Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 46 , Issue 8
Showing 1-50 articles out of 87 articles from the selected issue
  • Hajime Akimoto, Kinichi Obi, Ikuzo Tanaka
    1973 Volume 46 Issue 8 Pages 2267-2272
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The Rice-Ramsperger-Kassel-Marcus treatment has been applied to the energized ethylene produced in the vacuum-ultraviolet photolysis of C2H6, C2D6, C3H8, C3D8, n-C4H10 and n-C4D10. The energy spread in the energized ethylene has been evaluated assuming modified statistical distribution of liberated energy among fragment species. The calculated nonequilibrium unimolecular decomposition rate constant for the process C2H4(C2D4)→C2H2(C2D2)+H2(D2) could satisfactorily reproduce the experimental pressure dependence of ethylene to acetylene ratio. Non-statistical kinetic energy Ek seems to appear for the primary decomposition of the n-paraffins. Its value ranges from zero for the elimination of methane and ethane from propane and n-butane, respectively, at 147.0 nm to about 25 kcal mol−1 for the elimination of hydrogen from ethane at 123.6 nm.
  • Satoru Tsuda, Akira Yokohata, Toshikatsu Umaba
    1973 Volume 46 Issue 8 Pages 2273-2277
    Published: 1973
    Released: March 27, 2006
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    Negative ion mass spectra of acrylonitrile were measured for the electron energies of 80, 40 and 9.5 eV. Emphasis was laid on the abundance of the negative ions relative to the positive ions measured for the energies of 80, 40 and 15 eV, respectively. The ionization efficiency (IE) curves were also determined up to 25 eV for the ions of me 25(C2H), 26(CN), 27(HCN), 38(C2N), 39(CHCN), 40(CH2CN) and 50(C3N). The electron impact of 80 eV and 40 eV gave almost the same distribution of me for negative ion mass spectra. Besides the most intense peak of CN ions, relatively strong peaks of C3N, C2H, C2 and C2N ions were observed. In 9.5 eV, CN ions predominated over other ions. Yields of the ions showed a good linearity against the pressure in the range used for usual chemical analysis, irrespective of electron energy. Comparison of the yield of CN ions with that of C2H3CN+ gave the values 1.2×104 and 1.9×104 for C2H3CN+/CN at 80 eV and 40 eV, respectively, and 47.6 at 9.5 eV (15 eV for the positive ions). The plausible reaction schemes expected to occur at each onset observed in the IE curves were also sought thermochemically by using ΔHf values of the reactant and products. A value \gtrsim2 eV was obtained for the electron affinity of C2H.
  • Nobuko I. Wakayama, Yasuko Nakano, Yo-ichiro Mashiko
    1973 Volume 46 Issue 8 Pages 2277-2279
    Published: 1973
    Released: March 27, 2006
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    A glass sample tube is widely used in zone melting of organic substances since it is transparent, inert to most substances and easily prepared in the laboratory. The glass tube, however, is frequently broken owing to the volume increase of the sample. A new device was worked out to prevent breakage of the sample tube, to purify the sample efficiently and to make replacement of the atmosphere inside the sample tube possible. The apparatus requires much less space than for one ever reported and consists of a sample tube with a set of stainless steel spring and Teflon plug and a new mechanism for carrying it. It was successfully used for biphenyl and p-dichlorobenzene.
  • Shiro Konishi, Shigeya Niizuma, Hiroshi Kokubun, Masao Koizumi
    1973 Volume 46 Issue 8 Pages 2279-2284
    Published: 1973
    Released: March 27, 2006
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    Two calicene derivatives, 1,2,3,4-tetrachloro-5,6-diphenylcalicene and 1,2,3,4-tetrachloro-5,6-di-n-propylcalicene, were reduced with an alkali metal in degassed tetrahydrofuran and the ESR spectra of the resluting monoanion radicals were investigated. It was found that in both anion radicals the unpaired spin does not exist on the five-membered ring, and is localized only on the other part. In the latter anion radical, the five-membered and three-membered rings were found to be twisted toward each other at about 45°, a line width alternation caused by hindered internal rotation of two adjacent n-propyl groups being observed. The potential barrier for the hindered rotation was determined to be about 1.5 kcal/mol.
  • Azumao Toyota, Takeshi Nakajima
    1973 Volume 46 Issue 8 Pages 2284-2287
    Published: 1973
    Released: March 27, 2006
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    On the basis of the second-order Jahn-Teller effect and SCF MO method, we have examined the geometrical structures with respect to bond length and the ground-state multiplicity and stability of peri-condensed tetracyclic nonbenzenoid aromatic hydrocarbons. It was found that of the molecules examined, dibenzo[cd, gh]pentalene (III) and its seven-membered analogue (IV) should have a triplet ground-state, exhibiting no appreciable double-bond fixation in the peripheral carbon skeleton. The other molecules were predicted to suffer the first-order or second-order bond distortions, showing a more or less marked double-bond fixation. The electronic spectra were calculated using the bond distances obtained on the basis of SCF MO method.
  • Nobuaki Nakashima, Hidetoshi Inoue, Noboru Mataga, Chiyoe Yamanaka
    1973 Volume 46 Issue 8 Pages 2288-2290
    Published: 1973
    Released: March 27, 2006
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    Time-resolved fluorescence spectra and the fluorescence rise and decay curves have been measured for p-(N,N-dimethylamino)-benzonitrile. The results demonstrate the relaxation process to be due to the interaction between the solvent and the 1La state of the solute, leading to dual fluorescence.
  • Shigeru Yamashita, Teruo Hayakawa
    1973 Volume 46 Issue 8 Pages 2290-2292
    Published: 1973
    Released: March 27, 2006
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    Primary processes of the photolysis of 1,1′-azopropane were studied using a high intensity light beam and a collision-free photochemical reactor incorporated in the ion-source of a mass spectrometer. The photofragments produced by the following three one-bond fission primary processes were found.
