of the compound nucleus. In the energy range from 70 MeV up to 150 MeV, the cross sections are due to the contribution from the quasi-deuteron process. At energies above 150 MeV and up to 250 MeV, the quasi-deuteron and pion production processes compete. In the high-energy photonuclear reaction mechanisms, the quasi-deuteron and pion production processes must be considered at the initial cascade process, but the evaporation process may be considered after the cascade process.
  • Hitoshi Kanno
    1971 Volume 44 Issue 7 Pages 1808-1812
    Published: 1971
    Released: March 27, 2006
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    Isotopic fractionation behavior in a thermal ion source was theroretically studied. An equation relating to the observed isotope ratio with the evaporated fraction of the sample was derived under conditions where two kinds of chemical species, atomic (atomic ions and neutral atoms) and molecular (molecular ions and molecules) species, simultaneously evaporate from the filament. It was demonstrated that integrations of all ion currents for two isotopes do not necessarily give a true ratio of the two isotopes in the sample when two evaporating chemical species are ionized at different rates. Isotopic fractionation curves for halides and elements of lithium, potassium, and rubidium are presented.
  • Shunzo Katayama, Reita Tamamushi
    1971 Volume 44 Issue 7 Pages 1812-1815
    Published: 1971
    Released: March 27, 2006
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    The conductance behavior of mixtures was investigated for the systems tris(ethylenediamine)cobalt(III)chloride-sodium maleate and tris(ethylenediamine)cobalt(III)chloride-sodium fumarate in aqueous solutions of various ionic strengths at 25°C. Appreciable deviation of the measured conductivity from additivity was attributed to the ion-pair formation of tris(ethylenediamine)cobalt(III) ion with maleate Ma2− and fumarate Fu2− ions. The concentration formation constants Kc at various ionic strengths were determined by means of computer analysis of the deviation. The thermodynamic ion-pair formation constants K at 25°C were as follows: logK=3.60 for [Co(en)3]3+·Ma2− and logK=2.95 for [Co(en)3]3+·Fu−2.
  • Mutsuo Kodama, Sadatsugu Karasawa, Toshiyuki Watanabe
    1971 Volume 44 Issue 7 Pages 1815-1822
    Published: 1971
    Released: March 27, 2006
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    The substitution reactions of the nickel(II)-nitrilotriacetate complex with diethylenetriaminepentaacetic acid in the presence of ethylenediamine and of the nickel(II)-N-(2-hydroxyethyl)-iminodiacetate complex with ethylenediaminetetraacetic acid and cyclohexane-1,2-diamine-N,N,N′,N′-tetraacetic acid were studied by employing the polarographic method. In the presence of ethylenediamine, the reaction of the nickel(II)-nitrilotriacetate complex with diethylenetriaminepentaacetic acid was found to proceed through the following four pathways:
    (Remark: Graphics omitted.)
    where X3− and Z5− denote completely-deprotonated nitrilotriacetate and diethylenetriaminepentaacetate anions respectively, and A°, ethylenediamine. By comparing the rate constants of the substitution reactions of the nickel(II)-nitrilotriacetate and ethylenediamine complexes with their dissociation rate constants, the structure of the reaction intermediate was determined. From the concentration dependence of the reaction rate, the reactions of the nickel(II)-N-(2-hydroxyethyl)-iminodiacetate complex with ethylenediaminetetraacetic acid and with cyclohexane-1,2-diamine-N,N,N′,N′-tetraacetic acid were concluded to proceed through the following two reaction pathways:
    (Remark: Graphics omitted.)
    where X2− and Y4− mean completely-deprotonated N-(2-hydroxyethyl)-iminodiacetate and ethylenediaminetetraacetate or cyclohexane-1,2-diamine-N,N,N′,N′-tetraacetate anions. From a comparison of the rate constants for the reaction of the N-(2-hydroxyethyl)-iminodiacetate complex with those for the corresponding reaction of the iminodiacetate complex, it was found that the hydroxyethyl group in the N-(2-hydroxyethyl)-iminodiacetate anion rather accelerates the dissociation of the N-(2-hydroxyethyl)-iminodiacetate anion from the nickel(II) ion.
