Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 40 , Issue 11
Showing 1-50 articles out of 69 articles from the selected issue
  • Yoshikane Kawasaki, Mitsufusa Hori, Kazushige Uenaka
    1967 Volume 40 Issue 11 Pages 2463-2467
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The stability constants of several pyridine N-oxide complexes of trimethyltin chloride and dimethyltin dichloride have been measured spectrophotometrically in acetonitrile. The values decrease with an increase in the electron-attracting power of the substituent on the pyridine ring. The infrared spectra of several pyridine N-oxide complexes of tin(IV) have been measured from 60 cm−1 to 5000 cm−1. The Sn–O stretching vibration has been observed in the region of 300—400 cm−1, and the frequency depends considerably on the substituents of the tin atom. The Sn–O stretching frequency in the pyridine N-oxide complexes of tin(IV) is rather lower than those in alkyltin alkoxides, which have a large covalent character in the Sn–O bond, but it is higher than those in trialkyltin carboxylates, which have an ionic character in the Sn–O bond. The Sn–O bond in the pyridine N-oxide complexes has been assumed to have a rather large ionic character, from the fact that the dependence of the stability constant on the substituent of the pyridine ring is similar to that of the pKa of the ligand, and from the fact that the frequency of the Sn–O stretching vibration is rather close to that of the trialkyltin carboxylates.
  • Hiroshi Tsubomura, Sigenobu Sunakawa
    1967 Volume 40 Issue 11 Pages 2468-2674
    Published: 1967
    Released: March 27, 2006
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    Some aromatic anions in solutions show absorption spectra with many sharp bands in the visible and ultraviolet regions. It is pointed out that this is rather remarkable in view of the fact that aromatic molecules have very small electron affinities, nearly zero or even negative, in the gas phase. It is then emphasized that the potential for the electron in the negative ions is much more localized than the Coulomb potential. Accordingly, some of the features of the negative ions are deduced by the use of a simple well-type potential. The important conclusions obtained are: 1) Negative ions may have discrete electronic energy levels not only in the E≤0 region but also in the E>0 region, that is, higher than the detachment energy. 2) The larger the domain of the potential well for the electron, the discrete energy levels can exist at the higher energy. 3) These energy levels at E>0 should, of course, be unstable, mostly leading rapidly to the electron detachment, but their lifetime are the longer, the larger the domain of the potential well. These consequences seem to account well for the above-mentioned spectra of aromatic anions. Other features of the negative ions and the nature of the charge-transfer states in the charge-transfer complexes are also discussed.
  • Akira Kuboyama, Sanae Yabe
    1967 Volume 40 Issue 11 Pages 2475-2479
    Published: 1967
    Released: March 27, 2006
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    Phosphorescence bands, their life times, and the excitation spectra of anthraquinone, α-naphthoquinone, phenanthrenequinone, acenaphthenequinone, benzophenone, benzil, furil, and camphorquinone at 77°K in a rigid solution and in the crystalline state have been studied. In a rigid solution the lifetimes of these phosphorescence bands are in the range (10–0.1 msec). The solvent effect on lifetimes shows clear differences between o- and p-quinones. The behavior of these phosphorescence bands is similar to that of the n→π* bands of these compounds. From these facts, these bands are all safely identified as π*n bands. The phosphorescence bands of p-quinones in the crystalline state are at far longer wavelengths than those in a rigid solution, and the lifetimes of the former are far longer than those of the latter. The dichroism of excitation spectrum of the phosphorescence band of anthraquinone proved that the phosphorescence band is polarized perpendicularly to the 320 mμ band and parallel to the 270 mμ band.
  • Yoshihiro Nakato, Naoto Yamamoto, Hiroshi Tsubomura
    1967 Volume 40 Issue 11 Pages 2480-2485
    Published: 1967
    Released: March 27, 2006
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    The photo-ionization of N, N, N′, N′-tetramethyl-p-phenylenediamine (TMPD) in nonpolar solvents was found to occur by the two-step process, with the triplet state as the intermediate. It will be reported here that the photo-ionization of TMPD in polar solvents occurs by the same two-step process, both at 77°K and at room temperature. The flash method was used for the experiments at room temperature. On the other hand, the photo-ionization of TMPD occurs by the single-photon process in ethanol solutions at room temperature when a naphthalene molecule encounters TMPD in the singlet-excited state. The ionization mechanism will be discussed on the basis of these results.
  • Akira Kira, Masao Koizumi
    1967 Volume 40 Issue 11 Pages 2486-2492
    Published: 1967
    Released: March 27, 2006
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    Flash photolytic studies have been made to elucidate the behavior of the intermediates and to obtain the rate constants of the elementary reactions, which are related to the reactions between acridine and acridan in benzene solutions. Two transient species, triplet and semireduced acridine, have been detected. The elementary reactions the rate constants of which have been measured are:
    AT→A [1] k1=1–2×103sec−1
    AT+AT→ [2] k2=6.0×109M−1sec−1
    AT+O2→(A+O2*) [3] k3=6×109M−1sec−1
    AT+AH2→2AH [4] k4=3×108M−1sec−1
    2AH→(AH)2 [5] k5+k6=2–3×109M−1sec−1
    →A+AH2 [6]
    The quantity of AH produced in the presence of a small quantity of oxygen decreases with an increase in the oxygen concentration; if one assumes that Reaction [3] is mere deactivation, the decrease in acridine is too large to be expected from the values of k3 and k4. Hence, it has been inferred that O2* (or some other reactive intermediate) oxidizes AH2. The decrease in the yield of AH with the increase in the oxygen concentration has been attributed to the deactivation of O2* by a third substance. The other kinetic data have been found to be consistent with this scheme.
