Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 40 , Issue 9
Showing 1-50 articles out of 61 articles from the selected issue
  • Hisashi Okuda, Makoto Nagai
    1967 Volume 40 Issue 9 Pages 1999-2003
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The PMR spectra of 5 benzoxazole derivatives were measured in CCl4 (or CDCl3) and CF3COOH. It was found that, due to the magnetic anisotropy of heteroatoms and the electricfield effect, ring protons shift to a lower field than had been anticipated from the π-electron densities (in the case of 4-H, ca. 0.4 ppm). In acid media, the π-electron density distribution of benzoxazole is changed because of the protonation of the nitrogen atom, and these two effects vanish. Correcting the measured shifts with Pople’s and Buckingham’s expressions for these effects, the following relation has been found to hold between the corrected shifts and the π-electron densities calculated with the Hückel LCAO MO method:
    τ−2.95=3.37 (π−1)
  • Setsuo Kashino, Yutaka Mugino, Shigeo Hasegawa
    1967 Volume 40 Issue 9 Pages 2004-2008
    Published: 1967
    Released: March 27, 2006
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    The reaction of benzoyl peroxide with secondary amines, namely diphenylamine, diethylamine, piperidine and pyrrolidine was studied in benzene. The rates of reactions were followed by the thermal analysis and the titration method. The rates of reactions of these amines increase in the order diethylamine<diphenylamine<piperidine<pyrrolidine. The effect of the p, p′-substituents of benzoyl peroxide on the reaction rate was examined. The Hammett relationship with respect to p, p′-substituents held for all amines with positive ρ values. It was concluded that the reactions involve nucleophilic attack by the amines on the peroxide. Stoichiometry of the reaction was also examined by the method of thermal analysis. Diethylamine reacts with the peroxide in the 2 : 1 amine-peroxide ratio, while piperidine about 1.3 : 1 and diphenylamine 0.6 : 1, respectively. ESR spectra showed that diphenylamine and diethylamine produce fairly stable free radicals in low yields, while piperidine and pyrrolidine do not yield, detectable free radicals.
  • Isao Ikemoto, Haruo Kuroda
    1967 Volume 40 Issue 9 Pages 2009-2012
    Published: 1967
    Released: March 27, 2006
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    The crystal structure of the perylene-tetracyanoethylene (TCNE) complex has been determined by the two-dimensional Fourier synthesis and by difference synthesis. The monoclinic unit cell dimensions are: a=15.79, b=8.28, c=7.31 Å, and β=96.1°. Two perylene and two TCNE molecules are in a unit cell. The space group is P21a. Perylene and TCNE molecules are stacked alternately along the b-axis, making their molecular planes parallel to each other. The center of a TCNE molecule is not directly above that of the neighboring perylene molecule. The mean separation of the molecular planes is 3.23 Å.
  • Eizo Miyazaki, Iwao Yasumori
    1967 Volume 40 Issue 9 Pages 2012-2017
    Published: 1967
    Released: March 27, 2006
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    In order to reveal the selective action of nickel and copper in the catalytic decomposition of methanol, kinetic studies of the decomposition of methanol, and methanol-d1 (CH3OD), and also of that of formaldehyde and methyl formate, both the assumed intermediates of the methanol decomposition, were undertaken over the temperature range between 100 and 330°C and the pressure range up to 30 mmHg. We also made studies of the exchange reaction of methanol, formaldehyde, or methyl formate with deuterium. The obtained rate equation for the methanol decomposition and the results on the deuterium exchange lead to the following conclusion: the rate is controlled by the unimolecular dehydrogenation of adsorbed methanol, which gives formaldehyde at first and finally hydrogen and carbon monoxide via a more stable intermediate, methyl formate. A comparison of activities between copper and nickel was made on the basis of the different behavior of formaldehyde on these catalyst surfaces. The nature of the catalyst surface and of the sites effective for the reaction were also briefly discussed.
  • Kenichi Fukui, Hiroshi Fujimoto
    1967 Volume 40 Issue 9 Pages 2018-2025
    Published: 1967
    Released: March 27, 2006
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    A general stereoselection rule governing the electrocyclic interactions has been proposed with a molecular orbital rationale. The reactions discussed from a unified point of view cover the ring-closure of polyenes, the Diels-Alder additions, 1,4-dipolar additions, the Cope and the Claisen rearrangements, the hydrogen and the proton migrations, 1,3-dipolar additions, the ring-opening of cyclic olefins, the deamination of cyclic unsaturated imines, 1,2-noncycloadditions, 1,2-eliminations, the nucleophilic displacement with allylic rearrangements, and other cyclic intermediate or complex formations. The relation to the molecular orbital symmetry has been also discussed.
