Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 39 , Issue 7
Showing 1-50 articles out of 72 articles from the selected issue
  • Masanobu Hidai, Katsumi Tamai, Yasuzo Uchida, Akira Misono
    1966 Volume 39 Issue 7 Pages 1357-1364
    Published: 1966
    Released: March 27, 2006
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    In the oligomerization of butadiene with the catalyst composed of iron(III) acetylacetonate and triethylaluminum, the degree of digomerization and the structures of the oligomers were strongly affected by the addition of an electron donor as a catalyst component. When triphenylphosphine was added, linear dimers composed of 3-methylhepta-1, 4, 6-triene and n-octa-1, 3, 6-triene were formed, while the addition of 2, 2′-dipyridyl produced cyclic dimers composed of cycloocta-1, 5-diene and 4-vinylcyclohex-1-ene. Besides the above donors, triphenylphosphite, tri(o-tolyl)-phosphite, tri(p-tolyl)phosphite, phosphorus trichloride, triethylamine and pyridine as monodentate, and o-phenanthroline, 2(2′-pyridyl)imidazoline and oxine as bidentate ligands, were tried, and the effects of those donors upon the reaction were studied. The transition states in these catalyst systems were also considered by means of studies of the effects of the molar ratio of catalyst components and by the measurements of infrared, ESR and visible light absorption spectra or magnetic susceptibilities of the reaction solutions.
  • Kimio Kawakita, Yuhbun Tsutsumi
    1966 Volume 39 Issue 7 Pages 1364-1368
    Published: 1966
    Released: March 27, 2006
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    Several equations representing the relation between the pressure and the apparent volume of a powdered mass under compression, as proposed by various authors, sometimes have essentially the same form as one other, and sometimes have contradictory characters. Various equations can be modified so as to be a function of the porosity and thus compared with each other. As a result, they can be classified into two types by means of the gradient of the porosity with the pressure (−dndP, n=porosity). One is −dndP=knx (Athy: x=1, Kawakita: x=2), and the other is −dndP=k(1−n)yPz (Smith: y=0, z=2⁄3, Nutting: y=1, z\doteqdot1, Balshin: y=2, z∼1, Terzaghi: y=2, z∼1, Jones: y=3, z=1), where k is a constant and x,y and z are parameters. In Kawakita’s equation the rate of the decrease of the porosity is considerably larger in an early period of compaction than in Athy’s equation. The second type of equation indicates that a major part of the porosity disappears at lower pressures.
  • Yoshio Ito
    1966 Volume 39 Issue 7 Pages 1368-1372
    Published: 1966
    Released: March 27, 2006
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    The non-Newtonian flow of poly (dimethyl siloxanes) with a wide variety of degrees of polymerization (Z), 31.6 to 6.02×103, was studied by using short capillary viscosimeters. Measurements were performed in the range of rate of shear from 10−1 to 3×106 sec−1. It was found that the flow behavior was markedly affected by the value Z of the test materials. That is, the flow was practically Newtonian over the entire range of shear rates when Z was less than 1.55×102. For higher values of Z, however, typical non-Newtonian behavior was observed in the range of moderate shear rates. At extremely high shear rates, the materials with Z=3.23×102 to 2.63×103 exhibit the upper (or second) Newtonian flow, but the materials with still higher values of Z exhibit the spiral flow. It was also found that the Shishido equation (J. Chem. Soc. Japan, Pure Chem. Sect. (Nippon Kagaku Zasshi), 84, 889 (1963)) was applicable to this polymer in describing the observed viscosity vs. shear rate dependence. Finally, an empirical method was proposed for estimating the upper Newtonian viscosity value from the viscosities at zero shear stress and at the inflection point of the flow curve.
  • Yasuto Nakai
    1966 Volume 39 Issue 7 Pages 1372-1377
    Published: 1966
    Released: March 27, 2006
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    A series of alkylnitrobenzene anion radicals has been studied by both electron spin resonance and infrared spectroscopy. It has been shown that there is a relationship between the magnitude of the nitrogen hyperfine splitting constant and the steric effect of the bulky alkyl group adjacent to the nitro group. In addition to the physical deformation factors, the effects of solvents, counter-ions, and temperature variation have been discussed. In the infrared spectra, the differences between anion radicals and neutral molecules have been found to be small, except for the change in the absorption intensity of the nitro-group stretching vibration.
  • Hiroshi Kato, Kaichiro Yamaguchi, Teijiro Yonezawa
    1966 Volume 39 Issue 7 Pages 1377-1382
    Published: 1966
    Released: March 27, 2006
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    The electronic structures of dimers containing boron and aluminum atoms, i. e., B2H6, B2H2-(CH3)4, Al2Cl6, Al2Cl2(CH3)4 and Al2(CH3)6, are investigated by an extended Huckel method. The calculations show that the central linkages are weak and that their bonding natures are very different from those of the bonds between the metals and terminal atoms. Judging from the orbital energies and populations, these dimers still hold a strong acidity, like that in the monomers, an acidity which depends mainly on the existence of the almost unfilled pπ orbitals of the metal atoms, where the electrons occupying the lower vacant orbitals in these dimers are almost localized. The results are compared with other calculations and experimental results. It is, further, shown by examining the electronic structures of two hypothetical compounds that these dimers can be easily formed by using the vacant valence orbitals of the metal atoms, and that the metal-metal bonds in some dimers are considerably strong.