    & CH_3CH_2CH_2N_2CH_2CH_2CH_3+hν→CH_3CH_2CH_2N_2CH_2+CH_2CH_3\labeleq1
    & CH_3CH_2CH_2N_2CH_2CH_2CH_3+hν→CH_3CH_2CH_2N_2+CH_2CH_2CH_3\labeleq2
    & CH_3CH_2CH_2N_2CH_2CH_2CH_3+hν→2CH_3CH_2CH_2N\labeleq3
    The lifetime of these photofragments seems to be longer than 50 μs considering the experimental conditions.
  • Fusao Takusagawa, Ken Hirotsu, Akira Shimada
    1973 Volume 46 Issue 8 Pages 2292-2299
    Published: 1973
    Released: March 27, 2006
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    The crystal structure of dinicotinic acid has been determined by X-ray diffraction method. Two kinds of twinning crystals were obtained by changing the pH of the aqueous solution by recrystallization. The crystals are monoclinic with the space group of P21/c and with cell dimensions of a=9.702, b=11.153, c=6.587 Å, and β=107.8°. The crystal structure was solved by an inspection of the sharpened Patterson map. The final R value is 5.93% for 1181 observed reflections. The dinicotinic acid molecule takes an intermediate structure between the neutral molecule and the zwitter ion with an approximate C2v symmetry. The bond lengths and angles related by the C2v symmetry are equal within the limits of experimental error for those of the two carboxyl groups. The C(2)–N(1)–C(6) bond angle is 119.8°, which lies between those of protonated and unprotonated species of the pyridine ring. The molecules lie approximately on planes parallel to the (001) plane at z=1⁄4 and 3/4. Each molecules on the same plane is joined through two kinds of hydrogen bonds (O–H···O; 2.594 Å, O···H···N; 2.515 Å), related by two-fold screw axes, with four neighboring molecules. In the O···N hydrogen bond, the hydrogen bonding distance and angle are 2.515 Å and 174° and the O–H and N–H distances are 1.23 and 1.29 Å, which are equal within the limits of experimental error. Therefore, it may be considered as an example of the single minimum hydrogen bond of the O–H···N hydrogen-bond type. The existence of two kinds of twins may be interpreted on the basis of the layer structure.
  • Yozo Chatani, Katsuki Kitahama
    1973 Volume 46 Issue 8 Pages 2300-2305
    Published: 1973
    Released: March 27, 2006
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    The crystal structure of the cyclic pentamer of formaldehyde, 1,3,5,7,9-pentoxecane, has been determined by the X-ray diffraction method. The unit cell is orthorhombic, with a=8.154 Å, b=10.673 Å, c=7.666 Å. The space group is Pbcn, and there are four molecules per unit cell. The structure was refined by the blockdiagonal least-squares method to a final discrepancy factor, R, of 0.049, using 712 reflections observed with an automatic four-circle single-crystal diffractometer. The molecules in the crystals are ten-membered rings with an exact C2–2 symmetry; the torsion angles of the five independent C–O bonds are 72.9°, −118.7°, 84.2°, −123.4°, and 69.8°, and the two halves of the molecule are related by a twofold rotation axis. The averaged C–O bond length is 1.410 Å, and the averaged C–O–C and O–C–O bond angles are 115.6° and 111.8° respectively. The close intramolecular H···H distances are 2.17 Å and 2.20 Å.
  • Yoshihiro Mori, Akira Sakakibara, Hiroo Inokuchi
    1973 Volume 46 Issue 8 Pages 2305-2307
    Published: 1973
    Released: March 27, 2006
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    The magnetic susceptibility in solid oxygen-argon mixtures has been obtained as a function of the temperature from 12 K to the melting point. In case of the 95% O2–5% Ar system, the behavior of the magnetic susceptibility was similar to that of pure oxygen except for some dynamical effects caused by the addition of argon to the oxygen lattices. In the composition range between 92% and 66% O2, the appearance of a novel phase, δ, was observed from the magnetic susceptibility measurements; its temperature and concentration dependence was discussed qualitatively on the basis of the crystal structure.
  • Naoto Yamamoto, Michio Matsumura, Hiroshi Tsubomura
    1973 Volume 46 Issue 8 Pages 2307-2311
    Published: 1973
    Released: March 27, 2006
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    Triphenylmethane, irradiated in the near ultraviolet region in a non-polar rigid medium at 77 K, showed thermoluminescence consisting of three bands, fluorescence and phosphorescence of triphenylmethane and fluorescence of triphenylmethyl radical. With the increase of solute concentration the yield of the emissions from triphenylmethane decreased while that of the emission from the radical increased. It was concluded that the emissions from triphenylmethane were due to the recombination between triphenylmethane cation and the photoejected electron, and that the fluorescence from the radical was mainly due to the electron transfer reaction between triphenylmethane cation and triphenylmethyl anion. Detailed emission processes inlcuding electron transfer and energy transfer processes were discussed.
  • Takao Iijima
    1973 Volume 46 Issue 8 Pages 2311-2314
    Published: 1973
    Released: March 27, 2006
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    The structure parameters of ethane have been re-examined by the use of the spectroscopic moments of inertia and the electron diffraction results, on the basis of the large amplitude theory for the torsional motion. The results have been applied to the CH3CD3-species in order to see whether or not the change of the moment of inertia in the torsionally excited state observed by Hirota and Matsumura is consistent with the theoretical prediction on the deformation of the molecular frame upon torsion proposed by Veillard. The conclusion has been affirmative. The elongation of the C–C distance by 0.0028 Å and the decrease of the HCH angle by 0.05° in the torsionally excited state as expected from the theoretical calculation have been found to be consistent with the experimental result of microwave spectroscopy.
  • Toshio Chikaraishi, Eizi Hirota
    1973 Volume 46 Issue 8 Pages 2314-2316
    Published: 1973
    Released: March 27, 2006
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    The microwave spectrum of arsenic trifluoride was observed in the excited states of all the normal vibrations. The rotational constant at the equilibrium state was determined, and the equilibrium As–F distance was calculated to be 1.7044 Å assuming the FAsF angle to be 95°58′. The l-type doubling constant, q4, and the asymmetry parameter, η, of the As nuclear quadrupole coupling constant were determined in the v4=1 to be 10.24±0.02 MHz and −0.005±0.01, respectively.