  • Hitoshi Ohtaki, Georg Biedermann
    1971 Volume 44 Issue 7 Pages 1822-1826
    Published: 1971
    Released: March 27, 2006
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    The hydrolytic reaction of nickel ion was studied at 25°C in an aqueous 3M sodium chloride medium. In the range of the total nickel concentration of 0.0145–1.000M, the emf data obtained could be explained in terms of the formation of the complex Ni4(OH)4 (the charge is omitted), the formation constant of the species being found to be log*β4,4=−28.55±0.10, together with some minor species NiOH (log*β1,1≤−10.5) and Ni2OH(log*β1,2≤−10.5).
  • Yukito Murakami, Junzo Sunamoto
    1971 Volume 44 Issue 7 Pages 1827-1834
    Published: 1971
    Released: March 27, 2006
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    Influence of nickel(II), copper(II), and thorium(IV) ions on the hydrolysis of 3-pyridyl and 8-quinolyl phosphates was investigated at μ=0.10 in a lower pH region. The reaction in the presence of the bivalent metal ions followed apparent first-order kinetics with respect to the phosphates in homogeneous phase. The copper ion showed a positive catalytic effect only on the hydrolysis of 8-quinolyl phosphate, and such effect increased markedly as pH was raised. The nickel ion, however, did not show any significant effect on the hydrolysis of both phosphates. The requisites for effective catalysis of bivalent metals have been postulated previously: (1) preliminary chelate formation, and (2) transitional chelate formation. Accordingly, complex formation of the present phosphates with copper(II) and nickel(II) was studied by means of potentiometric measurements. The results strongly suggest the importance of (1) for yielding catalytic efficiency. The presence of the thorium ion resulted in a profound acceleration of hydrolysis of both phosphates in a relatively lower temperature range. The reaction rate did not follow the simple kinetic law although the reaction system was kept homogeneous under the present experimental conditions. The complex formation with the phosphate moiety, which would provide effective charge neutralization for the substrate, is most likely the necessary cause for the thorium-catalysis. Plausible reaction mechanisms and the corresponding potential energy correlations were postulated for the present catalysis.
  • Tadashi Iwachido
    1971 Volume 44 Issue 7 Pages 1835-1840
    Published: 1971
    Released: March 27, 2006
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    Aromatic compounds with an acidic group, such as –OH, –SH, –COOH, –SO3H, >NH, (Remark: Graphics omitted.)CH, and (Remark: Graphics omitted.)B (tetraphenylborate) were tested as extracting agents for potassium. The first four acids showed an extractability lower by far than that of the last three. Most inorganic acids exhibited no signs of extraction. Bulky and electronattracting substituents, such as nitro or halogen group, were proved to be effective in enhancing the extractability. The addition of iodine was also effective. A few kinds of surfactants showed considerably high extractability. Some factors influencing the extraction were speculated upon.
  • Akira Tomita
    1971 Volume 44 Issue 7 Pages 1840-1843
    Published: 1971
    Released: March 27, 2006
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    The kinetics of the oxidation of a cobaltous complex of ethylenediaminetetraacetic acid (EDTA) is determined volumetrically at 50.0°C in the presence of several kinds of carbon as catalysts. One mole of oxygen was used to oxidize four Co(II) ions, and all the Co(II) ions were oxidized to Co(EDTA) ions quantitatively. The rate of oxygen uptake was found to change from zeroth order to first order with respect to the complex ion during the course of oxidation; it was also found to be first order with the oxygen pressure and the amount of the carbon catalyst. The catalytic activity of the carbon was correlated to the quantity of surface basic oxides of the carbon. A possible mechanism which can account for the above results is proposed.
  • Minoru Yoshida, Kazuyoshi Takahashi, Norinobu Yonehara, Takejiro Ozawa ...
