Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 42 , Issue 4
Showing 1-50 articles out of 68 articles from the selected issue
  • Ryôjirô Iwaki, Isao Kamiya
    1969 Volume 42 Issue 4 Pages 855-863
    Published: 1969
    Released: March 27, 2006
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    The chemiluminescence of polyphenols with ozone in acetic acid was investigated in the presence and in the absence of rhodamine B. The emission intensity in the presence of rhodamine B (IM) was about 100–500 times as large as that in the absence of the dye (IP). From the measurement of the emission intensity vs. the reaction time, it was found that the time required to attain the peak intensity of IM is almost equal to that required to attain the peak of IP at equal concentration of polyphenol. A similarity was found in the spectral distributions of IM and the fluorescence emission of rhodamine B determined under comparable conditions. Rhodamine B was scarcely decomposed for the production of the enhanced emission; this lent support to the conclusion that the enhancement effect of rhodamine B is due to an energy-transfer from an excited species produced by the oxidation of polyphenols to the dye. Determining the changes in the absorption spectra during the luminescent reaction, we also found that the emission results not from the decomposition of polyphenols but from the decomposition of an intermediate compound. On the basis of these results, a reaction scheme was proposed. If the increment of the total light emitted by the enhancement effect, (Δ), is defined as:
    Δ = (Total light emitted in the polyphenol+rhodamine B system)−(Total light emitted in polyphenol alone)−(Total light emitted in rhodamine B alone),
    the scheme gave the following equation:
    Δ=A[R]0ln(1+[P]0A[R]0) (1)
    where [R]0 and [P]0 are the initial concentrations of rhodamine B and polyphenols respectively. A is the parameter, depending upon the experimental conditions. The values of Δ calculated from Eq. (1) were in fairly good agreement with the measured values.
  • Keiji Kuwata, Yasuhiro Shimizu
    1969 Volume 42 Issue 4 Pages 864-870
    Published: 1969
    Released: March 27, 2006
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    An electron spin resonance study on the complex formation between o-quinone anion and metal ions of group II was undertaken, and the change in g-factor and proton hyperfine splittings of o-quinone anion by the complex formation were examined in detail. The change in g-factor was closely related to both the change in the unpaired electron distribution and the change in energy difference between lone pair orbital of oxygen and unpaired electron orbital. The stabilization of the quinone anion against its coupling reaction was seemed to be related to the shift in g-factor by complex formation. The interaction between quinone anion and metal ions was deduced to be partly ionic. An open shell SCF calculation with CI for the free quinone anion was carried out in order to discuss the electronic spectra of the complex.
  • Katsue Shibata, Tadamitsu Kiyoura
    1969 Volume 42 Issue 4 Pages 871-874
    Published: 1969
    Released: March 27, 2006
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    The catalytic activity and the sintering property of iron oxide catalysts with and without potassium additives have been studied. The potassium oxide acts as a promoter and is effective under given conditions in increasing the activity of the catalyst from four to ten times. The effects of the promoter can be classified thus: (1) Structural promoter: The increase in the apparent bulk density and the shrinkage of the catalyst tablet upon calcination during the preparation of the catalyst are prevented by potassium additives. The differences in the specific surface area and in the pore volume of the catalyst between with and without potassium promoter are slight. These effects on iron oxide appear to be caused largely by the formation of K2Fe22O34. (2) Synergetic promoter: The potassium promoter changes the apparent energy of activation of the dehydrogenation reaction from 28 to 43 kcal/mol. The increase in the catalytic activity is due to the increase in the pre-exponential factor. The increase in the factor can be explained in terms of the higher concentration of the active center produced by the interaction of the potassium promoter with iron oxide. (3) Selectivity promoter: The formation of benzene by a side reaction is retarded by potassium additives.
  • Takashi Kojima, Hiroshi Fukutomi, Hidetake Kakihana
    1969 Volume 42 Issue 4 Pages 875-880
    Published: 1969
    Released: March 27, 2006
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    The equilibria involved in the extraction of HCl by tri-n-octylamine (TOA) in benzene have been investigated as a function of the HC1 and TOA concentrations. Two distinctly different extractions were observed for two different acidity ranges. From the extraction in the low acidity range (<0.001 M HCl), it has been found that two complexes of TOA·HCl and (TOA·HCl)2are formed in the organic phase and that the equilibrium constants for the two reactions,
    TOA(org)+H+(aq)+Cl(aq)=TOA·HCl(org)
    and
    2TOA(org)+2H+(aq)+2Cl(aq)=(TOA·HCl)2(org),
    are K11=(1.51±0.02)×104 and K22=(2.92±0.07)×109 respectively. For higher concentrations of HCl>3 M, it seems probable that two major complexes of (TOA·HCl)2HCl and (TOA·HCl)3-(HCl)2 besides the monomer and the dimer, and three minor complexes of (TOA·HCl)2(HCl)2, (TOA·HCl)3HCl, and (TOA·HCl)3(HCl)3 are formed in the organic phase.
  • Yoshiki Matsuura, Noritake Yasuoka, Tatzuo Ueki, Nobutami Kasai, Masao ...
    1969 Volume 42 Issue 4 Pages 881-886
    Published: 1969
    Released: March 27, 2006
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    The crystals of (π-C5H5Co)2(N-t-C4H9)2CO are orthorhombic, and the space group is Fdd2, with a=9.101, b=17.973, c=23.616 Å, and Z=8. The crystal structure was determined with use of MoKα counter data, the final R being 0.063 for 578 non-zero reflections. The molecules has a C2 symmetry, and the carbonyl group lies exactly on the two-fold axis. Unexpectedly, the molecule has the local structure of N,N′-di-t-huty urea, two nitrogen atoms being bridged to two cobalt atoms. The two crystallographically independent Co-N bonds are 1.942 and 1.951 Å, which are equal within the limits of experimental error. Two cobalt atoms are directly bonded to each other at a distance of 2.371 Å, which is shorter than that of 2.47 Å found in (CO)6Co2(C2Ph2).
  • Hiromichi Uehara
    1969 Volume 42 Issue 4 Pages 886-889
    Published: 1969
    Released: March 27, 2006
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    Four K-band electron paramagnetic resonance transitions of 3Σ 32S16O in the gas phase have been observed. One of these occurs between the Zeeman levels of the K=1, J=0→K=0, J=l states and three between the Zeeman levels of the K=2, J=2→K=3, J=2 states. The analysis of the spectra has led to the g values of gse, gle, and gr (in accordance with the notation by Tinkham and Strandberg). Knowledge of the rotational magnetic moment gave the equilibrium internuclear distance of Re=1.48101±0.00006 Å.