  • Okitsugu Kajimoto, Masaru Kobayashi, Takayuki Fueno
    1973 Volume 46 Issue 8 Pages 2316-2320
    Published: 1973
    Released: March 27, 2006
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    Charge distributions in vinyl methyl and divinyl ethers and their sulfur homologs bearing a polar substituent at the trans-β position were calculated by the CNDO/2 method. It was found that the effect of substituents on charge distribution is transmitted primarily through the successive π-polarization of the ethylenic units involved. In the divinyl compounds, the sulfur atom on the spd basis is calculated to transmit the substituent effects more effectively than the oxygen atom. The greater transmission efficiency of the sulfur atom is interpreted in terms of the pπ-dπ-pπ conjugation.
  • Aritada Hatta, Masao Suzuki, Kunio Kozima
    1973 Volume 46 Issue 8 Pages 2321-2323
    Published: 1973
    Released: March 27, 2006
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    The quadrupole hyperfine structure was resolved and analyzed for the vibrationally-ground state of the NH2 species. The quadrupole coupling constants are: χaa=2.34, χbb=1.86, and χcc=−4.20 MHz. The rotational constants obtained from the quadrupole corrected frequencies are as follows: A=5617.67, B=2593.88, and C=1777.04 MHz. The rotational constants of the ND2 species in the vibrationally-ground state were also determined. By the use of the moments of inertia of both species, the non-planarity of this molecule was ascertained. The dipole moments of the NH2 and the ND2 species were determined to be 1.15±0.02 D and 1.13±0.01 D respectively.
  • Kenichi Okamoto, Shigekazu Kusabayashi, Hiroshi Mikawa
    1973 Volume 46 Issue 8 Pages 2324-2331
    Published: 1973
    Released: March 27, 2006
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    Photoconductivity in a sandwich-type cell of a PVCz film was investigated in a high vacuum and in the air. A large photociirrent was observed in the π–π* absorption region and a small photocurrent in the visible region. The former showed the following interesting points in its behavior. In low applied fields, no difference was found between the photoconductivity with positive-electrode illumination and that with negative-electrode illumination. In moderate or high fields, however, the photoconductivity with positive-electrode illumination was significantly different from that with negative-electrode illumination. The former showed a superlinear dependence on the applied field (consequently, iph+>>iph) and a spectral response coinciding with the absorption spectrum. This photoconductive behavior was explained by assuming the mechanism of carrier generation, namely, the fieldassisted thermal dissociation of exciplexes and the detrapping of trapped carriers by singlet excitons. Carriers are supposed to migrate through the overlap of π-electrons of neighboring carbazyl rings in the same polymer chain.
  • Michiro Hayashi, Keiichi Ohno, Hiromu Murata
    1973 Volume 46 Issue 8 Pages 2332-2342
    Published: 1973
    Released: March 27, 2006
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    The vibrational assignments of the observed spectra of propyl bromide and its two asymmetrically-deuterated species have been worked out. Since the two gauche isomers come not to be equivalent for the asymmetrically-deuterated species, the infrared bands of the gauche isomer can be expected to be split into doublets, while the bands of the trans isomer remain singlets. The observed infrared bands for the gauche isomer were actually the doublets for the C–Br stretching and two CH2 rocking modes. The C–D stretching and deformation modes of the β-deuterated species were also in the expected spectral patterns. In order to confirm the vibrational assignments, the normal vibration calculation was carried out using a modified Urey-Bradley force field for the parent and two asymmetrically-deuterated species.
  • Mitsutomo Tsuhako, Itaru Motooka, Masamitsu Kobayashi
    1973 Volume 46 Issue 8 Pages 2343-2346
    Published: 1973
    Released: March 27, 2006
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    Changes in the structures of various aluminum phosphates as a result of grinding were studied by a variety of physical methods—X-ray analysis, DTA, TGA, infrared absorption spectroscopy and electron microphotography, and their acidic properties were investigated in order to obtain information on the surface activity of the compounds. The X-ray diffraction patterns indicated that the A, B, and C types of Al4(P4O12)3 and AlPO4 (Berlinite) did not become completely amorphous even after grinding for 72 hr; this shows that the crystal structures of these compounds were relatively stable to grinding. Substance K was structurally more fragile than the other aluminum phosphates (Al4(P4O12)3, AlPO4), becoming completely amorphous on being ground for 72 hr. On DTA and TGA, the ground aluminum phosphates exhibited an endothermic peak, accompanied by a weight loss due to the loss of adsorbed water in the vicinity of 100°C. A further weight loss at higher temperatures was presumably due to dehydration caused by the condensation of P–OH. The amounts of acids on the ground aluminum phosphates were almost independent of the acid strength, which was around +1.5 (pKa). The amounts of acids of the A, B, and C types and of AlPO4 tended to increase slightly with the grinding time. The amount of acid of the K substance reached a maximum after 6 hrs grinding but decreased slowly when grinding was continued for longer than 15 hr.
  • Koichi Oka, Hideo Yamazaki, Shoji Shida
    1973 Volume 46 Issue 8 Pages 2347-2352
    Published: 1973
    Released: March 27, 2006
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    The effect of various additives, i.e., nitrous oxide, sulfur hexafluoride, methyl chloride, and sulfur dioxide, on the yield of the trapped electrons produced in the γ-irradiated 3-methylhexane (3MHX) glass at 77 K have been investigated by the ESR technique. The yields of the trapped electrons were reduced by the addition of all the solutes examined; the efficiency of electron scavenging was found to be in the order of SF6>CH3Cl>N2O>SO2. The concentration dependence of the electron scavengers showed that the efficiency of the electron scavenging in the glassy state had values intermediate between those in the gas and liquid phases. The high efficiency observed in the glassy state suggests that the non-solvated electrons before being trapped move about rapidly in the glassy matrix as the form of quasi-free electrons. The ESR-power saturation of the trapped electrons was considerably reduced by the addition of N2O; a possible mechanism of the relaxation of the ESR is proposed.