    1971 Volume 44 Issue 7 Pages 1844-1850
    Published: 1971
    Released: March 27, 2006
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    The halogen contents of 49 Japanese volcanic rocks are; F: 50–1700 (average 410), Cl: 17–1220 (av. 270), Br: 0.09–8.10 (av. 0.85), I: 0.011–0.32 (av. 0.088) μg/g. The fluorine and chlorine were determined by usual photometric methods, and the bromine and iodine, by photometric methods based on their catalytic action, after decomposition and separation procedures suitable for each case. The bromine and iodine contents are appreciably lower than the values generally accepted for igneous rocks. The bromine content agrees with Sugiura’s value. The frequency distribution of each halogen content shows an approximate lognormality. The chlorine and bromine contents are strongly correlated, and the Br/Cl atomic ratio is in a narrow range (0.66–3.7)×10−3 (av. 1.5×10−3). No other correlation is observed among the halogen contents at all. Each halogen content has no marked relation to the type of rock. A regional difference is seen in the F/Cl and I/Br ratios. Three ultrabasic rocks have very low fluorine (≤20) and chlorine contents (≤50 μg/g). On the other hand, they have a slightly lower bromine content (0.15–0.34 μg/g) than, and almost the same iodine content (0.07–0.13 μg/g) as, the volcanic rocks.
  • Satoru Onaka, Takeshi Miyamoto, Yukiyoshi Sasaki
    1971 Volume 44 Issue 7 Pages 1851-1854
    Published: 1971
    Released: March 27, 2006
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    The nature of Mn–Sn bonds has been studied by 55Mn-NMR and IR spectroscopies of a series of compounds, R3−xXxSn–Mn(CO)5, where R is C6H5 or CH3 and where X is Cl or Br. Molecular orbital considerations have shown that the chemical shift of the 55Mn-NMR spectra is a measure of the σ-polarity of the L–Mn bond in L–Mn(CO)5-type complexes, and that the linewidth is mainly determined by the π-interaction between Mn and Sn. The π-interaction (back-donation from Mn to Sn) seems to be most pronounced in Br3Sn–Mn(CO)5 in the series of (CH3)3−xBrxSn–Mn(CO)5 compounds. The relationships among the chemical shift, the wave numbers of CO stretching modes, and the eqQ, are also shown.
  • Kenyu Kina, Haruo Miyata, Kyoji Tôei
    1971 Volume 44 Issue 7 Pages 1855-1857
    Published: 1971
    Released: March 27, 2006
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    The acid dissociation constants of the three isomeric phosphonophenylazochromotropic acids and their chelate stability constants with alkaline earth metals have been measured by the pH titration method at an ionic strength of 0.10 and at 25.0±0.1°C. The stability order with respect to the ligands is as follows: ortho->meta->para-, and the stability constant of each ligand decreases in the order: Mg>Ca>Sr>Ba; this order is parallel to the reciprocal of the ionic radii of the metal ions. From a comparison between the chelate stability of o-phosphonophenylazochromotropic acid and that of Neo-Thorin, it has been concluded that the magnesium ion forms a more stable chelate bond with the phosphonic group than with the arsonic group.
  • Nobuo Mori, Shinichi Kaido, Koichi Suzuki, Mikio Nakamura, Yojiro Tsuz ...
    1971 Volume 44 Issue 7 Pages 1858-1864
    Published: 1971
    Released: March 27, 2006
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    The SH stretching absorption spectra of some mercapto compounds in dilute carbon tetrachloride solutions and also in acetonitrile solutions have been measured at 20°C. Alkyl mercaptans show absorption bands which are suggestive of the rotational isomerism around the C–S bond. The spectral data indicate that benzyl mercaptan, ω-ethoxyalkyl mercaptans, and ethyl α- and β-mercaptoalkanoates form practically no intramolecular hydrogen bond between the SH group and the hydrogen-acceptor group. In thiosalicylic acid and its ethyl ester, the hydrogen-bonding to the carbonyl group is partially possible even in acetonitrile. On the other hand, the corresponding free carboxylic acids are not hydrogen-bonded between the S atom and the carboxyl group.