  • Goro Wada
    1969 Volume 42 Issue 4 Pages 890-893
    Published: 1969
    Released: March 27, 2006
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    The basic nature of dimethyl sulfoxide (DMSO) has been known in water, and so has its pKa value, which varies somewhat according to the measuring methods. In the present work, a spectrophotometric method employing thymol blue and o-nitroaniline as indicators was applied; the thermodynamical pKa° value of DMSO was determined to be −1.04 at 25°C. Since there is no dependence of pKa° upon the temperature, the proton transfer from water to DMSO in water is likely to be athermal.
  • Tetsuo Miyazaki, Tadahiko Kohama, Kenji Fueki, Zen-ichiro Kuri
    1969 Volume 42 Issue 4 Pages 894-897
    Published: 1969
    Released: March 27, 2006
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    The radiolysis of the N2-isoC4H10 (0.0153 mol/mol of N2) mixture has been studied by using such ion scavengers as ammonia and sulfur hexafluoride. It was found that the C3H7+ ion is formed by the fragmentation of the excited isobutane ion produced by the charge transfer from the nitrogen ion. Although nitrogen is an effective quencher of the excited ion, the yield of the C3H7+ ion is constant over the pressure range from 0.66 to 130 atm. It has been concluded that the excited isobutane ion produced by the charge transfer with 5 eV excess energy decomposes very fast and that it can not be deactivated by nitrogen of 130 atm, while it has been reported by other authors that the excited isobutane ion with 1.2 eV excess energy can be deactivated below 1 atm. This difference in the characters of the excited isobutane ions can be explained by the previously-proposed mechanism of the fragmentation.
  • Toyozo Uno, Katsunosuke Machida, Yutaka Saito
    1969 Volume 42 Issue 4 Pages 897-904
    Published: 1969
    Released: March 27, 2006
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    The infrared spectra of orthorhombic crystals of CH3CONH2, CD3CONH2, and their N-deuterated and partially N-deuterated samples have been recorded in the region between 4000 and 400 cm−1. The bands due to the trans- and cis-NHD species have been assigned by comparing the spectra of various samples containing the NH2, ND2 and NHD species in different proportions. In the spectra of the 50% N-deuterated samples, the absorption bands near 1530 and 1360 cm−1have been assigned to the amide II and III modes, respectively, of the trans-NHD species characteristic of the trans conformation of the -CONH- group, and those near 1480 and 1400 cm−1to the NH in-plane deformation and the CN stretching modes, respectively, of the cis-NHD species. These assignments were confirmed by the normal coordinates analysis of eight isotopic species of acetamide based on the Urey-Bradley force field.
  • Minoru Tsuda
    1969 Volume 42 Issue 4 Pages 905-908
    Published: 1969
    Released: March 27, 2006
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    The spectral sensitization of poly (vinyl cinnamate) is considered to occur by the triplet energy transfer from sensitizer to the cinnamoyl group of the polymer. The triplet state mechanism is useful for finding new sensitizers. Some new sensitizer were found on the basis of the theory, and the results may verify the mechanism.
  • Haruo Shizuka, Ikuzo Tanaka
    1969 Volume 42 Issue 4 Pages 909-913
    Published: 1969
    Released: March 27, 2006
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    The photolysis of acetanilide in the vapor phase at 2537 Å and 120°C has been studied by means of mass spectrometry, gas chromatography, and spectrophotometry. In the vapor phase, no such rearrangements of acetanilide as in the liquid phase occurred, only the decomposition of acetanilide. Carbon monoxide and ethane were formed as the main products, and the ratio of carbon monoxide to ethane was about 2. The quantum yield of the predissociation for the N–C bond of acetanilide in the vapor phase was estimated to be 0.28 from the data of the quantum yields for the formations of carbon monoxide and ethane. A small amount of methane and traces of hydrogen and benzene were also detected. The reaction scheme of acetanilide in the vapor phase at 2537 Å and 120°C has been proposed. On the other hand, the photochemical reactions of acetanilide in the rigid matrixes (MP, ME, and EPA) at −196°C and in the PVA sheet at room temperature have also been carried out by the use of a spectrophotometer and an ESR spectrometer. In the rigid matrixes at −196°C, the photochemical rearrangements did not occur, only the back reaction resulting in the distortional structure of acetanilide; this mechanism can be explained by the stiffness of the solvent cage. The cage effect on the photochemical reaction of acetanilide is also discussed.
  • Fumio Hine, Shusei Inuta
    1969 Volume 42 Issue 4 Pages 914-918
    Published: 1969
    Released: March 27, 2006
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    The solubility of chlorine in a mixed solution of HCl and CuCl2 under various conditions of concentration, temperature, and partial pressure was determined. The concentration of chlorine in a solution as the sum of Cl2 and Cl3 was found to be proportional to the partial pressure of chlorine in the gas phase; its slope decreased with an increase in the concentration of cupric ions due to the salting-out effect.
  • Hiroshi Kokubun
    1969 Volume 42 Issue 4 Pages 919-922
    Published: 1969
    Released: March 27, 2006
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    Fluorescence lifetime of acridine has been measured in water-ethanol and water-glycerol mixtures of different composition at 25°C. Remarkable decrease in lifetime value was found as the amount of organic component increases. The lifetime of 10.3 ns was obtained for the aqueous solution. The lifetimes in glycerol and in ethanol were determined as 3.2 and 0.72 ns, respectively. The observed ratio of the lifetime in the mixture to the lifetime in water, τ⁄τ0, has the same functional dependence on solvent composition as the ratio of fluorescence yield, Φ⁄Φ0. These quenching phenomena by organic molecules have been interpreted as due to the solvent effects upon the radiationless transition rate. Both static and dynamic mechanisms of quenching are not applicable in the present cases of solvent quenching.
  • Hiroshi Kato, Hajime Katô, Hideyuki Konishi, Teijiro Yonezawa
    1969 Volume 42 Issue 4 Pages 923-928
    Published: 1969
    Released: March 27, 2006
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    Using a semi-empirical ASMO SCF method for valence electron systems previously proposed by the present authors, the valence shell electronic structures of various protonated azines are investigated. The compounds treated in the present paper are monoprotonated pyridinium, mono-, and diprotonated diazinium cations. The calculated results show that quite large charge redistributions on both σ and π electron systems in these cations take place in the protonation, while about a 0.7 e charge migrates to the attached protons. As to the transition energies, the lowest π–π* transitions exhibit slight red shifts, while the n–π* transitions would be expected to cause large blue shifts by means of protonation. Several models for protonated cations are compared, and the configuration where the proton is situated on the bisector of the CNC(N) angle and in the molecular plane is shown to be the most stable one. The changes in Fock’s operators upon protonation are also briefly discussed.