  • Koichi Ohno, Tomohiko Hirooka, Yoshiya Harada, Hiroo Inokuchi
    1973 Volume 46 Issue 8 Pages 2353-2355
    Published: 1973
    Released: March 27, 2006
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    The orbital energies of several unsaturated hydrocarbon molecules have been calculated using a modified CNDO/2 method, with the electron repulsion integrals evaluated from Klopman’s formula and the σ–π separation factor proposed by Tinland and Jaffé. The empirical parameters are determined to reproduce the observed ionization potentials for ethylene and benzene via Koopmans’ theorem. The results are shown to agree well with the available experimental ionization potentials and with the assignments of the photoelection spectra.
  • Tatsuya Sekine, Jun-ichi Yumikura, Yu Komatsu
    1973 Volume 46 Issue 8 Pages 2356-2360
    Published: 1973
    Released: March 27, 2006
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    The rate of the solvent extraction of iron(III) in 4.0 M perchlorate ionic media with 2-thenoyltrifluoroacetone (TTA) into carbon tetrachloride has been measured under various conditions. The rate was found to be first order with respect to the concentration of iron(III) in the aqueous phase, first-order with respect to TTA in the organic phase, but independent and inversely first-order with respect to the hydrogen-ion concentration. From these results, it was concluded that the rate-determining step in this extraction is the formation of the first complex between the undissociated form, TTA(HA), and Fe3+ in the higher acid concentration range, but that the reaction between the anionic form, TTA(A), and Fe3+ also becomes a rate-determining step as the acid concentration decreases. It was also found that chloride ions accelerate the extraction; this was interpreted by more rapid reactions between TTA (in the both forms, HA and A) and an iron(III) chloride complex. From these results, the rate constants for the rate-determining reactions were calculated to be KHA=100.57 M−1 min−1 and KA=106.84 M−1 min−1 in 4.0 M(H, Na)ClO4 at 25 °C by means of these equations: −d[Fe3+]⁄dt=KHA[Fe3+][HA] (where [HA] is the total concentration of both enol and keto forms of uncharged TTA in the aqueous phase) and −d[Fe3+]⁄dt=KA[Fe3+]·[A]. The FeCl2+ species reacts with both HA and A more rapidly than does the Fe3+ species, and the rate constants of the reactions of the former are in both cases higher than those of the latter by a factor of 28.
  • Tokio Yamabe, Shingo Ishimaru, Kenichi Fukui
    1973 Volume 46 Issue 8 Pages 2361-2369
    Published: 1973
    Released: March 27, 2006
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    The variation method using the wave function of the modified Hassé form is applied to the problem of long-range interactions between hydrogen atom and proton and between two hydrogen atoms. The interaction energy is also related to the perturbation energy under the Unsöld approximation by the use of several pertinent approximations, and an “improved second-order Unsöld energy,” which will be higher than the exact second-order perturbation energy, is newly proposed. The numerical results show that the present trial wave function is quite effective; particularly, at R\gtrsim10 (a.u.), the dispersion energy between hydrogen atoms is better than that of Hirschfelder-Linnett, which might be the best variational result at a large nuclear separation. Furthermore, the importance of considering the degeneracy in treating the induction energy is numerically disclosed for an example of H–H+ interaction. The coefficients in the asymptotic form of the dispersion energy between two hydrogen atoms are briefly discussed, and, finally, a new method for the calculation of the second-order energy is suggested.
  • Norio Yui, Y\={o}ichi Kurokawa, Taketoshi Fujita
    1973 Volume 46 Issue 8 Pages 2369-2372
    Published: 1973
    Released: March 27, 2006
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    The distribution of uranyl nitrate between 1- or 2-butanol and aqueous phases and the effect of nitric acid or sodium nitrate on the distribution at 25°C have been studied. Conductance measurements have been carried out for the butanol solutions of uranyl nitrate. It was found that high water content in the butanol phase gives rise to the dissociation of the salt. Semi-empirical relations hold for the distribution considering the dissociation of salt in the butanol phase. Observed and calculated slopes agree in the plots of distribution ratio vs. nitrate concentration. The results were discussed in comparison with distribution data in literature.
  • Fusao Takusagawa, Ken Hirotsu, Akira Shimada
    1973 Volume 46 Issue 8 Pages 2372-2380
    Published: 1973
    Released: March 27, 2006
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    The crystal structure of quinolinic acid (2,3-pyridinedicarboxylic acid) has been determined by the method of X-ray diffraction. The crystal is monoclinic, with a space group of P21/c and with cell dimensions of a=7.421, b=12.729, c=7.850 Å, and β=116.96°. The crystal structure was solved by the inspection of a Patterson map. The final R value was 6.78% for 1224 observed reflections. The quinolinic acid molecule takes the form of a zwitter ion in the crystal. The pyridine ring in the molecules shows a significant deformation from the C2V symmetry of idealized geometry. The lengths of the two C–C bonds joining the carboxyl groups to the ring are longer than the normal value. There is an intramolecular hydrogen bond between the adjacent carboxyl groups. The bond lengths in the two C–O groups which participate in this intramolecular hydrogen bond are longer than those of the other two C–O groups. One of the two carbonyl oxygen atoms participates in a hydrogen bond, while the other is free from it. The molecules are arranged in layers closely parallel to the (0 1 0) plane. Each molecule on the same plane is hydrogen-bonded to form an endless chain along the a axis. These chains are packed by the van der Waals forces. The thermal diffuse scattering observed on Weissenberg photographs can be explained by this hydrogen-bond system.
  • Chihiro Tamura, Tadashi Hata, Sadao Sato
    1973 Volume 46 Issue 8 Pages 2380-2387
    Published: 1973
    Released: March 27, 2006
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    The crystal and molecular structure of the thymine-N,N-diethylmelamine complex monohydrate has been solved by means of the direct method. The crystals are monoclinic, with the space group of P21/c and with a=7.167, b=16.123, c=13.179 Å, and β=104.2°. The final R-factor for 1612 reflections is 0.087. These two components are hydrogen-bonded by a NH···N and two NH···O bonds with distances of 2.881, 2.821, and 3.006 Å. The complex formation ability for thymine and uracil has also been tested for some other organic compounds with amino and nitrogen heterocycles.