  • Shigekazu Kusabayashi, Hiroshi Mikawa, Misako Konda, Masano Hayashi
    1966 Volume 39 Issue 7 Pages 1383-1387
    Published: 1966
    Released: March 27, 2006
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    The band-gap energy has been calculated by a tight-binding approximation in a previous report. Although the value thus calculated coincided rather well with the experimental value, it might yet be possible that the band-gap energy will change appreciably when the interactions of all the energy levels are considered at one time. It was, therefore, calculated by the following method, which considers in principle all the level interactions. A repeating unit is composed of 30 atomic orbitals. Each atomic wave function makes three-dimensional Bloch functions. The crystal wave function is set up in the form of a linear combination of these 30 Bloch functions. The energy is then calculated by applying the variation principle and by using the Hückel approximation. The band-gap energy thus calculated is 1.20 eV. This value is near the experimental value, 1.36 eV.; it was also close to the previous result, 1.26 eV., thus confirming the previous calculations. The consideration of the band-widths and the density of the state may interpret the experimental results on the sign of the carrier. The results offer additional support for our previous conclusion regarding the conduction mechanism.
  • Yojiro Tsuzuki, Koko Tanabe, Kikuhiko Okamoto, Michiyo Fukubayashi
    1966 Volume 39 Issue 7 Pages 1387-1391
    Published: 1966
    Released: March 27, 2006
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    The rotatory dispersion (RD) and ultraviolet absorption of some α-hydroxy-carboxylic acids and their nitrates have been measured and analyzed. A distinct relation has been found between the configuration and the sign of the Cotton effect; namely, nitrates of α-D-hydroxy-carboxylic acids (R-configuration) show positive Cotton effects, while those of α-L-hydroxy-carboxylie acids (S-configuration) show negative Cotton effects. Thus a rotatory contribution by the nitrates of the α-hydroxyl group has been suggested, though it is opposite in sign to the xanthates of the α-hydroxy-carboxylic acids.
  • Yojiro Tsuzuki, Koko Tanabe, Kikuhiko Okamoto, Noriko Yamada
    1966 Volume 39 Issue 7 Pages 1391-1397
    Published: 1966
    Released: March 27, 2006
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    The rotatory dispersions (RD) and the ultraviolet absorptions of eight nitrates of galactopyranoside, altropyranosides, glucofuranoside, mannopyranosides and of glucopyranosides, and also of five hexosepyranosides, have been measured. Studies have also been made of the correlation between the configuration and the Cotton effect, the sign of which has been determined by the RD curve as well as by the dispersion constant computed from the dispersion data, and in some cases by means of the circular dichroism (CD). All the findings and conclusions are consistent with the generalized rule originally found with glucose derivatives (Y. Tsuzuki, K. Tanabe and K. Okamoto, This Bulletin, 39, 761 (1966)). The rule has been shown to be extensively applicable to several hexoses; namely, α-glycosides with a C–ONO2 chromophore of a β(or D)-configuration show negative Cotton effects, and those with a C–ONO2 group of a β(or L)-configuration exhibit positive Cotton effects, while with nitrates of β-glycosides the signs of the Cotton effects are exactly reversed (ref. Conclusion).
  • Teijiro Yonezawa, Isao Morishima, Hiroshi Kato
    1966 Volume 39 Issue 7 Pages 1398-1401
    Published: 1966
    Released: March 27, 2006
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    A molecular orbital interpretation of the carbon-13 chemical shifts of saturated hydrocarbons is presented. The shielding constant of the carbon atom is shown to be roughly proportional to the excess charge densities of 2p electrons, which is in accordance with experiments. The so-called β- and γ-effects in the carbon-13 chemical shifts are explained on the basis of an MO theory.
  • Manabu Sen\={o}
    1966 Volume 39 Issue 7 Pages 1401-1406
    Published: 1966
    Released: March 27, 2006
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    The thixotropic behavior is discussed on the basis of the thermodynamics of irreversible processes. The fundamental equations are given for the thixotropic fluids by accepting the concept that the internal structure of the system is destroyed by the applied forces, and the general phenomenological equations are written for all the processes occurring in this system. The process by which the thixotropic recovery takes place is non-stationary. A method of specifying this process is proposed by introducing the concept of a fictitious pressure tensor; the data on a rubber latex suspension given by Mooney is analyzed by this method.
  • Kozo Hirota, Michiyasu Itoh
    1966 Volume 39 Issue 7 Pages 1406-1409
    Published: 1966
    Released: March 27, 2006
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    The relative scission-probabilities of C–C bonds of n-propyl, n-butyl and isobutyl amines being formed by electron impact (90 V.) were determined by the use of mass spectrometers of the usual type and of the high-resolution type. They were in good accordance with the theoretical values calculated by the LCBO-MO theory which had been proposed and found successful in explaining the mass spectra of n-paraffins and methyl alkyl ketones.
  • Tatsuo Miyazawa, John Overend
    1966 Volume 39 Issue 7 Pages 1410-1414
    Published: 1966
    Released: March 27, 2006
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    Small variations in the G and F matrices can be related linearly to variations in the calculated frequencies and normal coordinates through a transformation matrix, J. Explicit expressions are given for the elements of J and J−1. Isotope effects on normal-coordinate coefficients are also treated.