  • Takeaki Iida, Hiroshi Nozaki
    1969 Volume 42 Issue 4 Pages 929-933
    Published: 1969
    Released: March 27, 2006
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    The photoconductivity of titanium dioxide (rutile type) synthesized by the flame-fusion method was studied. The photoconductivity spectra showed three peaks. The first is the maximum response around the edge of the fundamental absorption of rutile; the second is the peak at 630 mμ (1.98 eV), and the third is the broad-band spectra in the near infrared region of 1.0–1.9 μ. From the facts that Fe is found by chemical analysis to be a major impurity in rutile, that the peak at 630 mμ is enhanced by the increase in Fe concentration from 0.006 mol% to 0.02 mol%, and that the infrared quenching band of photoconductivity is observed at 1.23 μ (1.01 eV) in Fedoped rutile, it is concluded that this peak at 630 mμ results from the excitation of the electron from the Fe3+ level. The broad-band spectra at 1.0–1.9 μ are enhanced by the reduction and are decreased by the oxidation of the crystal, so these excitation spectra are ascribed to lattice defects originating from the non-stoichiometry of TiO2. These defects have much influence on the photoconductivity of rutile, i. e., on the relation between the photocurrent and the electrical applied field, and on the change the photocurrent versus the time.
  • Teijiro Yonezawa, Hideyuki Konishi, Hiroshi Kato
    1969 Volume 42 Issue 4 Pages 933-942
    Published: 1969
    Released: March 27, 2006
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    A semi-empirical SCF MO method for valence electron systems, a modification of our previous method made by introducing the zero-differential overlap approximation except for the one-center exchange integrals, is presented. The results calculated for benzene, pyridine, pyrimidine and thiophene, the parent molecules of benzyne and hetarynes, using this modified method are compared with those obtained by the other calculations and experiments. The unstable intermediates treated in the present paper are benzyne, pyridynes, pyrimidyne and thiophynes. The unknown bond lengths of benzyne and hetarynes are estimated by a semi-empirical relation given in the present treatment. The nature of the carbon-carbon triplet bonds of benzyne and hetarynes is studied on the basis of the bond lengths and the total π bond orders for these bonds. The charge distributions and excitation energies of benzyne and hetarynes, and the chemical reactivity of some hetarynes are also discussed. The lowest triplet states of these intermediates are shown to be close to the singlet ground states.
  • Tetsuo Morimoto, Mahiko Nagao, Teiji Omori
    1969 Volume 42 Issue 4 Pages 943-946
    Published: 1969
    Released: March 27, 2006
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    On anatase and rutile, three samples which differ in the extent of hydration treatment have been prepared, and the surface area, the water content, and the heat of immersion have been measured. The hydration treatment of the sample increases the water content of the sample and lowers the sintering temperature. These facts suggest that the condensation dehydration of surface hydroxyl groups from the facing surfaces of contacting particles is effective for sintering. The plot of the heat of immersion vs. the pretreatment temperature shows a maximum at about 400°C, and the heat of immersion is larger in the sample subjected to heavy hydration treatment. The heat of surface hydration, calculated from the plot of the heat of immersion vs. the water content, does not vary with the hydration treatment; it averages 25.2 and 19.0 kcal/mol H2O for anatase and rutile respectively.
  • Takeshi Tomita, Eishin Kyuno, Ryokichi Tsuchiya
    1969 Volume 42 Issue 4 Pages 947-951
    Published: 1969
    Released: March 27, 2006
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    The following chromium(III) complexes containing the anthranilicdiacetic acid (ATDA) were prepared: [Cr(atda)*(H2O)2]·3H2O (reddish-violet) (I), K[Cr(OH)(atda)(H2O)] (bluish-violet) (II), [Cr(atda)(phen)*]·3H2O (red) (III), [Cr(atda)(dipy)*·2H2O (red) (IV), [Cr(atda)(en)*]·2H2O (red) (V) and K[Cr(atda)(acac)*] (violet) (VI). From the results of electronic spectra, molar conductivities, chemical and thermal analyses and IR spectra, it was concluded that the Complexes I, II and VI belong to the [CrO5N], and III, IV and V belong to the [CrO3N3] type. ATDA in all these complexes obtained was found to behave only as a quadridentate ligand. The values of the effective magnetic moments were found to be 3.7–3.9 B. M., nearly equal to the spin-only values of the tervalent chromium. \ oindent(* atda, phen, dipy, en and, acac are the basic forms of anthranilic acid, o-phenanthroline, 2,2′-dipyridyl, ethylenediamine and acetylacetone respectively.
  • Toshiaki Nomura
    1969 Volume 42 Issue 4 Pages 952-955
    Published: 1969
    Released: March 27, 2006
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    After 5 ml portions of 1×10−4 M methylthymolblue (MTB or H2Me4−) and mercury(II) nitrate solutions had been added to an iodide sample solution adjusted to pH 7.3–8.8, it was diluted to about 50 ml with water. This solution was titrated with a 1×10−2 M standard mercury(II) ethylenediaminetetraacetate (Hg-EDTA or HgY2−) solution until it turned blue from greenish yellow. The iodide-ion content was calculated by applying the volume of the standard Hg-EDTA solution on the calibration curve determined with solutions of known iodide-ion contents. The iodide ion reacts with HgY2− and with greenish-yellow HgMe4− to form colorless [HgY(I)]3− and blue [HgMe(I)]5− complexes respectively. The [HgMe(I)]5− complex reacts subsequently with the iodide ion to form mercury(II) iodide and greenish-yellow H2Me4−. It has been found that, except when an excess amount of the iodide ion existed, the [HgMe(I)]5− complex is the most stable among these mixed ligand complexes and mercury(II) iodide. Therefore, the iodide ion can be titrated directly with a Hg-EDTA solution by using HgMe4− as an indicator according to the following equation:
    HgI2+H2Me4−+HgY2−→[HgMe(I)]5−+[HgY(I)]3−+2H+
  • Takahiro Kumamaru
    1969 Volume 42 Issue 4 Pages 956-960
    Published: 1969
    Released: March 27, 2006
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    A new application of atomic absorption spectrophotometry to the determination of iodide has been proposed. The method is based on solvent extraction into nitrobenzene of the colorless ion-pair formed between tris(l,10-phenanthroline)cadmium(II) and the iodide anion, and the subsequent determination of the cadmium concentration in the extract by atomic absorption in an air-acetylene flame at the 2288 Å cadmium line. The absorbance due to cadmium in the extract shows a linear relationship to the concentration of iodide over the range from 4×10−6 to 4×10−5 M initially present in the aqueous solution. The optimum conditions for the determination of iodide have been established, and the extraction efficiency and the effect of other anions have also been studied.