  • Tsutomu Koide
    1967 Volume 40 Issue 9 Pages 2026-2029
    Published: 1967
    Released: March 27, 2006
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    The molecular motion of solid hexamethylethane was studied by the proton magnetic resonance method from the liquid nitrogen temperature to 20°C. In the temperature range between about −160°C and −120°C, the methyl group rotates about its own axis, and also the molecule rotates about the molecular axis as a whole. Above −120°C, the molecule rotates almost freely. On the other hand, the molecular motion of hexamethyldisilane in the high temperature phase has been explained in terms of the facts that the molecule rotates freely and also has a degree of translational freedom. The difference in the molecular motion between hexamethylethane and hexamethyldisilane is caused mainly by the difference in the molecular interaction.
  • Yukihiko Ichikawa, Taku Matsuo
    1967 Volume 40 Issue 9 Pages 2030-2034
    Published: 1967
    Released: March 27, 2006
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    The high-field shifts of the proton signals of cyclic ketones and lactones in the benzene solutions have been investigated. The solvent effects on the chemical shifts for the β-methylene protons of these compounds are always larger than those for the α-methylene protons. The data may be explained by the use of a model in which benzene molecules are assumed to cluster around the carbonyl group of the solute. The affinity between the solute and the solvent molecules has been mainly ascribed to the fact that both the permanent electric dipole moment and the instantaneous dipole moment of the carbonyl (or carboxyl) group induce electric dipole moments in the near-by benzene molecules. The configuration and the number of the solvent molecules clustering around the solute have been suggested to be determined by the geometrical restriction around the carbonyl group.
  • Shin-ichi Ohno
    1967 Volume 40 Issue 9 Pages 2035-2038
    Published: 1967
    Released: March 27, 2006
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    The reactions of the photochemically-produced electron, eaq, in an aqueous solution of hexacyanoferrate(II) were studied when H2PO4, NO3, H2O2, CO2, [Fe(CN)6]3− and H3BO3 were used as the solute. The relative reaction rates, obtained by competition kinetics, are compared with those calculated using the published data on the absolute rate constants. The agreements are satisfactory in some cases, but not in other cases (e.g., H2PO4, H2O2 and CO2), for which a possible explanation is given. This explanation includes the postulation of an electrontransfer reaction between the solutes employed; it is shown that information on the efficiency of this electrontransfer reaction may be obtained by using the relative rates obtained both from competition kinetics and from pulse radiolysis.
  • Shin-ichi Ohno
    1967 Volume 40 Issue 9 Pages 2039-2042
    Published: 1967
    Released: March 27, 2006
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    A method for the determination of the relative rate constants for reactions of the OH radical is described. The OH radical is generated from the reaction between N2O and the photochemically-produced electron in a solution of 10−3 M hexacyanoferrate(II) irradiated at 2537 Å. The method has been applied to the determination of the rate constants for the reactions of OH with methanol, ethanol, 2-propanol, formate, bromide, glycine, and boric acid relative to that with [Fe(CN)6]4−. The values found are compared with those obtained by other methods, and their significance is discussed.
  • Niro Matsuura, Nobuyoshi Shinohara, Masaru Nishikawa, Masao Takizawa
    1967 Volume 40 Issue 9 Pages 2042-2047
    Published: 1967
    Released: March 27, 2006
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    The hydrogen and hydrogen peroxide produced in the radiolysis of CoIII-EDTA (CoIIIY) in 0.8 N sulfuric acid have been measured. The yields of hydrogen and hydrogen peroxide were found to be G(H2)=0.4 and G(H2O2)=2.5 for the aerated system, G(H2)=3.2 and G(H2O2)=0 for the deaerated system where G denotes the yield at the infinite solute concentration. The decomposition mechanism proposed previously was discussed in detail on the basis of the observed G(H2) and G(H2O2) and of the effect of chloride ion on the decomposition yield G(–CoIIIY). A similar experiment was carried out for EDTA alone and the decomposition mechanism was discussed.
  • Toshiaki Kabe, Toshihiko Mizuno, Iwao Yasumori
    1967 Volume 40 Issue 9 Pages 2047-2051
    Published: 1967
    Released: March 27, 2006
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    In order to measure the small surface area of metal foils down to a few ten square centimeters by making use of gas adsorption, an apparatus was developed, which made it possible to estimate the amount of adsorbed xenon at 77.5°K from the desorption of the gas on the surface by moving the foil from the adsorbing bulb into the hot furnace; the change in the surface area of palladium foil catalysts which had been annealed at various temperatures was followed by the use of this method. The roughness factor, the ratio of the real surface area to the geometrical one, of the palladium foil decreased from 1.7 to 1.1 with the progress of annealing at 150–300°C, but it increased to 1.9 after heating at 400°C and then decreased again under treatment at high temperatures to 1.0 for 800°C. The chemisorption of carbon monoxide on the same foil catalyst, which is often used for the surface-area determination, was also studied, and the difference between the adsorbed states of the respective molecule on the palladium surface was briefly discussed in order to compare these methods.