  • Haruo Hosoya, Saburo Nagakura
    1966 Volume 39 Issue 7 Pages 1414-1418
    Published: 1966
    Released: March 27, 2006
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    The ultraviolet absorption spectra of tropone (I) and tropolone (II) were measured with sulfuric acid solutions of various acidities. The accurate pKa values, as determined by the proposed method, were −1.02 and −0.86 for I and II respectively. The Raman spectra of II were measured with sulfuric acid solutions of various acid concentrations. The bands in the 6 and 15 μ regions change sharply when the solvent acidity changes from 5 to 25%, corresponding well to the ultraviolet absorption change. The infrared absorption spectra of II were measured with the concentrated deuterosulfuric acid solution in the 6 μ region. The vibrationals mode of the protonated tropolone were discussed.
  • Yusei Maruyama, Hiroo Inokuchi
    1966 Volume 39 Issue 7 Pages 1418-1422
    Published: 1966
    Released: March 27, 2006
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    The electrical conductivity of an evaporated film of quaterrylene varied with the pressure of the ambient oxygen. The resistivity was 1.1×1012 Ωcm. in a vacuum of 4×10−8 mmHg; this was very large compared with the previously-reported value, ∼106Ωcm., which was obtained after exposing the film to the air of an atmospheric pressure. The temperature dependence of the resistance of the film was also affected by the ambient oxygen. The intrinsic semiconductor model could be applied only in the case of a high vacuum (∼10−8 mmHg); the band gap, Δε, was 1.7 eV. in this case. From the resistance-temperature relations at the various oxygen pressures, it seems that two acceptor levels, 0.03 eV. and 0.6 eV. above the valence band respectively, exist.
  • Masahiro Tanaka, Masaaki Kato, Shin Sato
    1966 Volume 39 Issue 7 Pages 1423-1426
    Published: 1966
    Released: March 27, 2006
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    The benzene-photosensitized cis-trans isomerization of butene-2 has been reinvestigated, using 2537 Å as the light source. A comparative study with pentene-2 has also been carried out. In all experiments, pentene-2 behaved very similarly to butene-2. The quantum yield of the isomerization was estimated to be 0.27±0.03, irrespective of the olefin used. The following photostationary ratios of the cis to the trans isomer were obtained: 1.05±0.1 for butene-2, and 0.99±0.1 for pentene-2. The ratio of the initial rates of isomerization was, for both olefins, 1.15±0.15, in favor of the isomerization from the cis to the trans isomer. Both ratios are very close to unity; this finding is in agreement with our previous results (M. Tanaka, T. Terao and S. Sato, Bull. Chem. Soc. Japan, 38, 1645 (1965)).
  • Yoshinori Kato, Atsuo Nishioka
    1966 Volume 39 Issue 7 Pages 1426-1431
    Published: 1966
    Released: March 27, 2006
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    A quantitative study of some structural irregularities of polyethylenes by an improved proton magnetic resonance method is reported. The background noise of a nuclear magnetic resonance spectrometer can be remarkably eliminated with the aid of the Mnemotron Computer of Average Transients. The total numbers of methyl groups in polyethylenes were estimated by this method using 5% solutions of the polymer in tetrachloroethylene. Spectra were obtained at about 110°C in order to suppress the thermal degradation of the polymer. The results agree well with those estimated by an infrared compensating method. Information about the species of branches and, in some cases, the number-average molecular weight of the polymer can be obtained by examining the resonance shape of methyl groups. The chemical shift difference between the triplet due to ethyl branches and that due to the other longer branches was found to be less than 0.05 p.p.m. This method can also be applied to the detection of unsaturations in polyethylene. In this case, however, the signal-to-noise ratio has to be increased to a factor of at least 20. Thus, the purification of the solvent is very important in the experiment.
  • Masaji Miura, Akinori Hasegawa, Tokinori Fukui
    1966 Volume 39 Issue 7 Pages 1432-1436
    Published: 1966
    Released: March 27, 2006
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    Under irradiation with γ-rays at room temperature, the glass of sodium polyphosphate or its single crystal doped with sodium sulfate becomes red, whereas the pure single crystal remains colorless. The glass and the doped single crystal exhibit ESR spectra which can be attributed to the hole trapped in the non-bonding orbital on the oxygen atom. The pure single crystal, of course, exhibits no ESR spectra. The determination of the degree of polymerization in the aqueous solution of the glass showed a decrease in the length of the main chain caused by the γ-ray irradiation. It may be concluded from these facts that the P–O–P bond is ruptured under the irradiation and that the effect of γ-rays on sodium polyphosphate is closely correlated with the local strain of the P–O–P bond.
  • Toyosaburo Takeuchi, Masakazu Sakaguchi, Yoshio Togashi
    1966 Volume 39 Issue 7 Pages 1437-1439
    Published: 1966
    Released: March 27, 2006
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    The pyrolysis of toluene-1-14C was carried out by means of the semi-flow method at 800 and at 1000°C in the presence of the registers of porcelain, and the distributions of the radioactive carbon in gaseous products and that of the deposited carbon were determined. The molar c.p.m. of methane and that of a mixture of C2-compounds were about 1/20 of and twice the molar c.p.m. of the original toluene respectively, while the c.p.m. per gram-atom of the deposited carbon was about twice that of toluene, when the temperature of reaction was 800°C. In the case of the reaction at 1000°C, the c.p.m. per gram-atom of carbon of each product was found to be practically equal to that of the original toluene. It was proposed that methane is formed by the removal of the methyl group of toluene, and that the main source of the carbon of C2-compounds and the deposited carbon is the 1-carbon of toluene. The equalization of the radioactive carbon in every product at a high temperature was interpreted by assuming that the tropyl radical is formed as an intermediate after the formation of the phenyl radical in the initial stage of the reaction.