  • Seiichiro Matsumoto, Hiroshi Kobayashi, Keihei Ueno
    1969 Volume 42 Issue 4 Pages 960-968
    Published: 1969
    Released: March 27, 2006
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    The beryllium chelates of 2-hydroxy-3-methylacetophenone, 2-hydroxy-3-isopropylisobutyrophenone and 2-hydroxyacetophenone, and the copper- and nickel chelates of the ketimine derivatives of 2-trifluoroacetylphenol and 2-hydroxyisobutyrophenone in addition to the above o-acylphenols were synthesized. The thermal stability and relative volatility of these chelate compounds, measured by means of a thermogravimetric method, were found to be strongly increased by introduction of bulky alkyl or trifluoromethyl groups.
  • Michio Nanjo, Taro Yamasaki
    1969 Volume 42 Issue 4 Pages 968-972
    Published: 1969
    Released: March 27, 2006
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    The stability constants of ethyl xanthate complexes of cadmium(II), zinc(II), nickel(II), and cobalt(II) were determined spectrophotometrically in aqueous solutions. Complexes with the 1 : 1 composition, M(EX)+, were found in all cases; the stability constants of these metal complexes were calculated to be 1.2×104, 5.2×10, 4.4×10, and 1.1×10 for Cd(EX)+, Zn(EX)+, Ni(EX)+, and Co(EX)+ respectively at an ionic strength of 1.0 and at 25°C. These values were then compared with the stability constants of other metal complexes.
  • Michio Nanjo, Taro Yamasaki
    1969 Volume 42 Issue 4 Pages 972-976
    Published: 1969
    Released: March 27, 2006
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    The formation of 1 : 1 complexes was confirmed by means of the kinetic method. The acid decomposition of xanthate was delayed by the addition of metal ions because of the decrease in the concentration of ethyl xanthic acid in an equilibrium. By using the rate equation, the stability constants were found to be (1.0±0.2)×104, (1.7±0.4)×10 and (2.5±0.4)×104 for Cd(EX)+, Zn(EX)+, and Pb(EX)+ respectively.
  • Tsunenobu Shigematsu, Masayuki Tabushi, Masakazu Matsui, Takaharu Honj ...
    1969 Volume 42 Issue 4 Pages 976-980
    Published: 1969
    Released: March 27, 2006
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    The effects of carboxylic acids, such as formic, chloroacetic, acetic, propionic, butyric and caproic acid, on the extraction of europium with benzoyltrifluoroacetone were studied. The extraction is enhanced by the adduct formation between metal chelates and carboxylic acids in the organic phase, while it is hindered by the formation of metal-complex ions with anions of carboxylic acids in the aqueous phase. Caproic acid acts as an organic Lewis base and shows the synergism, but formic and chloroacetic acids have a masking effect. Acetic acid, propionic acid, and butyric acid behave both as synergists in the organic phase and as masking agents in the aqueous phase. Gaproic acid forms more stable adducts than does n-hexyl alcohol, and the composition of the chelate adduct is estimated to be Eu(BFA)3·2CH3(CH2)4COOH.
  • Yoshinaga Oka, Toyoaki Kato, Akira Yamadera
    1969 Volume 42 Issue 4 Pages 981-984
    Published: 1969
    Released: March 27, 2006
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    Beryllium, boron, carbon, oxygen, and fluorine targets with natural isotopic compositions were irradiated by bremsstrahlung with four maximum energies, 30, 45, 55 and 60 MeV, and the yields of 7Be from each of these targets were determined by means of chemical separation and gamma-ray spectrometric measurements. The yields were obtained relative to the yield of the 12C(γ, n)11C reaction at each bremsstrahlung energy. The possible reaction pathways leading to the production of 7Be were discussed. The exponential decrease in the yield value against the difference in mass between the target and the product nuclei was observed.
  • Yoshihisa Yamamoto, Masayasu Mori, Hayami Yoneda, Soichi Misumi, Kazuo ...
    1969 Volume 42 Issue 4 Pages 984-988
    Published: 1969
    Released: March 27, 2006
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    Cobalt(IV) compounds of the formulae: (Remark: Graphics omitted.) have been obtained by procedures analogous to that reported for cobalt(IV) ammine complexes with 5-nitrosalicylato ligands.
  • Sumio Kaizaki, Jinsai Hidaka, Yoichi Shimura
    1969 Volume 42 Issue 4 Pages 988-994
    Published: 1969
    Released: March 27, 2006
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    Two novel mixed chromium (III) complexes containing L-tartrates and 2,2′-dipyridyl or 1,10-phenanthroline have been prepared, and their electronic absorption and circular dichroism spectra and the rotatory dispersion have been measured in the region of near-infrared to ultraviolet. From the construction of molecular models and from the comparison of the CD bands of the present complexes with those of the resolved oxalato complexes, (−)546-K[Cr(ox)2(dip)]·3H2O and (−)546-K[Cr(ox)2(phen)]·4H2O, it has been concluded that the present complexes have a binuclear structure in which two Cr(III) ions are bridged by two tetradentate L-tartrato ligands and that the absolute configuration of the binuclear complexes is Λ(C2)-Λ(C2). Their formation is completely stereospecific and their formulae are represented by Ba[Cr2(L-tart2H)(dip)2]2·9H2O and NH4[Cr2(L-tart2H)(phen)2]·6.5H2O. The absolute configurations of several complexes which commonly belong to a general type, cis-[Cr(O)4(N)2] have been determined on the basis of circular dichroism studies of the present binuclear complexes. The circular dichroism in the spin-forbidden absorption band region have also been measured and discussed.
  • Takaharu Honjyo
    1969 Volume 42 Issue 4 Pages 995-999
    Published: 1969
    Released: March 27, 2006
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    The steric effect and the inductive effect of the functional groups of β-diketones on the adduct formation between lutetium chelates and TOPO in benzene was studied by using various β-diketones with aliphatic groups (acetylacetone, dipropionylmethane, pivaroylacetone, diisobutyryl-methane and dipivaroylmethane), aromatic groups (benzoylacetone, naphthoylacetone and dibenzoylmethane) and fluoromethyl groups (trifluoroacetylacetone, furoyltrifluoroacetone, thenovltrifluoroacetone, benzoyltrifluoroacetone and hexafluoroacetylacetone). The effect of the temperature on the adduct formation was then estimated. These results may be summarized as follows: (1) The stability of the adduct increases, and the larger synergism appears, as aliphatic groups, aromatic groups, and fluoromethyl groups are successively substituted for the functional groups of β-diketones. This effect may be due to the electron-withdrawing effect of the fluoromethyl group and the conjugation effect (with a metal chelate ring) of the phenyl group. (2) The adducts contain one molecule of TOPO per metal chelate except for the HFA adduct, which contains two molecules of TOPO. The steric hindrance of the terminal groups is hardly recognizable. (3) The extraction constant of the chelates increases, while the stability of the adducts decreases, with a rise in the temperature. The apparent enthalpy change (−ΔH kcal/mol) upon the adduct formation increases in the order: DPM (5.5)<BzA(5.9)<BFA(8.6) chelates.