  • Chihiro Tamura, Sadao Sato, Tadashi Hata
    1973 Volume 46 Issue 8 Pages 2388-2394
    Published: 1973
    Released: March 27, 2006
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    The crystal and molecular structure of a cytosine and resorcylic acid complex monohydrate has been solved by the direct method. The molecular complex is formed by two moles of cytosine and one mole of resorcylic acid. The crystals are monoclinic, with a space group of P21/n, and with a=8.335, b=20.605, c=10.159 Å, and β=95.5°. The final R-factor for 1820 reflections is 0.100. Resorcylic acid is hydrogen-bonded to one of the cytosine molecules with one hydrogen bond, and the two cytosine molecules with one hydrogen bond, and the two cytosine molecules are associated with three hydrogen bonds in a system similar to that of the guanine-cytosine hydrogen bond in the Watson-Crick model.
  • Takeshi Asai, Ryôiti Kiriyama
    1973 Volume 46 Issue 8 Pages 2395-2401
    Published: 1973
    Released: March 27, 2006
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    Magnetic, IR and electronic spectral studies were made on CuSeO3·2H2O, its crystal structure being refined. The IR band at 927 cm−1 was found to be due to a rocking vibration of a water molecule. The H-bonding scheme was suggested. The electronic spectrum shows a maximum of the d-d transition bands at ca. 14000 cm−1. This was explained on the basis of a square pyramidal coordination of a Cu ion. Above 100 K the magnetic susceptibility obeys the Curie-Weiss law with θ=−92·6 K and μeff=2.00βB. At lower temperatures it shows a broad maximum at ca. 45 K, a sharp peak at 26.4 K corresponding to TN. The behaviour could be explained from the antiferromagnetic superexchange interactions of Cu cations through the σ-bonds of SeO32− anions. The small anisotropy and the number of cations intermediated by each anion give rise to the 1-dimensional character. A linear Heisenberg model and the molecular field model gave Jk values of −33 and −31 K, respectively. The latter model also gave the observed ratio of |θ|⁄TN.
  • Sadato Sakurai, Hideko Shirai, Eiji Niki
    1973 Volume 46 Issue 8 Pages 2402-2405
    Published: 1973
    Released: March 27, 2006
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    In order to increase polarographic precision and sensitivity, the oscillopolarographic current was digitized and stored in a 100-channel pulse-height analyzer (PHA) operated in the multi-sealer mode (MS mode). An oscillopolarograph which could sweep the DC potential rapidly was combined with the PHA. The digitized oscillopolarographic current was repeatedly stored in the PHA, so that the statistical noise was reduced and the signal-to-noise ratio of the oscillopolarographic current was increased. Also, the drift due to the change in the experimental conditions was removed effectively by shortening the measurement time. Therefore, precision was efficiently improved by means of accumulation. The relative deviation was 0.25% at the concentration of the 5×10−7 M cadmium ion. As an example of the application, trace amounts of copper, lead, and cadimum in 99.99% indium metal were analyzed.
  • Yuzo Nishida, Hideharu Shimohori
    1973 Volume 46 Issue 8 Pages 2406-2410
    Published: 1973
    Released: March 27, 2006
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    ESR and reflectance spectra of low-spin five-coordinate cobalt(II) complexes [CoXdpe2]Y, where dpe represents 1,2-bis(diphenylphosphino)ethane and X,Y are Cl, Br, NCS, NO3 and ClO4 anions, were measured. From the results it was inferred that the structures of [CoCldpe2]ClO4 and [CoBrdpe2]ClO4 are distorted trigonal bipyramids whereas those [CoNCSdpe2]ClO4 and [CoNO3dpe2]NO3 are square pyramids.
  • Fujio Mizukami, Haruko Ito, Junnosuke Fujita, Kazuo Saito
    1973 Volume 46 Issue 8 Pages 2410-2416
    Published: 1973
    Released: March 27, 2006
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    New cobalt(III) complexes [Co(acac)2(2,4-ptn)]+, [Co(acac)(2,4-ptn)2]2+ and [Co(ox)(2,4-ptn)2]+ have been synthesized, resolved into optical isomers and their structures determined; 2,4-ptn=optically active (RR and SS) and meso (RS) 2,4-pentanediamine, acac=acetylacetonate ion, ox=oxalate ion. The patterns of circular dichroism spectra of these complexes in the first absorption band region are very similar to those of the corresponding α-diamine cobalt(III) complexes.
  • Tomoaki Inoue, Kazuo Saito
    1973 Volume 46 Issue 8 Pages 2417-2420
    Published: 1973
    Released: March 27, 2006
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    Racemization of trisacetylacetonatosilicon(IV) ions and their isotopic exchange reaction with acetylacetone-14C (Hacac) have been studied in tetrachloroethane (TCE) and acetonitrile (AN). No solvolysis takes place at least below 60°C, and the racemization rate R is expressed as follows: R=[complex] (k1+k2[acid]) (in TCE) and R=[complex] (k3+k4[base]) (in AN). The rate constants and activation parameters at 50°C are as follows: rate constants, 4.79×106 s−1, 1.35×10−4 M−1 s−1, 3.87×10−5 s−1 and 1.19×10−1 M−1 s−1, activation enthalpy (ΔH\ eweq/kcal mol−1) 31.6±0.1, 29.3±1.9, 25.7±0.2 and ca. 18, and activation entropy (ΔS\ eweq/cal mol−1K−1) 14.6, 14.2, 0.53, −5.75, respectively, for k1, k2 (for trichloroacetic acid), k3 and k4 (for 2,6-lutidine). No isotopic exchange is observed within 6 hr at 60°C in the solvents. The racemization should proceed intra-molecularly and presumably via an intermediate of coordination 5 with one of the ligands as unidentate.