  • Masaaki Ohara, Chau-Yang Chen, Takao Kwan
    1966 Volume 39 Issue 7 Pages 1440-1442
    Published: 1966
    Released: March 27, 2006
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    The asymmetric adsorption of D, L-mandelic acid and its homologues has been demonstrated on amylose by means of the column chromatographic and static techniques. The D-(−)-isomer of mandelic acid has been found to be adsorbed more weakly than the L-(+)-isomer; the separation factor of the two antipodes has been estimated to be 1.09 at 0°C. This value is greater than that on starch, suggesting that amylose may have a somewhat higher selectivity for the asymmetric adsorption of the optical antipodes than amylopectin. The anomalous interaction of D, L-atrolactic acid has been observed on the amylose much as in the case with starch reported previously.
  • Yoshiya Harada, Hiroo Inokuchi
    1966 Volume 39 Issue 7 Pages 1443-1448
    Published: 1966
    Released: March 27, 2006
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    The external photoelectric effect of thin films of tetracene, pentacene, violanthrene, quater-rylene and tetrathiotetracene was studied in the vacuum ultraviolet region. The contact potential differences between the emitters, organic crystals, and the collector (Aquadaq) were determined from the saturation points of the current-voltage characteristics. It was observed that the quantum yields of photoemission increase markedly with an increase in the photon energy, reaching the order of 10−2 electrons/quantum at hv=10 eV. The threshold energies were lower by 1–2 eV. than the molecular ionization potentials. An energy diagram for the external photoelectric process of organic molecular crystals was introduced on the basis of the intrinsic band model. With the aid of this diagram, the band gap energies, Δε, were obtained from the observed values of photoemission. The values of Δε thus obtained were in fairly good agreement with those based on the results of the temperature dependence of semiconduction.
  • Jiro Kashima, Takuo Yamazaki
    1966 Volume 39 Issue 7 Pages 1448-1452
    Published: 1966
    Released: March 27, 2006
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    The determination of oxygen in metals with high melting points is important for the development of metallurgy. This paper will describe a very simplified apparatus and a procedure which gives precise results almost without a blank test. A silicon fusion technique developed by the present authors is used instead of the platinum bath method for the purpose of decomposing oxides in metals. It enables us to determine oxygen in a small quantity of a sample by the use of a highly-sensitive gas chromatograph. The amount of oxygen in the purified tantalum and niobium was determined within a standard deviation of 0.0038%. The precision established in tests of titanium samples containing 0.074% of oxygen was 0.0018%; this observed value is in good agreement with that obtained by the vacuum fusion method.
  • Jiro Kashima, Takuo Yamazaki
    1966 Volume 39 Issue 7 Pages 1453-1456
    Published: 1966
    Released: March 27, 2006
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    Although the chemical distillation method is generally employed for the determination of nitrogen in metals, it has been found that this method involves some difficulties in cast iron and pig iron samples. This paper will, therefore, describe new, repreoducible methods for the determination of nitrogen in chilled cast iron. They are the inert gas fusion and the chemical distillation methods. The most suitable sample for obtaining almost the same results with regard to ordinary cast iron by both methods was found to be a thin plate chilled by a copper mold. The accuracy of both methods was ±0.0004% when thin-plate samples containing from 0.0030 to 0.010% nitrogen were used.
  • Tokiti Noda, Yasuhiko Endo, Masumi Ushio
    1966 Volume 39 Issue 7 Pages 1456-1462
    Published: 1966
    Released: March 27, 2006
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    Fluor-hydroxyl muscovite was synthesized from a mixture of gels and chemicals of the KAl3Si3O10Fx(OH)2−x composition, where x=0, 0.5, 1.0, 1.5 and 2.0, in the temperature range of 500–600°C under pressures ranging from 500 to 900 atm. The fluorine content of the synthetic muscovite increased with the increase in x, but the distribution coefficient of fluorine [(the fluorine content of the crystal)/(the fluorine concentration of the solution)] decreased with the increase in x, increased with the increase in the temperature of synthesis, and decreased with the increase in the pressure of synthesis. The synthetic fluor-hydroxyl muscovite crystallized mainly in 1M polymorph, and very little in 2M polymorph, at 500°C in 20 hr. The fraction of 2M muscovite increased with the increasing temperature of synthesis. The d005 and d060d lattice spacings of the mica were observed to decrease linearly with the increase in the fluorine content of the mica.
  • Bunji Iwasaki, Kenzo Kitayama, Takashi Katsura
    1966 Volume 39 Issue 7 Pages 1462-1468
    Published: 1966
    Released: March 27, 2006
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    Tertiary sediments were collected from the Miura group on the Miura Peninsula, and the total chlorine and fluorine in these sediments were determined colorimetrically, together with the water-soluble chlorine and fluorine. There was little correlation of the contents of insoluble chlorine and fluorine in the sediments to their locations and ages. The insoluble chlorine contents of the psammitic rocks were higher than those of the pelitic rocks, whereas the insoluble fluorine contents of the former were lower than those of the latter. There seemed to be a moderately negative correlation between the contents of insoluble chlorine and fluorine in the sediments. All the sediments analyzed contained very small amounts of water-soluble fluorine (0.001 to 0.002% F). The frequency distributions of the insoluble chlorine contents in both the psammitic and pelitic rocks were lognormal.