  • Yoshihisa Yamamoto
    1969 Volume 42 Issue 4 Pages 999-1006
    Published: 1969
    Released: March 27, 2006
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    The electric and magnetic properties of a series of 5-nitrosalicyclato ammine cobalt (IV) complexes (paramagnetic), the salicylato ammine cobalt (III) complex (diamagnetic), μ-superoxodicobalt ammine complexes (paramagnetic), and the μ-peroxodicobalt ammine complex were studied. The resistivity(ρ) at room temperature and the energy gap(ε) for paramagnetic complexes were in the range of, ρ=7.6×1011−1.5×1010Ω cm and ε=0.75−1.1 eV, whereas those for diamagnetic complexes were in the range of ρ=1012−1014Ω cm and ε=0.75−1.2 eV. The magnetic susceptibilities of the paramagnetic complexes obeyed the Curie-Weiss law, with comparatively large Curie-Weiss constants (−18−26°). The g-values and line widths (ΔHmsl) in the ESR signals at room temperature were determined for powdered samples of 5-nitrosalicylatotetraamminecobalt(IV) complexes and their derivatives. The ESR parameters obtained were in the range of g=2.0030−2.0070 and ΔHmsl=22.0−30.6 Oe for powders.
  • Shoji Motomizu, Kyoji Tôei, Tadashi Iwachido
    1969 Volume 42 Issue 4 Pages 1006-1010
    Published: 1969
    Released: March 27, 2006
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    The Hexyl(2,4,6,2′,4′,6′-hexanitrodiphenylamine) anion forms ion-pairs with alkali metal cations to some extent in an aqueous solution. The association constants of these ion-pairs were determined both in nitrobenzene by conductivity measurements and in water by the solvent extraction method. The association constants in nitrobenzene (KoMR) decrease in the following order: Li>Na>K>Rb>Cs. The plot of log KoMR against the ionic potential of the alkali metal ions was found to be linear. In nitrobenzene saturated with water, however, the constants vary from 2 to 4. In water the asscoiation constants (KaMr) vary from about 10 to 400, and the value increases as follows: Li<Na<K<Rb (<Cs). A plot of log KaMR against the reciprocal of the effective diameter of the hydrated alkali metal ions was found to be linear.
  • Ryoei Ishida
    1969 Volume 42 Issue 4 Pages 1011-1016
    Published: 1969
    Released: March 27, 2006
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    A simple spectrophotometric method for the determination of palladium was studied, using chromazurol S as a reagent. Palladium (II), in a slightly acidic or a nearly neutral solution, reacts with chromazurol S to form blue or red complexes, each consisting of one molecule of the reagent and one atom of palladium. The maximum absorption wavelengths of blue and red complexes are respectively 596 mμ and 500 mμ, against the reagent blanks. The color development of the blue complex formed in a slightly acidic medium is more sensitive, therefore, it was applied to the spectrophotometric determination of palladium. Several conditions for the color development were investigated; a calibration curve was made under the optimum conditions; and the influences of coexisting ions were also investigated. The blue complex gives a maximum absorbance at 596 mμ in the pH range from 4.3 to 5.3. About a 2-fold excess of the reagent over the palladium concentration is necessary in order to obtain the maximum color intensity. The color development is almost instantaneous, and the absorbance remains constant for at least 4 hr. The order of the addition of reagents has no effect upon the absorbance. The color system obeys Beer’s law over the concentration range up to 70 μg of palladium per 10 ml. The molar extinction coefficient at 596 mμ is 18600, which corresponds to a sensitivity index of 0.0058 μg/cm2 for an absorbance of 0.001. Sulfate, chloride, fluoride, phosphate and acetate ions do not interfere with the color reaction. Thiosulfate ion and polycarboxylate ions such as oxalate, citrate and EDTA etc. bleach the color of the complex. Cations such as Sc(III), Y(III), Th(IV), U(VI), Be(II), Al(III) and Cu(II) ions cause an over-estimation of palladium; the interference by these cations except copper, however, could be eliminated by the addition of appropriate amounts of either sodium fluoride or sodium phosphate as masking agent.
  • Teruo Nomura, Fumiyuki Marumo, Yoshihiko Saito
    1969 Volume 42 Issue 4 Pages 1016-1020
    Published: 1969
    Released: March 27, 2006
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    The structure of (−)D-[Co(tn)3]Br3·H2O (tn: H2N–CH2-CH2-CH2-NH2) has been solved by the heavy atom method and refined to R=0.11 by least-squares analysis based on 1845 threedimensional data. The substance crystallizes in the monoclinic space group P21 with unit cell dimensions: a=16.274, b=9.863, c=9.489 Å, β=126.4° and Z=2. The complex ion in the structure has approximately a three-fold axis of rotation. The three six-membered Co-tn rings are nearly identical and take chair form. The chelate ring is rather flattened out, owing to the strong H-H repulsion. The absolute configuration of (−)D-[Co(tn)3]3+ has been found to be the same as that of (+)D-[Co(en)3]3+.
  • Yuichi Sato, Nobuyuki Tanaka
    1969 Volume 42 Issue 4 Pages 1021-1024
    Published: 1969
    Released: March 27, 2006
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    Polarographic behavior of tris(2,2′-bipyridine)chromium(III) perchlorate and tris(ethylenediamine)chromium(III) perchlorate in acetonitrile solutions has been investigated by the measurement of d.c., a.c. and Kalousek polarograms. The bipyridine complex gives a six-step reduction wave when tetraethylammonium perchlorate is used as supporting electrolyte. The limiting currents of the first four steps are all diffusion-controlled, and each of them is of a one-electron reduction process. It has been proposed that at the fourth step univalent tris(2,2′-bipyridine)-chromate anions, [Cr(bipy)3], are formed at the electrode surface in acetonitrile. The limiting current of the one-electron reduction wave of tris(ethylenediamine)chromium(III) is increased upon the addition of 2,2′-bipyridine. It was explained as a reduction of an electroactive species, Cr(II)-bipyridine complex, which was formed by the reaction between Cr(II) produced by the reduction of tris(ethylenediamine)chromium(III) complex and 2,2′-bipyridine at the electrode surface.