  • Kenichi Fukui, Tokio Yamabe
    1967 Volume 40 Issue 9 Pages 2052-2063
    Published: 1967
    Released: March 27, 2006
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    A theory is presented for a general treatment of the molecular size distribution, the gel point, and the post-gelation phenomena with respect to polymerization with formations of various kinds of interunit junctions, assuming (1) that all functional groups are equally reactive, and (2) that no kind of intramolecular interunit junction occurs. These interunit junctions appear concurrently in a system composed of a mixture of monomeric molecules and with a distributions of functionalities. Two cases are treated: (1) when the interunit junction is characterized only by the number of functional groups involved in its formation, and (2) when the interunit junction is characterized not only by the number of groups, but also by the magnitude of the free energy of its formation. The former is illustrated by the poly condensation with bi- or terfunctional interunit junctions or with both. The latter is illustrated by the polycondensation between A and B groups in a mixture of A-monomers with equireactive A groups and B-monomers with equireactive B groups, where a B-monomer is regarded as a kind of interunit junction.
  • Kiyoshi Arakawa, Nobuo Takenaka
    1967 Volume 40 Issue 9 Pages 2063-2068
    Published: 1967
    Released: March 27, 2006
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    Ultrasonic investigations of aqueous solutions of polyethylene glycol solutions have been made by means of an ultrasonic pulse technique. Two samples of the polymer have been used, the molecular weights being 4000 and about 6000. The measurements of the sound velocity and of the absorption have been made on 5–30 wt% solutions of the polymers, together with an ethylene glycol-water mixture for the sake of comparison, over the frequency range of 5–45 Mc/sec. The temperature has been varied over the range of 10–70°C. It has been found that the velocity vs. temperature curve for each solution has a peak, and that the peak has a trend to shift to a lower temperature with the increase in the concentration. From the absorption data obtained, it has been found that a characteristic relaxation frequency appears near 40 Mc/sec at room temperatures. The magnitude of the absorption has been found to increase linearly approximately with the increase in the concentration, and to be independent of the molecular weight of the polymers at least in the range studied. From the temperature dependence of the relaxation frequency, the apparent activation energy of the relaxation process has been estimated to be not larger than 1 kcal/mol. It has been concluded from the results that the source of the relaxation process is not the hydrogen bonding between polymer molecules and water, as recently stated by G. G. Hammes et al. (J. Phys. Chem., 70, 1610 (1966)), but some intramolecular process.
  • Masako Maeda, Kimiko Matsuo, Mamoru Nakanishi, Masamichi Tsuboi
    1967 Volume 40 Issue 9 Pages 2068-2072
    Published: 1967
    Released: March 27, 2006
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    Three copolymers of riboinosinic acid and riboguanylic acid (poly IG), with guanylic acid contents of 21.6%, 33%, and 45%, have been prepared, as well as three homopolymers of ribocytidylic acid (poly C), riboinosinic acid (poly I), and riboguanylic acid (poly G). On mixing both the poly IG and the poly G with poly C in various mole ratios in an aqueous solution, a marked hypochromicity was observed in the 250 mμ region, and it was shown that there are double helical complexes similar to the well-known poly(I+C) formed in the solutions. The optical melting profile of each complex into random coils was examined, and it was found that the guanine-cytosine pair is 20% (in enthalpy) more stable than the hypoxanthine-cytosine pair. It was also found that actinomycin D, which has no effect on the melting of poly (I+C), stabilizes the helical structure of poly(IG+C).
  • Yusei Maruyama, Hiroo Inokuchi
    1967 Volume 40 Issue 9 Pages 2073-2077
    Published: 1967
    Released: March 27, 2006
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    In order to examine the effect of space-charge polarization in the course of drift-mobility measurements in anthracene single crystals, we employed a pulse electric field and measured the change in photoresponses according to the light-delay times. No distinct reduction of photoresponses was found, and the value of mobility was nearly the same as the one obtained by measurement with the conventional dc field. To obtain knowledge of the microscopic mobility in anthracene crystals, we also measured the photo-Hall effect of anthracene using the Redfield, Kobayashi and Brown method. The observed Hall mobility was in the range of 25–200 cm2/ V.sec. This large value of Hall mobility will be briefly discussed in terms of the multiple-trapping effect.