  • Toshie Shiba, Hiroshi Kato
    1971 Volume 44 Issue 7 Pages 1864-1868
    Published: 1971
    Released: March 27, 2006
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    Mesoionic 5-iminothiazoles were prepared by the cyclization of N-thiobenzoyl-methylaminoacetonitriles with hydrogen chloride or acyl chlorides. The reaction between a 5-aminothiazolium chloride and acyl chlorides, isocyanate, sulfonyl chloride, and nitrous acid gave the corresponding N-substituted mesoionic 5-iminothiazole derivatives. The spectral data of these compounds as well as the ready bromination of the ring support the view that this ring system is aromatic.
  • Akira Suzuki, Miki Goto
    1971 Volume 44 Issue 7 Pages 1869-1872
    Published: 1971
    Released: March 27, 2006
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    Four ribityllumazine compounds were isolated from the cultured medium of Pseudomonas ovalis. Three of them were characterized as 6-methyl-8-(1-D-ribityl)-2,4,7-trioxohexahydropteridine, 6-(3-indolyl)-8-(1-D-ribityl)-2,4,7-trioxohexahydropteridine and 6-(p-hydroxyphenyl)-8-(1-D-ribityl)-2,4,7-trioxohexahydropteridine by comparison with synthetic samples. The fourth compound, named putidolumazine, was supposed to be a new compound (2-carboxyethyl)-8-(1-D-ribityl)-2,4,7-trioxohexahydropteridine from its chemical and spectroscopic properties. This was confirmed from the identity of both natural and synthetic products.
  • Yasuhiro Yamamoto, Hiroshi Yamazaki
    1971 Volume 44 Issue 7 Pages 1873-1875
    Published: 1971
    Released: March 27, 2006
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    The reactions of trans-iodobis(phosphine)aklylplatinum(II) compounds with isocyanide were carried out. The reactions of isocyanide with the methyl and benzyl derivatives of platinum(II) with triphenylphosphine or dimethylphenylphosphine gave salt-like complexes [trans-Pt(PR3)2(CNR′)CH3]I (1) (PR3=PPh3, PPhMe2; R′=C6H11, C(CH3)3). When 1 was refluxed in benzene or toluene, an insertion of isocyanide took place, affording trans-iodobis(phosphine)(1-cyclohexylimino)alkylplatinum(II). Two P-CH3 proton resonances were observed in the NMR spectrum of trans-Pt(PPhMe2)2I[C(CH3)=NC6H11], indicating that the two methyl groups on the same phosphorus atom are magnetically nonequivalent. It was deduced from this NMR behavior that all the iminoacyl complexes prepared have a five-coordinate structure.
  • Michinori Oki, Minoru Suda
    1971 Volume 44 Issue 7 Pages 1876-1880
    Published: 1971
    Released: March 27, 2006
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    9-t-Butylanthracene was treated with dimethyl acetylenedicarboxylate and benzoquinone to give Diels-Alder adducts. The NMR spectra of these adducts suggest that the internal rotation about the C1–CBu bond is not taking place on the NMR time scale. On the other hand, a Diels-Alder adduct prepared from 9-isopropylanthracene and dimethyl acetylenedicarboxylate shows the coalescence phenomenon of the NMR signals when the temperature is raised. The possibility of optical resolution due to hindered rotation about the sp3sp3 carbon bond is pointed out.