  • Shuichi Hamada, Naosato Yoshida, Toshiaki Shirai
    1969 Volume 42 Issue 4 Pages 1025-1029
    Published: 1969
    Released: March 27, 2006
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    The viscosities of liquid selenium and partially-chlorinated liquid selenium were measured in the temperature range from 235°C to 305°C using an Ubbelohde-type tilting viscometer. The “intrinsic” viscosities, η0, were estimated by extrapolating the values of the viscosities, ηθ, of various rates of shear to a zero rate of shear. The “intrinsic” viscosities of the liquid selenium were estimated to be 20.18, 13.46, 9.11, 6.32, 3.67 and 2.30 poise at 235, 245, 255, 265, 285, and 305°C respectively. The viscosities of the chlorinated liquid selenium decreased with an increase in the chlorine content, but they varied discontinuously at a chlorine content of 0.0125% and then decreased linearly. The apparent activation energy for the viscous flow of the liquid selenium was estimated to be 17.9 kcal/mol. The apparent activation energies for the viscous flow of the chlorinated selenium varied discontinuously at a chlorine content of about 0.0125%, as in the case of the viscosity. The average-chain length of the selenium molecules was considered not to be changed, but the radicals at both ends of the linear chain vanish in forming the bonds with chlorine atoms with an increase in the chlorination below a chlorine content of 0.0125%. Therefore, it is concluded that the presence of radicals at the molecular ends would have an influence upon the viscosity and the apparent activation energy for the viscous flow of selenium. The notable large value of the apparent activation energy of such a non-branched polymer as selenium was attributed to the large amount of energy needed to transport the segments into the holes.
  • Hiroshi Kawabe, Masaya Yanagita
    1969 Volume 42 Issue 4 Pages 1029-1036
    Published: 1969
    Released: March 27, 2006
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    Bipolar ion-exchange membranes were prepared from graft copolymers of polyethylene (PE). Powders of styrene-grafted PE (I) and 4-vinylpyridine-grafted PE (II), or powders of ethyl acrylate-grafted PE (III) and II were blended in various proportions and melt-pressed to films. Ion-exchange groups were then introduced by the sulfonation (100%), alkaline hydrolysis (100%), or N-methylation (80–90%) of the blend polymer films. Although, in the titration curves of bipolar membranes, pH regions which apparently resemble the isoelectric point of polyampholytes appeared, no behavior based on the interaction between acidic and basic groups was indicated in the survey of their physico-chemical properties. The dependency of the concentration potential of the membranes (Em), containing one kind of ionized group, on the mole fraction of the group (Fi) is not remarkable. On the other hand, the Em of the membranes containing both positively- and negatively-charged groups is strongly dependent on Fi, because of the additive contribution of the oppositely-charged groups to the potential. The bi-ionic potential of the membrane, EK–Li, was found to be a function of Em⁄|E0|(|E0| is the absolute value of the concentration potential for ideal permselective membranes) in the cases of both I-II and II-III.
  • Yasuhiko Kondo, Takeki Matsui, Niichiro Tokura
    1969 Volume 42 Issue 4 Pages 1037-1047
    Published: 1969
    Released: March 27, 2006
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    The effects of selvents on ρ values have been systematically treated as a two-variable problem within a linear free-energy relationship framework. It is assumed that the standard activation free energy is a continuous function of σ, a substituent variable, and ξ, a solvent variable. The applicability of the resultant equations is proved by a test of the dissociation constants (obtained from the literature) of benzoic acids in various solvents. As a result, it is proposed that these effects on ρ values can be explained in terms of the interaction or cross-term of σ and ξ. The application to the reaction rates of a typical Menschutkin reaction, obtained by experiments in ten nonaqueous solvents, suggests that the solvent dependence in these reactivities is much more complicated.
  • Akira Takeda, Satosi Wada, Sigeru Torii, Yuji Matsui
    1969 Volume 42 Issue 4 Pages 1047-1051
    Published: 1969
    Released: March 27, 2006
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    The anodic methylation of enanthaldehyde, enanthaldehyde diethyl acetal, and 2-octanone was attempted by electrolyzing a mixture of acetic acid, ethanol (or tetrahydrofuran and/or acetone), water, and potassium hydroxide. The major products from the electrolysis of enanthaldehyde consisted of 2-octanone, 1-heptanol, 3-methyl-2-octanone, and enanthaldehyde diethyl acetal. Similar products were isolated from the reaction mixture of enanthaldehyde diethyl acetal. The anodic methylation of 2-octanone gave 3-methyl-2-octanone as a major product. Possible mechanisms of the formation of these ketones were discussed.
  • Yojiro Tsuzuki, Motoo Koyama, Kazuyuki Aoki, Tatsuo Kato, Koko Tanabe
    1969 Volume 42 Issue 4 Pages 1052-1059
    Published: 1969
    Released: March 27, 2006
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    It has been reported that some ortho-nitrophenyl glycosides exhibit anomalous optical rotation (Montgomery et al., J. Am. Chem. Soc., 64, 690 (1942)). To investigate this anomalous effect of the ortho-nitro group the authors have observed the RD spectra on twenty-five derivatives of o-nitrophenyl, p-nitrophenyl and phenyl glycosides. Every o-nitrophenyl derivative (I, IV, VII, XI, XIV, XVII and XX) exhibited a positive Cotton effect near 340 mμ. Furthermore, in order to inquire into this anomaly the authors have observed the CD and UV spectra of these compounds. It follows that the o-nitro group is twisted from the benzene ring plane, and that the o-nitrophenyl group itself becomes an optical active chromophore, so that the Cotton effects near 340 mμ are caused by the n→π* transition of the nitro group. Therefore, the anomaly of o-nitrophenyl glycosides in the [α]D values is concluded to be affected by the strong Cotton effect near 340 mμ.
  • Yoshinobu Takegami, Toshimitsu Suzuki, Takuya Okazaki
    1969 Volume 42 Issue 4 Pages 1060-1064
    Published: 1969
    Released: March 27, 2006
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    The insertion reaction of propylene into metal-ethyl bonds in TiCl4-AlEt3, TiCl3-AlEt3, TiCl3-AlEt2Cl, and TiCl3-ZnEt2 catalyst systems was studied. The insertion products were converted to the corresponding hydrocarbons by methanolysis, and then analysed by gas-liquid chromatography. From these hydrocarbons, the following three metal alkyls were considered to be formed in the reaction system;
    (Remark: Graphics omitted.)