  • Wataru Suëtaka
    1967 Volume 40 Issue 9 Pages 2077-2081
    Published: 1967
    Released: March 27, 2006
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    The infrared spectra of thin urea and thiourea films, several hundred Angstroms thick, on a steel plate were obtained using an optical system in which the beam polarized parallel to the plane of incidence was incident at 70° upon a steel plate covered with film. The spectra obtained showed that the c-axis of the urea crystal was parallel to the metal surface. However, the abnormal behavior of the NH2 bending and the NH2 twisting bands suggests that the urea molecule in the film was deformed from the planar structure. The intensities of the infrared bands of thiourea belonging to the B1 species decreased in the film, and it may be concluded that the c-axis of the crystal is nearly parallel to the metal surface. The considerable rise in frequency of the NH2 wagging band observed in the thin thiourea film may arise from the deformation of the crystal. As for the thioureacollodion film, thiourea A1 bands appeared to be very weak, corresponding to the C=S bond orientation parallel to the metal surface. The dichroism of the thiourea bands in the 3 μ region obtained about the thiourea and thioureacollodion thin films is in agreement with the Badger-Waldron assignment of the absorption bands.
  • Tsunehiko Nakagawa, Setsuo Takamuku, Hiroshi Sakurai
    1967 Volume 40 Issue 9 Pages 2081-2085
    Published: 1967
    Released: March 27, 2006
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    The γ-radiolysis of 1,4-cyclohexadiene vapor has been investigated at room temperature. The gaseous products are hydrogen, acetylene, and 1,3-butadiene. Benzene, cyclohexene, 1,3-cyclohexadiene, and 1,3,5-hexatriene are identified as the low volatile liquid products. The yield of each product is almost independent of the dose (0.87–9.11)×1019 eV, while it is remarkably dependent on the gas pressure (8–56 mmHg). The G values of hydrogen, the C2+C4 gas fraction, benzene, and cyclohexene are 1.95, 1.25, 28.5, and 14.0 respectively at 42 mmHg. The large yields of benzene and cyclohexene may be explained in terms of a chain mechanism. The pressure dependence of these products is very similar in both the Hg-sensitized photolysis and the γ-radiolysis of this diene vapor. The presence of the long-lifetime intermediates is as expected. The experiments with nitric oxide added as a radical scavenger suggest that the main path of hydrogen formation is the radical process.
  • Kyoji Tôei, Haruo Miyata, Hirosumi Kimura
    1967 Volume 40 Issue 9 Pages 2085-2089
    Published: 1967
    Released: March 27, 2006
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    o-, m-, and p-Nitrophenyl-azo-chromotropic acids were prepared as colorimetric reagents for thorium. The acid dissociation constants of the reagents have been determined spectrophotometrically, their pK1 values being 8.96, 8.60, and 8.77 for the and o-, m-, and p-compounds respectively at 25°C and when μ=0.1. The reagents form violet 1 : 1 complexes in an acidic solution. The apparent stability constants have been measured spectrophotometrically. The order of the apparent stability constants of the complexes agrees with that of the first acid dissociation constants of the reagents; m-nitro>p-nitro>o-nitro compounds.
  • Akira Misono, Yasuzo Uchida, Masanobu Hidai, Hideo Kanai
    1967 Volume 40 Issue 9 Pages 2089-2091
    Published: 1967
    Released: March 27, 2006
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    By the addition reaction of acrylonitrile to hydridobis (dimethyl- or diphenylglyoximato)-pyridinecobalt, only 1-cyanoethyl complexes were obtained. The 2-cyanoethyl complex was not formed from that reaction, but from the reaction of 3-bromopropionitrile with the hydride complex. NMR spectroscopy was used to confirm the structure of the complexes. The isomerization of the 2-cyanoethyl complex to the 1-cyanoethyl complex at 70°C was not observed by NMR measurements. The reaction of these complexes with acrylonitrile was carried out under a hydrogen atmosphere. It was observed that 2-methylglutaronitrile was formed from the reaction of the 1-cyanoethyl complex with acrylonitrile. The thermal decomposition and the reaction of the complexes with hydrochloric acid were also investigated.
  • Toshikazu Mitsuji
    1967 Volume 40 Issue 9 Pages 2091-2095
    Published: 1967
    Released: March 27, 2006
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    The liquid zinc amalgam method was developed as a rapid procedure for the reduction of pentavalent protactinium. Several minutes were sufficient for the complete reduction of 4.2×10−4 M pentavalent protactinium in both hydrochloric and sulfuric acid solutions. The stability of tetravalent protactinium in these media was investigated by spectrophotometry. Re-oxidation occurred gradually, even in the absence of atmospheric oxygen, and amounted to 8% in 15 hr. These results may be understood in terms of the slow rate of the (2Pa4++2H+\ ightleftarrows2Pa5++H2) reaction. The formation of sulfato complexes of tetravalent protactinium was inferred by spectrophotometry with relation to the similarity of the electronic structure between Pa4+(5f1) and Ce3+(4f1).