  • Makoto Otomo, Kazunobu Kodama
    1973 Volume 46 Issue 8 Pages 2421-2424
    Published: 1973
    Released: March 27, 2006
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    Picolinaldehyde 2-hydroxyanil and its methyl, chloro and nitro derivatives at the 5-position of benzene nucleus were synthesized for the purpose of investigating their applicability as an analytical reagent. The acid dissociation constants were determined by means of potentiometric titration in aqueous dioxane of various concentrations. It was found that the basicity of donor atoms of the parent compound increases with the introduction of a methyl group and decreases with that of a chloro or nitro group. The three compounds other than the nitro derivative are light-colored and react with many divalent metal ions in slightly basic media to form strongly colored chelates, which can be extracted into organic solvents such as partially halogenated hydrocarbons. The distribution coefficients of the three compounds between chloroform and water were also determined spectrophotometrically, that of the chloro derivative being the largest.
  • Keiji Matsumoto, Hiroshi Kawaguchi, Hisao Kuroya, Shinichi Kawaguchi
    1973 Volume 46 Issue 8 Pages 2424-2428
    Published: 1973
    Released: March 27, 2006
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    The crystal structure of (−)589-[Co acac tn2][As-(+)-tart]2·H2O has been determined by the X-ray diffraction method. The crystals are monoclinic, with lattice constants of a=12.02(1) Å, b=13.73(2) Å, c=9.02(1) Å, and β=107.4(3)°, and with the space group of P21, containing two formula units in a cell. The structure was determined by the application of Patterson and Fourier techniques and was refined by the least-squares method to an R factor of 10.4%. The absolute configuration of (−)589-[Co acac tn2]2+ can be denoted as Δ. The two Co-tn chelate rings assume the chair form, and the Co-acac chelate ring is almost planar. The geometry of [As-(+)-tart]22− is identical with that of [Sb-(+)-tart]22−.
  • Sigeo Kida, Yuzo Nishida, Masatomi Sakamoto
    1973 Volume 46 Issue 8 Pages 2428-2430
    Published: 1973
    Released: March 27, 2006
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    Elucidation of the origin of near-ultraviolet absorption believed to be characteristic of binuclear copper(II) complexes was attempted. The absorption was attributed to charge transfer transitions from nonbonding orbitals of bridging oxygen atoms to the vacant metal d-orbital. Appearance of the band in the near-ultraviolet region was interpreted in terms of the red-shift due to the decreasing s-character of the nonbonding orbitals enforced by the steric requirement of the complex. On this basis, the spectra of dialkoxo- or dihydroxo- bridged complexes and of copper alkanoates can consistently be explained.
  • Akira Ohyoshi, Satoshi Shida, Shuichi Izuchi, Futoshi Kitagawa, Katsut ...
    1973 Volume 46 Issue 8 Pages 2431-2434
    Published: 1973
    Released: March 27, 2006
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    The kinetics of aquation and anation reaction have been studied with pentaamineruthenium(III) complexes containing halogenoacetates (fiuoro-, monochloro-, dichloro-, trichloro-, bromo-, and iodoacetates). It has been found that the aquation reaction proceeds through two kinds of paths, i.e. the acid-catalysed path and the aciduncatalysed path, except the cases of dichloro- and trichloroacetate complexes. The aquations of dichloro- and trichloroacetate complexes are not catalysed by a proton because these ligand acids are strong acids. The equilibrium constants between [RuH2O(NH3)5]3+ and [RuO2CRX(NH3)5]2+ (O2CRX=halogenoacetate), Keq, were calculated from the anation and aquation rate constants. The kaq and Keq values for the fiuoro-, chloro-, dichloro-, trichloro-, bromo-, and iodoacetatocomplexes are, respectively: kaq, 10×10−5, 7.5×10−5, 19.1×10−5, 49.0×10−5, 6.8×10−5 and 6.7×10−5 sec−1; Keq, 5.2×10−3, 3.6×10−3, 9.0×10−3, 23×10−3, 3.5×10−3, and 3.3×10−3 M, at 60°C. The free energy plot, logkaq vs. logKeq, gave a straight line with a gradient of 1.0. It has been concluded that the acid-uncatalysed reaction proceeds via a SN1 mechanism, while the acid-catalysed reaction seems to take place with a SN2 mechanism. Some remarks have been made on the molecular interaction between the complex and the acid catalyst.
  • Kenzo Nagase, Nobuyuki Tanaka
    1973 Volume 46 Issue 8 Pages 2435-2438
    Published: 1973
    Released: March 27, 2006
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    Kinetics of the thermal decomposition reactions of [Cr(NH3)6]X3 (X=Br, I and NCS) and [Cr(NCS)(NH3)5](NCS)2 in solid state were studied by the manometric method. The rate constants, activation energies and activation entropies of the substitution reactions of outer-sphere anions for coordinated ammonia molecules were presented, and possible reaction mechanisms were discussed.
  • Keiz\={o} Hiraki
    1973 Volume 46 Issue 8 Pages 2438-2443
    Published: 1973
    Released: March 27, 2006
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    As fluorometric reagents for the determination of Al, Ga, In, etc., 11 derivatives of o,o′-dihydroxyazobenzene were examined in an attempt to determine the most desirable structure of azo compounds. o,p,o′-Trihydroxyazobenzene type compounds were more sensitive than o,o′-dihydroxyazobenzene; CH3O-group substitution at the para position was also efficient. The SO3H substitution increased, whereas the Cl substitution decreased the fluorescence of metal complexes, and the CH3-substituted compound did not form fluorescent metal complexes because of its low solubility in water and because of the steric hindrance. Superchrome Garnet Y and Lumogallion seemed to be excellent fluorometric reagents for Al and Ga; 2-(2,4-dihydroxyphenylazo)-1-hydroxybenzene and 3-(2-hydroxy-4-methoxyphenylazo)-4-hydroxybenzene sulfonic acid were also useful. Therefore, the several conditions for the fluorometric determination of Al and Ga with those compounds were also investigated.