    These metal alkyls were formed in the solid phase of the catalyst at first and were then transferred to the liquid phase of the catalyst. The amount of the metal alkyls formed in the reaction system was dependent on the catalytic system used. The active polymerization system TiCl3-AlEt3 gave a very small amount of metal alkyls, but the less active TiCl3-ZnEt2 and -AlEt2Cl systems gave a much greater quantity of the metal alkyls, (I) and (III). In the case of the TiCl4-AlEt3 system, metal alkyl formation was much affected by the Al/Ti molar ratio and the reaction time. Finally, it was concluded that the metal alkyls formed in the system were connected to the polymerization of propylene.
  • Teruzo Asahara, Hideo Kise
    1969 Volume 42 Issue 4 Pages 1065-1071
    Published: 1969
    Released: March 27, 2006
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    The cationic telomerization of butadiene with its hydrobromides (1-bromo-2-butene and 3-bromo-1-butene) in the presence of metal halide was investigated. It was found that the molecular weights of the telomers depend on the conversion of the telomerization, initial bromide/ butadiene ratio and the solvent used. When halogenated hydrocarbons were used as solvents, telomers with high molecular weights and low unsaturations were obtained. On the other hand, the telomerizations in ether solvents gave telomers with low molecular weights, which contained appreciable amounts of the simple adducts of butadiene and bromobutene. The infrared spectra of the telomers suggested that the addition of butadiene occurred mainly at 1,4-position. On the basis of the analyses of the telomers, the reactivities of the carbonium ion to the basic species which were present in the reaction system were estimated.
  • Nobuhiro Nakamizo
    1969 Volume 42 Issue 4 Pages 1071-1077
    Published: 1969
    Released: March 27, 2006
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    The aminolysis reaction of benzyloxycarbonyl-L-phenylalanine p-nitrophenyl ester (I) with glycine t-butyl ester (II) was kinetically investigated in anhydrous dioxane. The spontaneous reaction was confirmed to follow the equation:
    d[p-nitrophenol]⁄dt=kobs[I]=(k0+kamine[II])[I][II]
    The catalytic actions of various additives were studied at a 2×10−3M concentration of I and II, where the amine-catalyzed term could be neglected. Of the many additives, only carboxylic acids and α-pyridone were effective as catalysts. The catalytic effect apparently decreased in the sequence: trimethylacetic acid>acetic acid>α-pyridone>monochloroacetic acid. For these catalyses, a bifunctional, concerted mechanism was proposed which involves an 8-membered transition state.
  • Nobuhiro Nakamizo
    1969 Volume 42 Issue 4 Pages 1078-1082
    Published: 1969
    Released: March 27, 2006
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    The kinetics of the aminolysis reaction of benzyloxycarbonyl-L-phenylalanine p-nitrophenyI ester with glycine t-butyl ester in dioxane were studied in the presence of high concentrations of several carboxylic acids. Bell-shaped curves were obtained when the rate constants observed for the trimethylacetic acid-, acetic acid-, and monochloroacetic acid-catalyzed reactions were plotted against the logarithms of the reciprocals of the acid concentrations. Cyanoacetic acid and trichloroacetic acid did not accelerate, but, rather, retarded the reaction. In the mathematical derivation the catalyst apparently exhibits no accelerating effect, if k0K>kcat, where k0 and kcat are the uncatalyzed and the true catalyzed rate constants respectively, and where K is the acidbase equilibrium constant between the nucleophile and the catalyst in a given solvent. The true catalyzed rate constants, kcat, from which the effect of the protonation of the nucleophile had been eliminated were estimated for the trimethylacetic acid- and acetic acid-catalyzed reactions. The fact that the kcat value (63M−2 min−1) for trimethylacetic acid, the weaker acid, was greater than that (53M−2 min−1) for acetic acid strongly supports the bifunctional, concerted mechanism presented in the preceding paper.
  • Sango Kunichika, Yasumasa Sakakibara, Mamoru Taniuchi
    1969 Volume 42 Issue 4 Pages 1082-1089
    Published: 1969
    Released: March 27, 2006
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    Allyl chloride has been pyrolyzed in a flow system over a wide range of conditions (temperature, 800–1200°C; contact time, 0.665×10−3–78.9×10−3 sec; concentration, 4.0–13.5 mol%; pressure, atmospheric pressure) to find suitable conditions for producing methylacetylene and allene. In addition, a study on the mechanism of pyrolysis of allyl chloride at high temperatures (800–1200°C) has been made. A total yield of allene and methylacetylene of 14 mol per 100 mol of allyl chloride pyrolyzed was obtained under suitable conditions. By means of the zero conversion method, hydrogen, propylene, allene, diallyl, 1,3-cyclohexadiene, and benzene have been found to be the main reaction products in the early stage of the pyrolysis, while methane, acetylene, ethylene, methylacetylene, butene-1, and butadiene have been found to be the side reaction products. The over-all activation energy of decomposition was 39.4 kcal/mol for an A factor of 108.7 sec−1. On the basis of the observed results, a free-radical mechanism has been proposed for the main reactions and the principal side reactions. It was further concluded that the pyrolysis was a radical decomposition initiated by the reaction C3H5Cl→C3H5·+Cl and that the over-all mechanism in the early stage of the pyrolysis was represented essentially by the reaction 2C3H5Cl→C3H5·+\dotC3H4Cl+HCl.
  • Norio Kunieda, Kazuo Sakai, Shigeru Oae
    1969 Volume 42 Issue 4 Pages 1090-1094
    Published: 1969
    Released: March 27, 2006
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    Sulfoxides are known to undergo concurrent oxygen exchange and racemization reactions with various reagents (Bull. Chem. Soc. Japan, 41, 1025 (1968)). Especially well studied are the oxygen exchange reactions in acid media. We have found a similar concurrent oxygen exchange and racemization reaction of sulfoxides with liquid dinitrogen tetroxide. The pseudo first order reaction rates of both oxygen exchange and racemization reactions have been determined using both optically active and 18O-labeled sulfoxides. The kexkrac value was found to be unity, and the polar effect of substituents on the rates of oxygen exchange of substituted diphenyl sulfoxides was found to be considerably large, and correlated with σ+ values with ρ=−1.30. From these results a plausible mechanism for this reaction has been discussed.