  • Kichisuke Nishimoto
    1967 Volume 40 Issue 11 Pages 2493-2497
    Published: 1967
    Released: March 27, 2006
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    The electronic structures of uracil, lumazine, and alloxazine, and all their possible tautomeric isomers have been calculated by the LCAO MO SCF method based on variable beta approximation. The calculated singlet transition energies for diketo forms agree quite well with the experimental results. The present theory suggests that some tautomeric forms of lumazine and alloxazine will behave as both electron donors and electron acceptors. In biological systems, uracil, lumazine, alloxazine, and isoalloxazine will act as both oxidizers and reducers through hydrogen bonds with some molecules, such as protein and DNA.
  • Mitsuhiko Hida
    1967 Volume 40 Issue 11 Pages 2497-2501
    Published: 1967
    Released: March 27, 2006
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    It has been reported that a zinc-methylene complex prepared from methylene iodide and a zinc-copper couple reacts with olefins to give cyclopropanes, and with aldehydes to give olefins. The former reaction was suggested to be electrophilic, and the latter, nucleophilic. In this report this duality of the zinc-methylene complex and the reactivities of double bonds will be discussed in terms of the interaction between the reagent orbitals and the substrate orbitals. The reactivity of the carbonyl group will mainly be determined by the nucleophilic superdelocalizability of carbonyl carbon, while that of the olefinic double bond will mainly be determined by the electrophilic total delocalizability (SsE+StE+2PstE). The theoretical predictions of these reactivities are consistent qualitatively with the experimental results.
  • Akira Yokohata, Satoru Tsuda
    1967 Volume 40 Issue 11 Pages 2502-2507
    Published: 1967
    Released: March 27, 2006
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    Although most of the reaction systems hitherto treated are limited to acidic solutions in the series of this present research, this work has been extended to neutral solutions. Silent discharge leads to production of hydrochloric acid from neutral aqueous chloralhydrate. A linear correlation was observed between yield of hydrochloric acid and electric discharge current. This finding has been successfully interpreted in terms of absorbed dose, the value of which can be estimated at a given electric discharge current. Yields of hydrochloric acid were not significantly affected by chloralhydrate concentration between 1×10−2 M and 1×10−3 M. The experiments of the radical scavenging effect of cupric ion and bromide ion showed that KH+Cu2+KH+CCl3CH(OH)2≈0.2 and KOH+BrKOH+CCl3CH(OH)2≈9, and also that the following formula holds approximately irrespective of kind of gas used in low solute concentration and dose rate used in this work: values of hydrogen atom G(HCl)\simeq3G(OH)+G(H). Moreover, these findings also suggested that the G values of and hydroxyl radical obtained in the acidic aqueous solution can be applied approximately to the neutral region. The relation of G(HCl) to solute concentration was qualitatively identical to gamma-ray irradiation, although they are different in detail because of the difference in value of LET and in the mechanism of radical formation.
  • Akira Yokohata, Satoru Tsuda
    1967 Volume 40 Issue 11 Pages 2507-2511
    Published: 1967
    Released: March 27, 2006
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    The silent discharge reactions of aqueous solution have been extended to an alkaline region. Potassium ferricyanide was selected as reaction system. The results show the reduction of ferricyanide ions. The situation is very similar to that in the case of radiation chemistry. The G value of the disappearance of ferricyanide ions was almost the same as that of cerous ions formed from the acidified eerie solution by silent discharge reaction under the same experimental condition. Moreover, the yield of hydrogen peroxide produced in the alkaline solution was almost the same as those of acidic and neutral solutions. Those findings suggest that the radical yields will be also almost equal, irrespective of pH in the range studied. This work gives a further evidence that most of silent discharge reactions of the aqueous solutions in inert gases can be well interpreted in terms of the radiolysis by slow electrons generated in the gas phase.
  • Jun Yamauchi, Hiroaki Nishiguchi, Kazuo Mukai, Yasuo Deguchi, Hideo Ta ...
    1967 Volume 40 Issue 11 Pages 2512-2518
    Published: 1967
    Released: March 27, 2006
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    A series of diaryl nitric oxide radicals have been studied by the use of the electron spin resonance (ESR) technique. Several methyl derivatives of diphenyl nitric oxide were synthesized and their ESR spectra investigated. It has been shown that the hyperfine coupling constants of 14N, especially those of protons, are much affected in the case of the ortho-methylated compounds as a result of steric hindrance, which is discussed using the Hückel molecular-orbital theory and the valence-bond theory. In conclusion, two benzene rings of diphenyl nitric oxide derivatives are equivalently distorted for the symmetrically-substituted compounds and unequiv-alently for the unsymmetrically-substituted compounds. Furthermore, this tendency is strengthened by ortho-substitution.