  • Itaru Motooka, Genzo Hashizume, Masamitsu Kobayashi
    1967 Volume 40 Issue 9 Pages 2095-2099
    Published: 1967
    Released: March 27, 2006
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    The effect of the atmosphere, particularly of the relative humidity, on the process of grinding of sodium trimetaphosphate was examined, and the following results were obtained: 1) In the case of grinding in air, as the relative humidity increased, the grinding effect—for example, the time required to reduce trimetaphosphate molecules to one half—decreased in the humidity range from 20 to 60%. 2) In the case of grinding in nitrogen or carbon dioxide gas, the grinding effect was the same as that in air. In view of these results, it may be said that humidity is one of most important factors in the process of grinding sodium trimetaphosphate.
  • Nobuyuki Tanaka, Masaru Kimura
    1967 Volume 40 Issue 9 Pages 2100-2106
    Published: 1967
    Released: March 27, 2006
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    The kinetics of the substitution reaction of nickel(II) and copper(II)-nitrilotriacetate complexes and that of nickel(II) and cobalt(II)-nitrilotriacetate complexes in acetate buffer solutions have been studied by a similar method in principle to that reported previously. The reactions were treated as to proceed through both hydrated metal ions and monoacetato complexes. The rate constants of eight reaction paths, of which four involve hydrated nickel(II) ions and the others, monoacetatonickel(II) complexes, were determined at ionic strength 0.2 at 0°C. The backward reactions were found to proceed also through eight reaction paths in which the dissociation of Ni(II)-nitrilotriacetate complexes is rate-determining. The values of rate constants obtained for the forward and the backward reactions indicate that all the reactions proceeding through monoacetatonickel(II) complexes are faster than the corresponding reactions through hydrated nickel(II) ions.
  • Akiko Satô
    1967 Volume 40 Issue 9 Pages 2107-2110
    Published: 1967
    Released: March 27, 2006
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    Various methods for the reduction of hexavalent uranium to the trivalent state were examined. It was found that the liquid-zinc-amalgam method is simple and rapid, and gives a high yield with a good reproducibility in hydrochloric, sulfuric, and perchloric acid solutions. The percentage of reduction is over 99% in a 0.5 N hydrochloric acid solution. Next, the stability of trivalent uranium in these media was investigated; it was observed that the trivalent uranium ion is fairly stable in any hydrochloric, sulfuric and perchloric acid solutions at a low concentration of the acids in the absence of atmospheric oxygen, but that it becomes unstable as the acid concentration increases. Both the percentage of reduction by the liquid-zinc-amalgam method and the stability of trivalent uranium are highest in a hydrochloric acid solution, next highest in a perchloric acid solution, and lowest in a sulfuric acid solution.
  • Yasukazu Ohkatsu, Tetsuo Osa, Akira Misono
    1967 Volume 40 Issue 9 Pages 2111-2116
    Published: 1967
    Released: March 27, 2006
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    A possible configuration of the pale blue precipitated divalent cobalt catalyst, synthesized by the addition of a saturated solution of deionized water in acrolein to a vigorously stirred solution of Co(acac)2 in benzene, is deduced from the infrared spectrum and thermal analyses; it is considered to be Co(acac)2-H2O-acrolein, in which acrolein is coordinated through its aldehyde oxygen. When the precipitated catalyst is used in the oxidation of acrolein, the induction period of oxygen absorption is shorter, the rate of oxygen absorption is higher, and the amount of oxygen absorbed is more than when any other divalent cobalt-acetyl-acetonate are employed. From these results, it is considered that the precipitated catalyst contains a species which is converted into a more active trivalent form faster than the other divalent catalysts. Furthermore, Co(acac)2 and Co(acac)2·2H2O are considered to take part in the oxidation via Co(acac)2-H2O-acrolein.
  • Yasukazu Ohkatsu, Tetsuo Osa, Akira Misono
    1967 Volume 40 Issue 9 Pages 2116-2121
    Published: 1967
    Released: March 27, 2006
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    Some water was added as a model to a reaction solution containing Co(acac)2 before the beginning of the reaction by two methods in order to examine the effects of water formed during the reaction. These two methods gave different phenomema in the induction periods and different oxygen absorption rates. From these results and those with Co(acac)2·2H2O, the water added is considered to act in two ways, increasing the reaction rate by the coordination with the catalyst and decreasing the reaction rate when not bonded with the catalyst. The latter effect is considered in detail on the basis of the oxygen absorption rate: −dO2/dt=k(acrolein)0.88. (catalyst)0.39(H2O)r, wherein r is −0.1 or −0.21. This rate equation accorded well with the derived rate equation considering the reaction phenomena and the interaction among the catalyst, acrolein, and water in the initiation reaction.