  • Michinori Oki, Nobuo Nakamura
    1971 Volume 44 Issue 7 Pages 1880-1885
    Published: 1971
    Released: March 27, 2006
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    1-(1-Hydroxyethyl)-4,6,8-trimethylazulene (3) was prepared by the lithium aluminum hydride reduction of 1-acetyl-4,6,8-trimethylazulene, and by the reaction of methylmagnesium iodide with 1-formyl-4,6,8-trimethylazulene. 3 showed various melting points according to its crystallization conditions and the reaction solvent. Their IR spectra both in solid states and in solutions, the NMR spectra at various temperatures, and the results of X-ray diffraction studies led to a conclusion that this phenomenon is attributable to polymorphism. From the temperature dependence of the NMR spectra of the t-butyl protons of 1-t-butyl-4,6,8-trimethylazulene, the internal rotation around the CBu–Cazulene was concluded to be slow only at the lower temperature.
  • Tadashi Sato, Itomi Homma
    1971 Volume 44 Issue 7 Pages 1885-1891
    Published: 1971
    Released: March 27, 2006
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    When α,β-unsaturated ketone tosylhydrazones (5) were heated in 85% aqueous acetic acid, a smooth decomposition was induced and β-tosylketones (4) were obtained in fair yields. Tosylhydrazones, devoid of an olefinic group in the specified position, failed to undergo the present reaction. When allyl halides (17) were reacted with the anion of tosylhydrazide in DMSO, substitution occurred on the N-1 of tosylhydrazide, unlike as in the case of the reaction of chlorides with tosylhydrazide in pyridine, which effected the substitution on N-2. On warming in acetic acid, these 1-allyltosylhydrazides (18) afforded olefins (19) in fair yields, with a complete allylic rearrangement. A concerted cyclic mechanism was proposed for the 54 and 1819 reactions.
  • Koichi Kojima, Susumu Iwabuchi, Kuniharu Kojima, Niro Tarumi
    1971 Volume 44 Issue 7 Pages 1891-1895
    Published: 1971
    Released: March 27, 2006
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    The graft copolymerization of methyl methacrylate by trialkylborane onto hemoglobin has been studied at 37°C. In aqueous media, graft copolymers were obtained in the form of a light brown powder or granules, while no grafting occurred in organic solvents, such as cyclohexanone, n-hexane, tetrahydrofuran, and toluene. The presence of water seems to be essential to the grafting. The hydrogen peroxide-decomposing property of hemoglobin was well preserved in the graft copolymers so obtained. The mechanism of the initiation is discussed.
  • Otohiko Tsuge, Shuntaro Mataka
    1971 Volume 44 Issue 7 Pages 1896-1900
    Published: 1971
    Released: March 27, 2006
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    The reaction of p-substituted N-sulfinylanilines with styrene oxide in the presence of tetraethylammonium bromide gave the corresponding 1,2,4,5- and 1,2,4,6-tetraarylpiperazines, whose configurations were established on the basis of the NMR spectral studies. On the other hand, while a similar reaction of p-substituted N-sulfinylphenylhydrazines with the oxide in benzene gave the corresponding diaryl disulfide, diaryl sulfide, and p-substituted biphenyl, the reaction in acetonitrile did not give the biphenyl. The pathways for these reactions are suggested.
  • Atsuyoshi Ohno, Tomo’o Saito, Akio Kudo, Gen-ichi Tsuchihashi
    1971 Volume 44 Issue 7 Pages 1901-1904
    Published: 1971
    Released: March 27, 2006
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    Kinetics of the cis-trans isomerization of 1,2-bis(phenylthio)ethylene induced by benzenethiyl radicals and the exchange of phenylthio group have been studied by using thiophenol-phenyl-14C Pseudo-first order rate constants for the isomerization and the exchange are 2.08±0.22×10−5 sec−1 and 2.03±0.26×10−5 sec−1 at 50°C, respectively. The cis/trans ratio of this olefin is 55–58/45–42 at the completion of the reaction, which differs from the value obtained from the reaction induced by iodine (48–49/51–52). The difference has been interpreted with the idea that the isomer composition in the cis-trans isomerization is determined by kinetic factors when the reaction is initiated by thiyl radicals.