  • Satoru Onaka
    1973 Volume 46 Issue 8 Pages 2444-2450
    Published: 1973
    Released: March 27, 2006
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    The infrared absorption spectra (2200–50 cm−1) have been measured for four metal-metal bonded molecules, Cl3Si–Mn(CO)5, Cl3Ge–Mn(CO)5, Br3Ge–Mn(CO)5, and I3Sn–Mn(CO)5. Vibrational normal coordinate analyses have been made for each of these molecules on the basis of a modified Urey-Bradley force-field. The calculated frequencies agree closely with validly-assigned frequencies. The metal-metal stretching force constant, K(M–Mn), or the F-matrix element, f(M–Mn), varies with the halogen atom, and increases as the electronegativity of X increases. The force constant, K(M–Mn), or f(M–Mn) depends also on the IVb metal atom, and increases in the order of: K(Si–Mn)≥K(Ge–Mn)>(Sn–Mn), or f(Si–Mn)≥f(Ge–Mn)>f(Sn–Mn). However, there is no clear relationship between the electronegativity of M and the K(M–Mn) or (M–Mn). These dependences of K(M–Mn) or f(M–Mn) on X and M are discussed, along with the bonding implications of the M–Mn bonds, on the basis of the sets of the force constants, or the sets of the F-matrix elements, and are interpreted in terms of the predominant σ-bonding framework of the M–Mn bonds.
  • Shoji Harada, Hideyuki Tanabe, Tatsuya Yasunaga
    1973 Volume 46 Issue 8 Pages 2450-2453
    Published: 1973
    Released: March 27, 2006
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    The rate constants of the complex formation and the dissociation of the nickel phthalate (o-phthalate) complex have been determined by the pressure-jump method. The thermodynamic parameters of the reaction were obtained from studies at various temperatures between 10 and 30°C. Upon a comparison of the data on the nickel complexes of the succinate, adipate, maleate, and phthalate, no systematic relationship between the nature of the ligands and the kinetic values has been found; this can be ascribed to the monodentated form of these complexes. The rate-determining step is the loss of the water molecule from the inner-coordination sphere of the nickel ion when the monodentated complex is formed.
  • Nobuhiko Ishibashi, Kenyu Kina
    1973 Volume 46 Issue 8 Pages 2454-2456
    Published: 1973
    Released: March 27, 2006
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    Ion-selective electrode membranes responsive to the thiocyanate ion were prepared by using ion-association extraction systems. A crystal violet or tetraphenylarsonium cation was used as an ion exchange-site in the liquid nitrobenzene membrane. The liquid membrane electrode exhibits an ideal Nernstian response to the thiocyanate ion down to 10−5 M. The selectivity of the liquid membrane largely depends on the extractability of the diverse anion into nitrobenzene. The order of the selectivity coefficients, Kj, is as follows:
    ClO_4^->IO_4^->SCN^->I^->ClO_3^->NO_3^->Br^->BrO_3^->Cl^-
    High selectivities for thiocyanate over SO42−, H2PO4, Cl, BrO3, and Br were observed. The membrane potential is independent of the pH variation in the region from pH 2 to 12.
  • Tasuku Murakami, Tsunenori Nozawa, Masahiro Hatano
    1973 Volume 46 Issue 8 Pages 2456-2459
    Published: 1973
    Released: March 27, 2006
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    The absorption and circular dichroism(CD) spectra of some ternary mixed complexes of copper(II) with diethylenetriamine(dien) and various optically active α-amino acids have been measured in an aqueous solution at various pH values. The amino acid may coordinate to one of the planar positions, with its carboxylate or amino group as a unidentate ligand, in a neutral or a very high pH region. On the other hand, from the red shift of the d–d absorption band and the augmentation of the visible CD magnitude, it seems reasonable to expect that a large portion of the amino acid will form a chelate ring with an axial ligation in the pertinent pH region.
  • Hiroshi Ogino, Toshiyuki Watanabe, Jong-Jae Chung, Nobuyuki Tanaka
    1973 Volume 46 Issue 8 Pages 2460-2464
    Published: 1973
    Released: March 27, 2006
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    The kinetics of the ligand substitution reaction of tetramethylenediaminetetraacetatocobaltate(II)(cobalt(II)–TDTA) with trimethylenediaminetetraacetate (TRDTA) was investigated by two different polarographic methods. The kinetic data at pH 4.9 to 5.6 were obtained by means of a conventional method in which the reaction was initiated by the mixing of two reactant solutions and was followed polarographically. However, this method could not be applied to solutions with pH values lower than 4.9, for the rate of the reaction is immeasurably fast in such a low pH region. The kinetic data at pH values down to 3.7 were obtained by analyses of the polarographic current which was observed in solutions containing TRDTA and the substitution-inert cobalt(III)–TDTA complex. From these data, it was found that the reaction proceeds through four simultaneous reaction paths, two paths of which are the nucleophilic substitution reactions, while the others are the dissociation reactions of cobalt(II)–TDTA complex ions.
  • Hisashi Okawa, Tadashi Tokii, Yoneichiro Muto, Sigeo Kida
    1973 Volume 46 Issue 8 Pages 2464-2467
    Published: 1973
    Released: March 27, 2006
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    Two types of binuclear copper(II) and nickel(II) complexes, OK-3(H), 3(H)-M2 and [OK-m, 3(H)-M2]ClO4 (m=2 or 3), have been synthesized, where OK-3(H),3(H) is a macrocycle composed of two 2,6-diformyl-4-methylphenol and four hydroxylamine, and OK-m,3(H) is a macrocycle composed of two 2,6-diformyl-4-methylphenol, one diamine (ethylene diamine (m=2) or 1,3-diaminopropane (m=3)), and two hydroxylamine. It was found that a very strong antiferromagnetic exchange interaction is operating between two copper(II) ions for OK-3(H), 3(H)-Cu2 and [OK-2,3(H)-Cu2]ClO4. The complex [OK-2,3(H)-Ni2]ClO4. DMF was found to be a novel-type binuclear nickel(II) complex, in which one nickel (II) ion is diamagnetic and the other is paramagnetic.