  • Teruo Nomura, Yoshihiko Saito
    1966 Volume 39 Issue 7 Pages 1468-1471
    Published: 1966
    Released: March 27, 2006
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    The structure of 2AgNO3·NC(CH2)2CN has been determined by X-ray analysis. It is mono-clinic; a=5.87, b=17.79, c=4.61 Å, β=118.2°, space group P21a, two formula units in the cell. The structure is essentially ionic and consists of the complex cations, [AgNC(CH2)2CNAg]2+ (Ag–N, 1.97 Å), and the nitrate anions. All the bond lengths are normal. The molecule of succinonitrile was found to take the trans configuration; this is in conformity with the conclusion drawn from the infrared study.
  • Yasuo Nakao, Ken-ichi Sakurai, Akitsugu Nakahara
    1966 Volume 39 Issue 7 Pages 1471-1476
    Published: 1966
    Released: March 27, 2006
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    The relationship between the structure of fused-ring systems and the relative stability of copper(II) Schiff base chelates has been discussed, on the basis of the properties of six copper(II) complexes, in connection with the transamination reaction. As the conclusion it has been suggested that the transamination reaction in fused-ring systems containing copper(II)-glyoxylate- or -pyruvate-Schiff bases may be expected only in such appropriately unstable systems as have two five-membered rings and that it is generally accompanied by a stabilization of the system. The preparation and properties of the two new copper(II) chelates, glyoxylidene-β-alaninatoaquo-copper(II) and pyruvidene-α-alaninatoaquocopper(II), have been described.
  • Tsutomu Mizoroki, Mikitake Nakayama
    1966 Volume 39 Issue 7 Pages 1477-1482
    Published: 1966
    Released: March 27, 2006
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    In the synthesis of acetic acid from methanol and carbon monoxide in the presence of cobalt(II) iodide as a catalyst, the addition of an acetate has been shown to have a great influence upon the methanol conversion into total acetic acid. When the added amounts of potassium acetate are from one to two times as much as that of cobalt (II) ion, both methanol conversion and its reaction rate reach a maximum, and methanol is prevented from forming dimethyl ether. On the other hand, the reaction nearly stops when the amount of potassium acetate becomes more than four times as large. The variation in the absorption spectrum of cobalt (II) ion in course of the reaction shows that the increase in the added amount of an acetate is favorable for the formation of cobalt carbonyls and that most cobalt(II) ions are tetrahedral species of the [Co(AcO)4−n-In]2− type so long as the reaction is promoted with the catalyst. From these experimental results, the course of the reaction has been discussed.
  • Hiroshige Muramatsu, Soyao Moriguchi, Kan Inukai
    1966 Volume 39 Issue 7 Pages 1482-1486
    Published: 1966
    Released: March 27, 2006
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    The new ethylenes, with a 2-hydroperfluorocyclobutyl, 2-chlorotetrafluoro-1-cyclobutenyl or 2-chlorohexafluoro-1-cyclopentenyl group, were synthesized in good yields by the dehydration of the 1 : 1 adducts prepared by the addition of the alcohols to perfluorocyclobutene, 1, 2-di-chlorotetrafluorocyclobutene or 1, 2-dichlorohexafluorocyclopentene respectively. The dehydro-fluorination of 2-hydroperfluorocyclobutylalkylethylenes gave a mixture of perfluoro-1-cyclo-butenyl- and perfluoro-2-cyclobutenylethylene. In the mixture, the former was predominant over the latter. Some polyfluorocycloalkenylethylenes prepared polymerized in the presence of peroxide to yield transparent polymers.
  • Naoya Ogata, Tomohiko Asahara
    1966 Volume 39 Issue 7 Pages 1486-1490
    Published: 1966
    Released: March 27, 2006
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    The addition reaction of amino alcohols with acrylates were studied. The addition takes place at the amino group of amino alcohol, producing N-(hydroxyalkyl)-β-alanine in a good yield. The reaction rate becomes slower as the ester group of acrylate becomes larger, and phenyl acrylate gives a polymer as soon as it is mixed with ethanolamine. The rates of the addition reaction with acrylate are in the following order: NH2CH2CH2OH>CH3NHCH2CH2OH>>RNH2>NH(CH2CH2OH)2.
  • Nobuo Mori, Yoshiteru Tanaka, Yojiro Tsuzuki
    1966 Volume 39 Issue 7 Pages 1490-1495
    Published: 1966
    Released: March 27, 2006
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    The infrared OH spectra of an ArCH(OH)(CH2)nCOOMe series (n=0 and 1) in dilute carbon tetrachloride solutions have been measured at 25°C with a Perkin-Elmer 21 spectrometer. A comparison of the data with those of other related compounds shows that the OH group forms a hydrogen bond predominantly with the carbonyl-oxygen atom and also with the ether-oxygen atom and/or the π-electrons of the phenyl group, while, practically speaking, no free OH group is present. Further, the NMR chemical shifts of the methine- and the methyl-protons when n=0, as measured with a Varian A-60 spectrometer, have been correlated with the Hammett substituent constants; the shift of the methine-proton, when the ring-substituent is a halogen, does not fall on the correlation line, but falls on a separate line.
  • Yoshinobu Takegami, Yoshihisa Watanabe, Hiromitsu Masada, Yasukazu Oku ...