  • Yusaku Ikegami, Shuichi Seto
    1971 Volume 44 Issue 7 Pages 1905-1908
    Published: 1971
    Released: March 27, 2006
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    The electron spin resonance spectra of 2- and 6-methoxyazulene anion radicals have been examined. The radicals were generated from neutral species either by electrolytic reduction in N,N-dimethylformamide or by the reduction with alkali metals in ethereal solvents. The experimental splitting constants are explained satisfactorily in terms of the calculated spin densities by McLachlan’s procedure.
  • Mutsuo Kataoka, Takashi Ando, Masazumi Nakagawa
    1971 Volume 44 Issue 7 Pages 1909-1914
    Published: 1971
    Released: March 27, 2006
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    Concerning the studies on the effect of ring strain on the electronic spectra of cylcic acetylenes, a series of polymethylene ether derivatives of p,p′-dihydroxydiphenyldiacetylene (VIn, n=13, 14, 15, and 18) has been prepared by the oxidative coupling of p-hydroxyphenylacetylene polymethylene ethers (Vn, n=13, 14, 15, and 18) under a high dilution condition. A slight bathochromic shift accompanied by hypochromism was observed in the electronic spectra of VIn resulting from the increase of the ring strain. The same trend has been observed in the p,p′-bridged cyclic tolans. However, the bathochromic shift observed in the p,p′-series makes a contrast with the hypsochromic shift in the strained o,o′-bridged cyclic diphenyldiacetylene (I) and o,p′-bridged cyclic tolans (II). The NMR and IR spectra of VIn were discussed.
  • Fumio Toda, Takashi Ando, Mutsuo Kataoka, Masazumi Nakagawa
    1971 Volume 44 Issue 7 Pages 1914-1916
    Published: 1971
    Released: March 27, 2006
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    Characteristic features of the electronic spectra of o,o′-bridged cyclic diphenyldiacetylenes (In), o,p′-bridged cyclic tolans (IIn), p,p′-bridged cyclic diphenyldiacetylenes (IIIn) and p,p′-bridged cyclic tolans (IVn) are compared. The hyperchromism observed in the longest-wavelength absorption maxima (λmax) in the higher homologues of In, IIIn, and IVn as compared with the absorption intensities of the respective open-chain analogues is explained in terms of the coplanarity of the chromophore system, and the marked hypochromism observed in the lower homologues of these cyclic acetylenes is attributed to ring strain. The hypochromism observed in the series of IIn is ascribed to the superposition of the effects of ring strain and the twisting of phenyl groups. The bathochromic shifts of λmax with the increase of ring strain in the p,p′-bridged series (IIIn and IVn) are explained by the pronounced increase of the energy of the ground state of the strained molecule of this series. On the other hand, the hypsochromic shifts of λmax of o,o′-bridged series (In) are regarded as the result of the minor increase of energy of the ground state along with the increase of the ring strain.
  • Masayoshi Ishige, Koji Sakai, Masatoshi Kawai, Kazuo Hata
    1971 Volume 44 Issue 7 Pages 1917-1922
    Published: 1971
    Released: March 27, 2006
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    This paper will describe the reaction of benzyl alcohol in the presence of various kinds of modified stabilized nickel catalysts, which had been prepared from the mother catalyst by treating it with solutions of appropriate metal chlorides. The catalytic activities of each modified catalyst for the formation of benzene, toluene, and benzaldehyde were compared in terms of the fH,fCH3, and fCHO values; the selectivities for the formation of benzene and toluene against that of benzaldehyde, SH and SCH3, were also evaluated. In general, the formation of toluene and benzene was greatly affected both by the kind and by the amount of metal chlorides used as additives. The reaction was promoted by the addition of a proper quantity of alkali metal chloride. In the cases of the reactions by lowlymodified catalysts, the decreasing order of the fH and fCH3 values according to the kind of metal ion adsorbed on the catalyst was as follows: Na+≥K+>Co2+>Ca2+>Cd2+>Ba2+>Hg2+>Cu2+. On the other hand, in the higher degrees of modification, the corresponding order of the fH and fCH3 values was altered to be as follows: K+>Na+>Co2+>Cd2+>Ba2+≥Ca2+>Cu2+>Hg2+. With regard to the modified nickel catalysts treated with 0.08 N solutions, it was found that the sequence of the fH and fCH3 values due to the kind of metal ion was roughly correlated with that of the atomic numbers of the corresponding metals. The results are discussed in connection with the general concept of catalytic chemistry.