  • Takashi Maeda
    1967 Volume 40 Issue 9 Pages 2122-2128
    Published: 1967
    Released: March 27, 2006
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    The acetonation reaction of L-sorbose with acetone dimethyl ketal was investigated. The products and the yields were greatly influenced by the reaction conditions. The reaction at 45°C gave 1, 3 : 4, 6-di-O-isopropylidene-β- (VIIa), 1, 2 : 4, 6-di-O-isopropylidene-α- (Va) and 2, 3 : 4, 6-di-O-isopropylidene-α-L-sorbofuranose (IVa) and the β-anomer of Va (VIa). At the refluxing temperature, the reaction afforded IVa and the 2-O-methyl derivative of VIIa (VIIe), while at room temperature it yielded 1, 2 : 3, 4-di-O-isopropylidene-α-L-sorbopyranose (VIIIa), 1, 2 : 4, 5-di-O-isopropylidene-α-L-sorbopyranose (IXa), and 5-O-α-methoxyisopropyl-1, 2 : 3, 4-di-O-isopropylidene-α-L-sorbopyranose (VIIIc).
  • Ichiro Moritani, Naoki Toshima, Shiro Nakagawa, Masatoshi Yakushiji
    1967 Volume 40 Issue 9 Pages 2129-2134
    Published: 1967
    Released: March 27, 2006
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    Photoreactions of conjugated or non-conjugated, five-membered, cyclic ketones were investigated. Irradiation of 2,3,4,5-tetraphenyl-2-cyclopenten-1-one in 2-propanol with ultraviolet light under a slow stream of nitrogen or oxygen gave 1-oxo-2,3-diphenyl-2,3-dihydro-1H-cyclopenta[l]phenanthrene (55%) and 1-oxo-3-hydroxy-2,3-diphenyl-2,3-dihydro-1H-cyclopenta[l]phenanthrene (about 20%). Similar irradiation of 3,4-diphenyl-3-cyclopenten-1-one under a nitrogen stream gave 2-oxo- and 2-hydroxy-2,3-dihydro-1H-cyclopenta[l]phenanthrene in 33% and 11% yields respectively. In both cases, there was observed photocyclization of a cis-stilbene skeleton to a phenanthrene. However, on irradiation of 2,2-dimethyl-3,4-diphenyl-3-cyclopenten-1-one, there was obtained a decarbonylation product, 1,1-dimethyl-1,2-dihydrocyclobuta[l] phenanthrene. The reaction courses of these photoreactions are proposed.
  • Kunihiro Ichimura, Masaki Ohta
    1967 Volume 40 Issue 9 Pages 2135-2139
    Published: 1967
    Released: March 27, 2006
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    The reaction of either N-(p-chlorophenyl)diphenylketenimine or N-(p-chlorophenyl)diphenylacetimidoyl chloride with ethyl cyanoacetate gave the identical α, β-unsaturated ester. Whilst the reaction of the ketenimine with diethyl malonate yielded β, γ-unsaturated diester, the isomeric α, β-unsaturated diester was obtained by the reaction of the imidoyl chloride with the malonate. These remarkable different phenomena could be ascribed to the difference in bulk between cyano and carbethoxy groups. The structures of these products were discussed on the basis of the infrared and ultraviolet spectroscopic data and the reaction mechanisms were proposed. Additionally, the pyrolysis of the products was studied and the β, γ-unsaturated diester was found to give quinolin-4-one together with an α-naphthol derivative under elimination of ethanol, whilst only quinolin-4-one was isolated on the pyrolysis of the isomeric α, β-unsaturated diester.
  • Katsutoshi Yasufuku, Sumio Hirose, Shun’ichi Nozakura, Shunsuke ...
    1967 Volume 40 Issue 9 Pages 2139-2145
    Published: 1967
    Released: March 27, 2006
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    To investigate the steric effect of β-substituents of styrene derivatives on their reactivities in radical copolymerization, fourteen cis- and trans-β-alkylstyrenes were synthesized and copolymerized with acrylonitrile. The reactivities of β-alkylstyrenes toward the acrylonitrile radical decreased in the order: CH3>C2H5\gtrsimn-C3H7\gtrsimn-C4H9>iso-C3H7>s-C4H9>t-C4H9 in both the cis- and trans-series. Linear relationships were found between the relative reactivities and Taft’s or Hancock’s steric parameter. These relationships and the study of the monomer structures led to the following conclusions: 1) The low reactivity of β-alkylstyrenes in radical polymerization is to be attributed to the steric hindrance of β-alkyl substituents. 2) The effect of the hyper conjugation of the β-alkyl groups is not important. 3) The difference in the reactivities among intramolecularly-hindered cis-β-alkylstyrenes is due not to the difference in resonance of the monomer, but to the difference in the steric hindrance of the β-alkyl groups toward the attacking radicals.