    1966 Volume 39 Issue 7 Pages 1495-1498
    Published: 1966
    Released: March 27, 2006
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    The isomerization of C5-acyl(n-valeryl- and α-methylbutyryl-) and C6-acyl(n-caproyl-, α-methylvaleryl- and α-ethylbutyryl-) cobalt carbonyls has been studied and compared with that of C4- acyl(n- and isobutyryl-) cobalt carbonyls previously reported. It has been observed that solvents have great effects on the isomerization (the rate and equilibrium) of the C5-acylcobalt carbonyls. The equilibrium proportion of the isomers (iso/normal) is almost 1 in diethyl ether and tetrahydrofuran. In solvents such as dioxane, ethyl acetate and benzene it seems difficult for this isomerization to occur. α-Ethylbutyrylcobalt carbonyl appears to isomerize directly to n-caproylcobalt carbonyl. However, n-caproylcobalt carbonyl isomerizes only to α-methylvaleryl-cobalt carbonyl; the reverse isomerization also occurs, but it seems very difficult for any other isomerization between the two of them to occur.
  • Yoshinobu Takegami, Yoshihisa Watanabe, Hiromitsu Masada, Chikao Yokok ...
    1966 Volume 39 Issue 7 Pages 1499-1501
    Published: 1966
    Released: March 27, 2006
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    The reaction between benzyl halide and potassium cobalt carbonylate has been studied. o-Toluylcobalt carbonyl is found among the reaction products. This carbonyl seems to be formed by the isomerization of benzyl cobalt carbonyl via phenylacetylcobalt tricarbonyl or o-tolylcobalt carbonyl. This isomerization occurs only at relatively high temperatures (30–50°C). At 0°C, only phenylacetyl cobalt carbonyl is formed in a good yield. The isomerization is highly promoted by the addition of cobalt hydrocarbonyl. The reaction atmosphere (carbon monoxide and nitrogen) also has a great effect on the isomerization. Such additives as oxalic acid, p-toluenesulfonic acid, trichloroacetic acid, and ethyl alcohol-hydrogen chloride have no promoting effect on the isomerization.
  • Eberhard W. Neuse, Kazuko Koda
    1966 Volume 39 Issue 7 Pages 1502-1507
    Published: 1966
    Released: March 27, 2006
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    Based on previous investigations involving the self-condensation of the ferrocenyl Mannich base, N, N-diniethylaminomethylferrocene (I), the present paper describes the co-condensation of this Mannich base with ferrocene. The reactions are conducted in the melt phase in the presence of a ZnCl2/HCl catalyst system. The resulting polymeric products are soluble and partially fusible and have number-average molecular weights in the 500–4000 range (unfrac-donated). The polymers, exhibiting the idealized structure III, are closely related to the products of self-condensation (II), with recurring units composed of ferrocenylene and methylene groups and homoannular substitution predominating along the chain. Due to the presence of ferrocene, however, an additional termination step is introduced into the overall reaction,, leading to a reduced degree of polymerization. The considerable excess over the stoichiometric amount of ferrocene required to achieve this competitive termination and concomitant decrease in Mn suggests that pronounced inductive and hyperconjugative effects are operative in the fer-rocenylene-methylene system, resulting in activation of the methylene-substituted ring. The isolation of the lowest homolog possible, diferrocenylmethane, lends further support to the proposed structure of the recurring unit. Spectroscopic evidence obtained on subfractionated material suggests the substitution pattern along the chain to be essentially the same as in the earlier described homocondensation polymers, which is consistent with the assumption of essentially like propagation mechanisms in both cases. A small degree of branching is also inferred from spectroscopic data.
  • Eberhard W. Neuse, Edward Quo
    1966 Volume 39 Issue 7 Pages 1508-1514
    Published: 1966
    Released: March 27, 2006
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    The Lewis acid-catalyzed polycondensation of ferrocene with formaldehyde or its dimethyl-acetal gives rise to the formation of soluble, novolac-type polymers comprising ferrocenylene units interlinked by methylene bridges. In contrast to earlier work performed by other investigators in liquid hydrogen fluoride or sulfuric acid media, where only non-polymeric products were described, propagation is accomplished in the present case by condensing the reactants in a closed system in bulk at temperatures up to 170°C. The resulting polymers, with Mn values up to 4000 (unfractionated), are shown by elemental and spectroscopic analyses and viscometric data to be essentially identical with the previously reported polycondensation products of N, N-dimethyl-aminomethylferrocene with ferrocene. Infrared spectroscopy shows the intralinear substitution to be predominantly homoannular, which is expected as a result of the electronic effects exercised by the methylene substituent. Under appropriate conditions, additional methylene groups can be incorporated into the polymer, giving rise to double-bridged segments and inter-chain bridging. Strongly crosslinked polymers are obtained if excess aldehydic reactant is employed at temperatures in the 170–185°C range.
  • Sadao Yoshikawa, Oh-Kil Kim
    1966 Volume 39 Issue 7 Pages 1515-1519
    Published: 1966
    Released: March 27, 2006
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    The catalytic effects of polymeric sulfonic acids in ester hydrolysis in aqueous acetone were inferior to that of hydrochloric acid. However, the hydrolysis rate was accelerated by increasing the water content of acetone-water mixtures, and, in a water solution, polymeric sulfonic acids were much more effective catalysts. Furthermore, the catalytic efficiency of polymeric sulfonic acid in ester hydrolysis in water increased with the length of the ester molecule. The polymeric sulfonic acid with a strong hydrophobic character was more effective; 69% sulfonated polystyrene-sulfonic acid, for example, hydrolyzed methyl hydrogen azelate in water over five times more rapidly than hydrochloric acid. The specificity thus obtained suggests that, in the hydrolysis of electrically-neutral esters in water, ester molecules are concentrated in the neighborhood of the polymer by the hydrophobic interaction between catalyst and substrate. Besides, in the hydrolysis of aliphatic esters catalyzed by polyvinylsulfonic acid in 50% aqueous acetone, there was a linear relationship between the reciprocal of the rate constant and the intrinsic viscosity of the polymer, while in the case of polystyrenesulfonic acid hardly such any relationship was found. These remarkably different behaviors of the two kinds of polymer catalysts should be attributed to the difference in the expansion of the polymer chain in solutions.