  • Ichiro Hirao, Yasuhiko Kato, Toshiyuki Hirota
    1971 Volume 44 Issue 7 Pages 1923-1927
    Published: 1971
    Released: March 27, 2006
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    5-[2-(5-Nitro-2-furyl)-1-(4-nitrophenyl)vinyl]-1,3,4-oxadiazoles and -1,3,4-thiadiazoles have been prepared from 3-(5-nitro-2-furyl)-2-(4-nitrophenyl)acrylic acid. All of these compounds exhibited strong antibacterial activities against Staphylococcus aureus.
  • Shozo Kato, Jun′ichi Nakaya, Eiji Imoto
    1971 Volume 44 Issue 7 Pages 1928-1933
    Published: 1971
    Released: March 27, 2006
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    Three isomers of 1-methylcyanoquinolinium perchlorates were reduced by controlled potential electrolysis for one-electron transfer, and the reduction products were identified in order to clarify their reduction mechanisms and the effect of the cyano group on the stabilities of cyanoquinolinyl radicals. The 1-methyl-4-cyanoquinolinyl radical was stable enough to survive at room temperature under anaerobic conditions. The 1-methyl-2- and 1-methyl-3-cyanoquinolinyl radicals were short-lived and were subsequently dimerized to the 1,4-dihydrotype. The 1-methyl-4-cyanoquinolinyl radical was autoxidized to 1-methyl-4-cyanoquinolinium salts in an electrolyte solution and to 1-methyl-4-cyano-2-quinolone in an ethanol solution.
  • Yoshio Ueno, Takeshi Nakai, Makoto Okawara
    1971 Volume 44 Issue 7 Pages 1933-1938
    Published: 1971
    Released: March 27, 2006
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    With a view toward demonstrating the structural effect on the reactivity of iminodithiocarbonates, the reactions of some electrophilic reagents with the following four iminodithiocarbonates have been studied; 2-methylimino-(IVa) and 2-phenylimino-1,3-dithiolane (IVb) and S,S′-dimethyl-N-methyl-(Va) and S,S′-dimethyl-N-phenyliminodithiocarbonate (Vb). Cyclic IVa and its N-ethyl homologue reacted with an equimolar amount of phenyl isocyanate at room temperature giving 1:2 cycloadducts. However, the other imino compounds (IVb, Va, and Vb) did not react at all even at elevated temperature. All these imino compounds reacted with acid chlorides to afford the corresponding N-acyliminium salts which could, in some cases, be isolated; however the rate of formation of the salts varied significantly with the structure of the imino compound. Some reactions with alkyl halides and phenyl isothiocyanate were also attempted. From the present results and those previously obtained on their reactions with epoxides and with ketenes, it has been concluded that the nucleophilic reactivity of the imino compounds increases in the order Vb<Va<IVb<IVa. Furthermore, it was found that the basicity of the imino compounds increased in the order Vb<IVb<Va<IVa. The observed ring effect and N-substituent effect on the reactivity and basicity of the imino compounds are discussed in connection with similar effects on the stability of closely related tri(hetero)carbonium ions, i.e., bis(alkyl thio)-dialkylaminocarbonium ion (I).