  • Katsutoshi Yasufuku, Shun’ichi Nozakura, Shunsuke Murahashi
    1967 Volume 40 Issue 9 Pages 2146-2149
    Published: 1967
    Released: March 27, 2006
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    The radical copolymerizations of cyclopentene, cyclohexene, cycloheptene, cyclooctene, trimethyl-, and tetramethyl-ethylene with acrylonitrile (AN, M1) were carried out, and the reactivities of these monomers toward the AN radical (1/r1) were found to be as follows: cyclopentene, 0.21; cyclohexene, 0.13; cycloheptene, 0.15; cyclooctene, 0.35; trimethylethylene, 0.37, and tetramethylethylene, 0.25. The reactivity of these internal olefins in radical polymerization was discussed.
  • Toshio Nakagawa, Hisao Tokuoka, Kazuhiko Shinoto, Juji Yoshimura, Tets ...
    1967 Volume 40 Issue 9 Pages 2150-2154
    Published: 1967
    Released: March 27, 2006
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    D-Arabinitol and xylitol were acetonated, benzylated and then hydrolyzed with a mineral acid to afford in good yields the corresponding 1-O-benzyl derivatives, which were identified by a periodate oxidation and a chemical identification. A preferential acetonation of the pentitols is discussed in a view of stereochemistry. Synthesis of 2-O-benzyl-D-arabinitol and 3-O-benzylxylitol are also described.
  • Hideo Okai, Naokazu Imamura, Nobuo Izumiya
    1967 Volume 40 Issue 9 Pages 2154-2159
    Published: 1967
    Released: March 27, 2006
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    The ammonolysis of cis-epoxy succinic acid yielded threo-hydroxy-DL-aspartic acid exclusively, but that of trans-epoxy acid produced a mixture of 68% erythro- and 32% threo-hydroxyaspartic acid. This mixture was separated into the two pure diastereomers through either a Dowex 1 column chromatography or fractional crystallization after the mixture had been changed to ammonium salt. The threo- and erythro-DL-amino acids so prepared were resolved by optically active lysine and ornithine respectively. The contribution (partial molar rotation) of the α-and β-asymmetric centers to the observed molar rotations of the optically active diastereomeric hydroxyaspartic acids in water and 5 N hydrochloric acid was calculated.
  • Toshio Hayashi, Isaburo Hori, Hideo Baba, Hiroshi Midorikawa
    1967 Volume 40 Issue 9 Pages 2160-2163
    Published: 1967
    Released: March 27, 2006
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    The NMR spectra of α-cyano-β-amino-β-alkylacrylic esters prepared from α-cyano-β-methoxy-β-alkylacrylic esters and simple amines have been studied. It has been found that these aminoesters, in a variety of solvents, are all present in an intramolecular hydrogen-bonded enamine form with a chelate ring.
  • Shumpei Sakakibara, Yasutsugu Shimonishi, Yasuo Kishida, Masanori Okad ...
    1967 Volume 40 Issue 9 Pages 2164-2167
    Published: 1967
    Released: March 27, 2006
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    The properties of anhydrous hydrogen fluoride (HF) as a reagent for the acidolysis of various protective groups have been studied. Amino acids with various protective groups were each treated with HF at 0 or 20°C in the presence of anisole, and the reaction products were tested. Thus, HF was found to be much better than the other known reagents, such as hydrogen bromide and trifluoroacetic acid. In the present study, the following groups were shown, for the first time, to be removed safely: the nitro group in nitroarginine, the diphenylmethyl group in diphenylmethylamide, the t-butyl group in S-t-butylcysteine, the isopropyloxycarbonyl group, and the isopropyl ester group. A new and convenient apparatus was designed for the safe handling of HF for peptide synthesis.
  • Masajiro Kawana, Sakae Emoto
    1967 Volume 40 Issue 9 Pages 2168-2171
    Published: 1967
    Released: March 27, 2006
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    Asymmetric synthesis of atrolactic acid was investigated by the reaction of methylmagnesium Iodide with phenylglyoxylic ester containing such an optically active component as 1,2 ; 5,6-di-O-cyclohexylidene-D-glucose, its isopropylidene derivative 5-O-ethyl-1,2-O-isopropylidene-D-xylose, its 5-deoxy-5-S-ethyl derivative, or 5-deoxy-1,2-O-isopropylidene-D-xylose. All of the resulting sugar atrolactates were very easily hydrolyzed with alkali at room temperature to afford the levorotatory acid in 22–38% optical yield. The asymmetric reactions proceeded in accordance with Prelog’s rule, but a Prelog’s scheme for asymmetric induction was slightly modified when the steric course for 3-O-phenylglyoxyloyl-1,2 ; 5,6-di-O-cyclohexylidene- and -isopropylidene-D-glucose was discussed.