  • Shinichi Motoki, Sadayoshi Satsumabayashi, Takashi Masuda
    1966 Volume 39 Issue 7 Pages 1519-1521
    Published: 1966
    Released: March 27, 2006
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    β-Cyanopropionaldehyde dimethyl acetal was brominated in the presence of calcium carbonate to give α-bromo-β-cyanopropionaldehyde dimethyl acetal. This was then dehydro-brominated with 10% alcoholic potash at −5 to 0°C, β-cyanoacrolein dimethyl acetal was thus obtained in a high yield. Free aldehyde of a light green liquid was given by the hydrolysis of the acetal. A similar procedure using α-chloro-β-cyanopropionaldehyde dimethyl acetal was also examined. On the other hand, β-cyanoacrolein was prepared by the direct dehydro-genation of β-cyanopropionaldehyde with selenium dioxide.
  • Kunio Okamoto, Noboru Tanaka, Kiyoshi Adachi, Haruo Shingu
    1966 Volume 39 Issue 7 Pages 1522-1524
    Published: 1966
    Released: March 27, 2006
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    The catalytic pyrolysis of 1, 2-dichloroethane on active carbon, carried out at 300 and 400°C in the presence of toluene, benzene and n-hexane, resulted predominantly in ethylene instead of vinyl chloride, which is known in the literature as the major pyrolysis product of the titled compound; the pyrolysis rates were suppressed by these hydrocarbons. These results have been explained by assuming a radical-chain mechanism similar to that suggested for the “homogeneous” pyrolysis of this compound. The chain length derived from the proposed mechanism has been estimated to be 20 to 50.
  • Hiroshi Suginome
    1966 Volume 39 Issue 7 Pages 1525-1529
    Published: 1966
    Released: March 27, 2006
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    The structure of sophorol was confirmed to be 2′:7-dihydroxy-4′:5′-methylenedioxyisoflavanone by the synthesis of dehydro-O-dimethylsophorol, 2′:7-dimethoxy-4′:5′-methylenedioxyisoflavone.
  • Hiroshi Suginome
    1966 Volume 39 Issue 7 Pages 1529-1534
    Published: 1966
    Released: March 27, 2006
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    This isolation and determination of the structure of a new, naturally-occurring chromano-coumaran, maackiain (I) R=H, are described. On the basis of these results, the structure of pterocarpin is revised to (I) R=CH3.
    (Remark: Graphics omitted.)
  • Hiroshi Suginome, Tsukasa Iwadare
    1966 Volume 39 Issue 7 Pages 1535-1541
    Published: 1966
    Released: March 27, 2006
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    The synthesis of chromanocoumaran (I) (R1= R2= H), the skeleton of pterocarpinoids, is described. This method, which follows a plausible biogenetic pathway, is then extended to the synthesis of d, l-homopterocarpin (I) (R1= R2= OMe). The synthesis and NMR studies allow us to assign a cis B/C ring junction to the compounds of this class.
    (Remark: Graphics omitted.)
  • Hiroshi Suginome, Toshiro Kio
    1966 Volume 39 Issue 7 Pages 1541-1543
    Published: 1966
    Released: March 27, 2006
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    Some biogenetic aspects of the co-occurrence of pseudobaptigenin, maackiain and sophorol are discussed.
  • Hiroshi Suginome
    1966 Volume 39 Issue 7 Pages 1544-1547
    Published: 1966
    Released: March 27, 2006
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    By rotatory-dispersion studies, it was confirmed that sophorol, (−) maackiain, pterocarpin, equol and homopterocarpin have the same absolute configuration at position 3. The results of the O. R. D. examination of (−) halostachine and pterocarpinoids allow us to assign the 3R, 4R configuration to pterocarpin and to the related compounds.
  • Tadao Nakaya, Minoru Imoto
    1966 Volume 39 Issue 7 Pages 1547-1551
    Published: 1966
    Released: March 27, 2006
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    The synthesis and the absorption and fluorescence spectra of 2, 5-dimethoxy-1, 4-distyryl-benzene derivatives and the related compounds are reported on. Their absorption and their fluorescence spectra, are then discussed. According to the spectra, some of the compounds synthesized here are better wavelength shifters in plastic scintillators that the compounds described in the literature.
  • Tadao Nakaya, Takanori Tomomoto, Minoru Imoto
    1966 Volume 39 Issue 7 Pages 1551-1556
    Published: 1966
    Released: March 27, 2006
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    Fifteen anthracene derivatives have been synthesized, and their absorption and fluorescence spectra have been measured. The spectra will be discussed in this paper. According to the spectra, some of anthracene derivatives synthesized here are better wavelength shifters than the compounds previously described in the literature.