  • Yukito Murakami, Junzo Sunamoto
    1971 Volume 44 Issue 7 Pages 1939-1944
    Published: 1971
    Released: March 27, 2006
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    The spontaneous hydrolysis of 3-pyridyl and 8-quinolyl phosphates was investigated at 60, 70, and 80°C over the −log[H+] range from 1 to 7 in aqueous media with an ionic strength of 0.10. The reactions followed apparent first-order kinetics with respect to the unreacted phosphate species, and the maximum rate was observed around −log[H+]=2.5. Reactive species of each phosphate in hydrolysis were the neutral zwitterion and the monoanion, the former being found to be more labile. In a moderately acidic region (−log[H+]<2.0), an apparent enhancement of the reaction rate was detected for both phosphates, which was attributed to the acid catalysis acting on the zwitterion species. The activation enthalpy for hydrolysis of the zwitterion and the monoanion falls near 30 kcal mol−1. This is consistent with the reaction mechanism expected for hydrolysis of ordinary monoalkyl or monoaryl phosphate, in which the P–O bond cleavage takes place. The activation entropy data also provide an evidence for the unimolecular nature of the transition state. The kinetic solvent isotope effect kH2o/kD2o for the hydrolysis of both phosphates falls near unity. The isotope effect in this magnitude is consistent with the intramolecular proton-transfer mechanism. The results are, therefore, consistent with a mechanism for the hydrolysis of the zwitterion species of 8-quinolyl phosphate in which the quinolinium group donates a proton intramolecularly to the leaving ester oxygen atom in the transition state.
  • Hideki Sakurai, Shun-ichi Hayashi, Akira Hosomi
    1971 Volume 44 Issue 7 Pages 1945-1949
    Published: 1971
    Released: March 27, 2006
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    Relative reactivities in dibenzoyl peroxide-catalyzed addition of bromotrichloromethane to nine nuclearsubstituted styrenes have been investigated with unsubstituted styrene. The effect of meta substituents upon the relative rates was correlated with the simple Hammett equation using either σ or σ+ constants. The relative rates of para-substituted styrenes, however, did not obey the simple Hammett relation, with the results best explained on the basis of polar (ρσ+) and resonance (ED) terms. All para substituents examined increase the reactivity.
    log(kkH)=ρσ++ED
    The ED term shows a striking correlation with logQ, of the corresponding para styrene in Alfrey-Price′s Q-e scheme of free-radical copolymerization. That the polar term originates in charge-transfer interactions between the olefin and the electrophilic trichloromethyl radical and can be expressed by ρσ+ is further supported by the evidence that charge-transfer energies of substituted styrenes showed good correlation with σ+. Factors influencing the reactivity have been discussed.
  • Hiroshi Yoshida, Tsuyoshi Ogata, Saburo Inokawa
    1971 Volume 44 Issue 7 Pages 1949-1951
    Published: 1971
    Released: March 27, 2006
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    New alkyl acyl dithiol- and trithiocarbonates (1 and 2) were prepared from acid chlorides and tetramethylammonium alkyl dithiol- and trithiocarbonates (3 and 4). 1 and 2 decomposed at around 100°C to give the corresponding thiolesters in good yields. The kinetic studies of the decomposition of 1 and 2 showed that, in o-dichlorobenzene, the decomposition reaction was first order and that it proceeded via a four-membered intramolecular cyclic mechanism.
  • Tetsuo Nozoe, Kahei Takase, Kohei Shimizu, Masafumi Yasunami
    1971 Volume 44 Issue 7 Pages 1951-1956
    Published: 1971
    Released: March 27, 2006
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    The chemical properties of the acetyl side-chain of 4-acetyltropolone and its methyl ethers in relation to some oxidizing and reducing reagents were examined. The selenium-dioxide oxidation of one of the methyl ethers afforded a glyoxyloyl derivative in its hydrate form. The catalytic reduction of 4-acetyltropolone gave a mixture of 4-(1-hydroxyethyl)- and 4-ethyltropolones. The reduction of two isomeric methyl ethers with sodium borohydride gave 4-(1-hydroxyethyl)-2-methoxy- and 6-(1-hydroxyethyl)-2-methoxytropones respectively, from which two isomeric methyl ethers of 4-ethyltropolone were prepared in pure states.
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