  • Katsuhiko Wakabayashi, Yoshio Kamiya, Nobuto Ohta
    1967 Volume 40 Issue 9 Pages 2172-2176
    Published: 1967
    Released: March 27, 2006
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    For the purpose of elucidating the catalysis of the binary system consisting of Sn and Sb oxides, recommended in the patent for the oxidation of propylene to acrolein, the oxidation of propylene has been studied; in addition, the X-ray patterns of the system have been investigated. The mixtures of this binary system after sintering were different in color according to the catalyst composition and the calcination conditions. It was found that the color of the catalyst is closely connected with the formation of acrolein, and also that the blue-colored catalysts are effective in the selective production of acrolein. The pure tin oxide catalyst yielded mainly carbon dioxide and monoxide, while the pure antimony yielded scarcely any product. However, a selectivity to acrolein of more than 70% was obtained at 450°C over a catalyst with an optimal composition, for example, one with a Sn to Sb atomic ratio of 3 : 1 which had been calcined at 1000°C for 3 hr. The formation of acrolein was investigated as a function of the catalyst composition and the calcination conditions. According to the X-ray data, Sb oxide was soluble in Sn oxide, thus forming solid solutions, and the mixtures’ becoming colored was attributable to the formation of the solid solutions. It was concluded that the formation of acrolein over this binary system is closely connected with the solid solutions formed between Sn and Sb oxides.
  • Harusuke Tokui, Kiroku Yamazaki
    1967 Volume 40 Issue 9 Pages 2177-2181
    Published: 1967
    Released: March 27, 2006
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    Some characteristic properties of a polybutadiene - acrylic acid - acrylonitrile terpolymer (PBAN) and of the elastomers derived from it were determined to obtain the fundamental information as fuel binders for propellants. The chemical composition of the prepolymer (RF-2) was determined to be:
    [{−CH2−CH=CH−CH2−}84.0{−CH2−CH(CN)−}12.6{−CH2−CH(COOH)−}3.4]n,
    and it was found to be a Newtonean fluid. Since the prepolymer was found to be, on the average, 1.2 functional, much mono- or non-functional portion is probably included in it. The tensile properties of the elastomer, based on the cured PBAN, were not as good as those of telechelic elastomers, as far as the same curing agents were concerned. This may be attributed to the influence of the random distribution of the cross-linking sites and to that of the resultant terminal sections of the elastomer. The ultimate tensile strength and ultimate elongation of the PBAN elastomers were in the range of 3–6 kg/cm2 and 100–400% respectively. It should be remembered that the elastomers contained as much as 30–50% sol fractions.
  • Toshinobu Imanaka
    1967 Volume 40 Issue 9 Pages 2182-2183
    Published: 1967
    Released: March 27, 2006
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  • S. M. Verma, R. C. Srivastava
    1967 Volume 40 Issue 9 Pages 2184-2186
    Published: 1967
    Released: March 27, 2006
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  • Kenichi Murata
    1967 Volume 40 Issue 9 Pages 2187-2189
    Published: 1967
    Released: March 27, 2006
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  • Nobuo Mori, Emiko Nakamura, Yojiro Tsuzuki
    1967 Volume 40 Issue 9 Pages 2189-2190
    Published: 1967
    Released: March 27, 2006
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  • Nobuo Mori, Emiko Nakamura, Yojiro Tsuzuki
    1967 Volume 40 Issue 9 Pages 2191-2192
    Published: 1967
    Released: March 27, 2006
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  • Jun Niwa
    1967 Volume 40 Issue 9 Pages 2192-2194
    Published: 1967
    Released: March 27, 2006
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  • Shiro Kuroiwa, Minoru Ogawa, Matao Nakamura
    1967 Volume 40 Issue 9 Pages 2195-2197
    Published: 1967
    Released: March 27, 2006
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  • Minoru Hirota, Kenji Kitajima
    1967 Volume 40 Issue 9 Pages 2197-2199
    Published: 1967
    Released: March 27, 2006
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  • Satoshi Suzuki, Hiroaki Baba
    1967 Volume 40 Issue 9 Pages 2199-2200
    Published: 1967
    Released: March 27, 2006
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  • Chie Mugiya, Hiroaki Baba
    1967 Volume 40 Issue 9 Pages 2201-2202
    Published: 1967
    Released: March 27, 2006
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  • Tsutomu Mizoroki, Mikitake Nakayama
    1967 Volume 40 Issue 9 Pages 2203
    Published: 1967
    Released: March 27, 2006
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  • Takeshi Matsui, Akira Komatsu, Tatsuo Moroe
    1967 Volume 40 Issue 9 Pages 2204
    Published: 1967
    Released: March 27, 2006
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  • Atsushi Ogata, Yoneho Tabata, Hiroshi Hamaguchi
    1967 Volume 40 Issue 9 Pages 2205
    Published: 1967
    Released: March 27, 2006
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