  • Makoto Watanabe
    1973 Volume 46 Issue 8 Pages 2468-2469
    Published: 1973
    Released: March 27, 2006
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    Glassy substances of the NaPO3–Sb2O4 system with P/Sb ratios in the range from 5.0 to 300 were prepared by heating a mixture of NaPO3 glass and Sb2O4 at 1000 °C and by then rapidly quenching the melt of the mixture. From the results of the colorimetric determination and the average degree of polymerization of the condensed phosphates, it has been found that the chain length of the phosphates increases with an increase in the P/Sb ratio. When the glass was treated with water, antimony trioxide was deposited. By using these results, a theoretical treatment for the average degree of polymerization of condensed phosphates has been made and it has been concluded that there are P–O–Sb linkages in the glass of the NaPO3–Sb2O4 system.
  • Kazuhiro Maruyama, Tetsuo Otsuki, Akio Takuwa, Seiichi Arakawa
    1973 Volume 46 Issue 8 Pages 2470-2474
    Published: 1973
    Released: March 27, 2006
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    Photo-reduction of p-benzoquinone, 1,4-naphthoquinone, and their methyl- or chloro-derivatives has been investigated by means of CIDNP technique. Strongly polarized PMR signals due to unstable reaction intermediates, p-quinones, and hydroquinones were observed during the course of reaction. Structures of the unstable reaction intermediates, none of which accumulated as reaction products, were determined, their polarized PMR signals being compared with those of the unstable reaction intermediates resulting from the deuterated substrates. From these results, a reaction scheme for these photo-reduction was proposed.
  • Akio Wakahara, Masaru Kido, Takaji Fujiwara, Ken-ichi Tomita
    1973 Volume 46 Issue 8 Pages 2475-2480
    Published: 1973
    Released: March 27, 2006
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    5-Hydroxy-DL-tryptophan was crystallized from a methanol solution in the monoclinic space group C2/c, with cell-dimensions of a=16.765, b=5.892, c=20.887 Å, and β=92.06°. The molecular structure and stereoconfiguration have been elucidated by the direct method for non-primitive space group. A Fourier map, calculated with the largest 198 normalized structure factors as Fourier coefficients, revealed the whole structure which was refined by the least-squares method. The molecule is a zwitterion as in the crystal structure of amino acids, each amino nitrogen atom having an extra proton. The indole ring plane forms a dihedral angle of 40° with that formed by an acid group. With respect to the conformation about the C(α)–C(β) bond, the orientation of C(β)–C(γ) bond is trans with respect to the C(α)–COO–. The molecules are arranged in double layers parallel to the ab-plane. The layer by polar groups is held together by a series of hydrogen bonds in a three-dimensional network, and by non-polar groups in the other layer, indole rings being stacked by van der Waals forces. The D-and L-forms of 5-hydroxytryptophan are hydrogen-bonded into two types of dimer related by the center of symmetry, one through N–H···O, and the other through O–H···O hydrogen bonding.
  • Akio Wakahara, Takaji Fujiwara, Ken-ichi Tomita
    1973 Volume 46 Issue 8 Pages 2481-2486
    Published: 1973
    Released: March 27, 2006
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    The crystal structure of tryptamine hydrochloride has been solved by the application of the symbolic addition method, and refined by successive Fourier syntheses and least-squares procedures. The crystals are orthorhombic, space group Pbca, with lattice parameters a=8.545, b=10.025 and c=24.252 Å. All the positions of hydrogen atoms were found in the difference Fourier map and included in the refinement. The ethylamine side chain bound to the indole ring is in a folded configuration as found in the crystal structure of serotonin picrate monohydrate. A weakly basic nitrogen atom of the indole ring takes part in the hydrogen bonding with the adjacent ion. Every chloride ion behaves as an acceptor for four hydrogen bonds. This is in line with the absence of any marked cleavage where indole rings are packed together to form a pleated sheet and a three-dimensional network structure is essentially stabilized by the hydrogen bond formation.
  • Noboru Kito, Atsuyoshi Ohno
    1973 Volume 46 Issue 8 Pages 2487-2489
    Published: 1973
    Released: March 27, 2006
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    Photochemical reactions of thiobenzophenone and its 4,4′-dimethoxy derivative in ethereal solutions such as tetrahydrofuran and diethyl ether have been studied by means of product analyses and ESR spectroscopy. It was found that the reaction involves quite stable transient free-radicals of the type Ar2CSR. The efficiency of free-radical trapping by diaryl thioketones and the reaction mechanism are discussed.
  • Hataaki Yoshimoto, Hiroshi Itatani
    1973 Volume 46 Issue 8 Pages 2490-2492
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The oxidative coupling reaction of aromatic compounds proceeds catalytically with palladium salt under oxygen pressure. Yields and isomer distributions are attributed to the reaction variables such as temperature, additives, and the nature of the substituent on a benzene ring. Naphthalene was converted mainly into 1-substituted products and o-xylene into 4-substituted products. The coupling of diphenyl ether afforded diphenylene oxide with coupling dimers. An intramolecular two stage dehydrogenation process is proposed.
  • Tsuneo Okubo, Norio Ise
    1973 Volume 46 Issue 8 Pages 2493-2497
    Published: 1973
    Released: March 27, 2006
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    Garbamoylation reaction of ions of polyethylenimine and its low molecular weight analogues, i.e., ethyl-enediamine, triethylenetetramine, and tetraethylenepentamine, with cyanate ions are investigated in the presence of simple-, micelle-, and poly-electrolytes and in their absence. The rate constants are practically independent of the valency of the cations and are much larger than that previously found for the ammonium cyanate reaction. Both of the activation enthalpy and entropy decrease with increasing valency of the cations. Added electrolytes are found to decelerate the reactions. The reactions of poly cations are retarded more strongly by simple cations than by catalyst polycations, whereas those of simple cations are decelerated more effectively by polycations than by simple cations. The kinetic data are discussed thermodynamically in terms of the Bronsted theory and the activity coefficients of the reactant ions. The interaction parameters between reactant electrolyte and added electrolyte are also derived thermodynamically and discussed.
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