  • Naoya Ogata, Shyunroku Tohoyama
    1966 Volume 39 Issue 7 Pages 1556-1559
    Published: 1966
    Released: March 27, 2006
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    The bicyclic lactam ether, 3-aza-10-oxabicyclic[4.3.1]decane-4-one has been attempted to synthesize by the Beckmann rearrangement of the oxime of 9-oxabicyclo[3.3.1]nonane-3-one; this rearrangement caused polymerization through the cleavage of the ether group in acidic media. Therefore, it may be presumed that the cationic polymerization of lactam ethers in the presence of Lewis acid proceeds through the opening of the ether linkage.
  • Shunsuke Murahashi, Heimei Yuki, Koichi Kosai, Fumihiro Doura
    1966 Volume 39 Issue 7 Pages 1559-1562
    Published: 1966
    Released: March 27, 2006
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    Various condensation products were obtained by the reaction between pyruvic acid and urea. They are 5-hydroxy-5-methyl-hydantoin, homoallantoin, homoallantoic acid, and dipyruvic triureide. 5-Methylene-hydantoin was prepared from some of these compounds, or directly from pyruvic acid and urea, by reactions in organic acid. The most convenient method was the dehydration of 5-hydroxy-5-methyl-hydantoin, which is a new compound melting at 166°C. 5-Methylene-hydantoin, m. p. 214°C, is a new monomer of the vinylidene type which polymerizes easily by means of a free radical mechanism. 3-Methyl-5-methylene-hydantoin was also prepared from 5-hydroxy-5-methyl-hydantoin through its 3-methyl derivative.
  • Shunsuke Murahashi, Heimei Yuki, Koichi Kosai, Fumihiro Doura
    1966 Volume 39 Issue 7 Pages 1563-1567
    Published: 1966
    Released: March 27, 2006
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    5-Methylene-hydantoin was polymerized easily by free radical initiators, and showed a higher reactivity in copolymerization with styrene. From the copolymerization of styrene (M1) and 5-methylene-hydantoin (M2), the monomer reactivity ratios, r1 and r2, were found to be 0.03 and 24, while the Q and e values in Alfrey-Price’s Q-e scheme were found to be 21 and −0.23, respectively. As is shown by the large Q value, the high reactivity of 5-methylene-hydantoin is based on the high resonance stabilization of its radical, a stabilization which results from the conjugation system. This was also confirmed by a study of the ultraviolet spectrum. Poly-5-methylene-hydantoin showed electrolytic behavior in its solubility and solution viscosity. This property is due to the dissociation of NH at the 3 position of the hydantoin group. The polymers of 3-methyl-5-methylene-hydantoin and 3-phenyl-5-methylene-hydantoin were observed to show very weak acidities, resulting from the NH at the 1 position. Poly-α-aminoacrylic acid was obtained by the alkaline hydrolysis of poly-5-methylene-hydantoin. This polymer was soluble in water, and showed an unusual amphoteric behavior in solution viscosity.
  • Shumpei Sakakibara, Noriyoshi Inukai
    1966 Volume 39 Issue 7 Pages 1567-1572
    Published: 1966
    Released: March 27, 2006
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    When p-nitrophenyl trifluoroacetate (I), 2, 4, 5-trichlorophenyl trifluoroacetate (II) and N-hydroxysuccinimide trifluoroacetate (III) were subjected to Anderson’s racemization test, only reagent III showed resistance against racemization. However, reagents I and II were also found to be useful for fragment-condensation with acylpeptides possessing glycine or proline at the C-terminus. Bradykinin was prepared using these reagents. During the synthesis, a combination of the t-amyloxycarbonyl N-protecting group and the benzyl ester was mainly used, and the alkaline hydrolysis procedure of the ester group was eliminated. Thus, colorless bradykinin with full activity was obtained in a satisfactory yield without any purification procedure.
  • Noboru Sugiyama, Choji Kashima, Makoto Yamamoto, Toki Sugaya, Ryotaro ...
    1966 Volume 39 Issue 7 Pages 1573-1577
    Published: 1966
    Released: March 27, 2006
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    Alternaria Kikuchiana Tanaka is a fungus which produces a black spot disease in pears. The metabolite of this fungus contains a phytopathogenic substance for which the name “Altenin” has been proposed. A drop of an aqueous solution of altenin (2×10−5 mg./ml.) produces a black spot on pear leaves. The stability of altenin at 80, 60, and 40°C, and the behavior of altenin in relation to some adsorbents and solvents, were studied. Its isolation from the culture filtrate was found to be properly accomplished by adsorption with active charcoal, elution with acetone, and chromatography with silica gel and alumina columns. By these procedures, besides altenin, six metabolites, diheptyl phthalate, myristic acid, succinic acid, and the ester of C15-carboxylic acid, C19-steroid and trihydroxy anthraquinone, were obtained.
  • Hiroo Inoue, Kentaro Tamaki, Nobuyuki Komakine, Eiji Imoto
    1966 Volume 39 Issue 7 Pages 1577-1582
    Published: 1966
    Released: March 27, 2006
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    The photochemical reactions of ethylene glycol, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether with ferric chloride have been carried out under a nitrogen atmosphere and with irradiation by ultraviolet light. These reactions have involved the cleavage of the carbon-carbon bond to give formaldehyde and chloromethyl methyl ether; of the carbon (–CH2–)-oxygen bond to give acetaldehyde, methanol and water, or of the carbon (CH3–) -oxygen and hydrogen-oxygen bonds to give methane, ethane, hydrogen chloride and methyl chloride. Furthermore, they have been accompanied by the photo-reduction of ferric chloride to ferrous chloride. From these results, it has been assumed that ferric chloride acts as an oxidizing reagent and Lewis acid in the photochemical reactions.
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