  • Tsutomu Kagiya, Tomizo Kondo, Kozo Nakao, Kenichi Fukui
    1969 Volume 42 Issue 4 Pages 1094-1098
    Published: 1969
    Released: March 27, 2006
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    The effect of solvents on the cationic polymerization of N-phenylethyleneimine with formic acid catalyst has been studied quantitatively. The polymerization rates in the various solvents used increase in the following order: diethyl ether\simeqtetrahydrofuran<toluene\simeqcarbon tetrachloride<anisole<methyl acetate<ethylene dichloride<N,N-dimethylacetamide<dimethyl sulfoxide<epichlorohydrin<acetonitrile. In polar solvents with high dielectric constants, the rates are much larger than those in nonpolar solvents with low dielectric constants. However, in the solvents with similar dielectric constants, such as acetonitrile and N,N-dimethylacetarnide, ethylene dichloride, methyl acetate and tetrahydrofuran, and anisole and diethyl ether, the rates decreased with an increase in the nucleophilicity of the solvents, and the dependence of the polymerization rate on the nucleophilicity of the solvents is much larger in polar solvents than in nonpolar solvents. The propagation rate was markedly influenced by the nature of the solvent, whereas the initiation rate was only a little influenced.
  • Noboru Sugiyama, Hiroshi Kataoka, Choji Kashima, Kazutoshi Yamada
    1969 Volume 42 Issue 4 Pages 1098-1100
    Published: 1969
    Released: March 27, 2006
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    The irradiation of methyl trans-β-acetylacrylate (I-A) in methanol or acetone or without any solvent gave the cis-isomer (I-B). On the contrary, the irradiation of the free acid of I-A, trans-β-acetylacrylic acid (II-A), in methanol or without any solvent gave the angelica lactone, 5-methyl-5-hydroxy-2-oxo-2,5-dihydrofuran (II-C). The irradiation of trans-β-pivaloylacrylic acid (III-A) in methanol also afforded the angelica lactone, 5-t-butyl-5-hydroxy-2-oxo-2,5-dihydrofuran (III-C). The reaction route from a cis-isomer to an angelica lactone was explained in terms of the inductive effect.
  • Takeshi Endo, Ryozo Numazawa, Makoto Okawara
    1969 Volume 42 Issue 4 Pages 1101-1104
    Published: 1969
    Released: March 27, 2006
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    N-Glycidyl-2-oxazolidone was synthesized by the reaction of N-sodium-2-oxazolidone with epichlorohydrin. N-Glycidyl-2-oxazolidone was polymerized with such Lewis acids as boron trifluoride etherate and aluminum chloride to give a white powder. These polymers adsorbed phenol and methyl bromide effectively. In addition, the copolymerization of N-glycidyl-2-oxazolidone with styrene was carried out, and the amount of the adsorption of methyl bromide on the copolymers was measured. The amount of the adsorption of methyl bromide increased in the copolymers as the content of 2-oxazolidone moiety increased. A 1 : 1 molar complex of stannic chloride with N-glycidyl-2-oxazolidone was isolated; when the complex was heated, poly(N-glycidyl-2-oxazolidone) was obtained quantitatively.
  • Kazuaki Kawamoto, Yoshiharu Nishimura
    1969 Volume 42 Issue 4 Pages 1105-1109
    Published: 1969
    Released: March 27, 2006
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    The present investigation was undertaken to find out whether or not the relative amounts of acrylonitrile obtained by the reaction between ethylene and hydrogen cyanide in a silent discharge are affected by the substances (Hg(CN)2, Cu, CuCN, Al, Zn and Fe) placed in a glass filter of the special discharge tube, and to examine the possibility of the direct introduction of a cyano radical into propylene by means of the silent discharge. The yield of acrylonitrile depended upon the packing materials in the glass filter. When the discharge wall of the glass filter was filled with Hg(CN)2, the yield of acrylonitrile was at its maximum. When a mixture of propylene and hydrogen cyanide was discharged in an ozonizer in the absence of air, the main liquid products were crotononitrile, methacrylonitrile, and n-propyl cyanide. Besides these compounds, the reaction products were confirmed to consist of isopropyl cyanide, acetonitrile, acrylonitrile, 4-methyl-1-pentene, 2,3-dimethylbutane, 1,5-hexadiene, 2-methylpentane, 1-hexene, n-hexane, and gaseous products. Judging from the relative concentration of each compound in the reaction products, it may be said that 2-methylvinyl, isopropenyl, propyl, allyl, isopropyl, and cyano radicals are the main intermediates in this reaction system.
  • Shigeru Oae, Yoshihito Kadoma, Yumihiko Yano
    1969 Volume 42 Issue 4 Pages 1110-1112
    Published: 1969
    Released: March 27, 2006
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    The rates of aminolyses of methyl, isopropyl, allyl and benzyl iodides have been determined in acetonitrile. Bases used were hydrazine, morpholine, imidazole and piperidine. The rates of all the aminolysis reactions can be correlated nicely with the basicities. Hydrazine also did not show any positive deviation from the Brφnsted plots. This fact suggests that the α-effect is not operative in these displacement reactions on the saturated carbon atom.
  • Akio Ohnishi, Katsuya Hayashi, Junzo Noguchi
    1969 Volume 42 Issue 4 Pages 1113-1118
    Published: 1969
    Released: March 27, 2006
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    The synthetic copolymer of L-tryptophan and L-glutamic acid exhibited two specific bands, around 292 mμ and 234 mμ, in the difference spectrum at pH 4.68 vs. pH 7.60 in a 0.1M phosphate buffer. The former, that at 292 mμ, might be caused by the red shift of the ordinary absorption band around 280 mμ, and the latter, that at 234 mμ, by the red shift of the far-ultraviolet absorption band, around 220 mμ, of the tryptophanyl residue in the copolymer. This specific peak at 234 mμ in the difference spectrum of the tryptophan copolymer may be distinguished from that at 222 mμ, which is due to the hyperchromisity (n→π* transition) of the amide group in the peptide bond reported with poly-L-glutamic acid. The peak at 230–235 mμ appearing in the difference spectrum between native and denaturated proteins may be due to the same red shift (π→π* transition) of the far-ultraviolet absorption band of the tryptophanyl residue as that shown by the tryptophan copolymer. The difference in absorption at 234 mμ was five times larger than that at 292 mμ, and both of them increase proportionally with a lowering of the pH. The relation between the difference absorption and the pH was quite similar to that between the helical content and the pH. The relative fluorescence intensity of the tryptophanyl residue was also depressed with a lowering of the pH, and the profile of the pH-dependence curve on the fluorescence intensity was almost identical with the titration curve of the copolymer. Therefore, it may be said that the appearance of the difference spectrum at 234 mμ corresponds to the formation of the α-helix in polypeptide and that the protonation of the glutamyl residue induces the quenching of the fluorescence of the tryptophanyl residue.
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