  • Akio Furusaki
    1967 Volume 40 Issue 11 Pages 2518-2525
    Published: 1967
    Released: March 27, 2006
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    The molecular structure of the compound of the formula C12Cl12, mp 273°C, obtained on the pyrolysis of perchloro-(3, 4-dimethylenecyclobutene) at about 250°C, has been determined by a three-dimensional X-ray crystal analysis. The crystal of the compound is monoclinic with four molecules in the unit cell of the dimensions a=16.78, b=6.80, c=17.10 Å and β=116.5°; the space group is C2⁄c. The positions of all the chlorine atoms were elucidated by using the minimum function method, and then those of all the carbon atoms were obtained from an electron density distribution calculated with the phases of chlorine atoms alone. The positional parameters of all the atoms thus obtained were refined by the block-diagonal matrix least-squares method with anisotropic temperature factors. The final discrepancy factor R is 0.094 excluding zero intensity data. As a result of the present study, it is concluded that the compound is perchloro-(4, 8-dimethylene-tricyclo[3.3.2.01,5]deca-2, 6-diene). Except the contacts between the chlorine atoms attached to the same carbon atom, there are several intramolecular Cl···Cl contacts with distances smaller than twice the ordinary van der Waals radius of the chlorine atom; i.e., 3.06, 3.12, 3.13, 3.18 and 3.32 Å. However, it is found that these very close contacts do not seriously affect the bond lengths and angles in the molecule.
  • Taku Matsuo, Toshiaki Yoshida, Osamu Higuchi
    1967 Volume 40 Issue 11 Pages 2526-2529
    Published: 1967
    Released: March 27, 2006
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    The chemical shifts of methoxyl protons of a series of methoxybenzenes and the related compounds in cyclohexane, carbon tetrachloride, and benzene solutions have been investigated. The benzene-induced high-field shifts for methoxyl protons are large if the substituent at the benzene ring is a highly electron-withdrawing group. In carbon tetrachloride, the methoxyl proton signals appear at lower field than those in cyclohexane solutions. The low-field shifts also increase with the electronegativities of the substituents. An attempt has been made to interpret the solvent effects by the use of a model where benzene molecules are assumed to cluster around the methoxyl group and the benzene ring of the solute molecule. The attraction between solute and solvent molecules has been suggested to be due to the van der Waals interactions and partly to the charge-transfer interaction.
  • Masatoshi Hirayama
    1967 Volume 40 Issue 11 Pages 2530-2536
    Published: 1967
    Released: March 27, 2006
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    The ESR spectra of the anion radicals of dimethyl, diethyl, and diisopropyl esters of biphenyl-o, o′ and -p,p′-dicarboxylic acids, and of the di-t-butyl ester of the o, o′-derivative, have been studied. The anion radicals were prepared by electrolytic reduction in acetonitrile, and also by reduction with sodium and potassium metals in dimethoxyethane and tetrahydrofuran. The MO calculations of the spin densities were made by McLachlan’s method; all the splitting constants observed were assigned to the ring protons and the α-protons in the ester groups. A comparison of the experimental splittings with the calculated spin densities suggests that the anions ofp, p′-derivatives are in a planar conformation, while those of o,o′-derivatives have a twisted structure in which the twisting angle between the two rings was about 35–60°. A structural model was proposed for an ion complex formed between the anion of the o, o′-derivative and a sodium or a potassium cation.
  • Hitoshi Ohtaki, Hidetake Kakihana
    1967 Volume 40 Issue 11 Pages 2536-2538
    Published: 1967
    Released: March 27, 2006
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    Based on thermodynamic considerations an equation was derived for ion exchange equilibria in mixed solvent systems. In mixtures of water, W, and non-aqueous solvent, S, a selectivity coefficient of ion exchange of A and B ions, KAB, was expressed in terms of partial molal volumes of ions, \barvA and \barvB, partial molal volumes of solvents, \barvW and \barvS, and distribution coefficient of the solvents, D, between the external and the resin phases, thus
    lnKAB=[(\barvA–\barvB)+(\barhWA–\barhWB)\barvWA]lnD⁄(\barvS–\barvW)
    where \barhWA and \barhWB represent hydration numbers of A and B ions and \barvWA is partial molal volume of hydrated water. Symbols with bar denote quantities in the resin phase. Using the above equation and values from literatures, selectivity coefficients for sodium-potassium ion exchange in water-ethanol mixtures were calculated and compared with those experimentally obtained for examination of the validity of the equation.
  • Yoichiro Sato, Minoru Kinoshita, Mizuka Sano, Hideo Akamatu
    1967 Volume 40 Issue 11 Pages 2539-2543
    Published: 1967
    Released: March 27, 2006
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    Phenothiazine, N-methylphenothiazine and thianthrene are oxidized with antimony pentachloride, and give the corresponding monopositive ion radicals. These aromatic positive ions form crystalline salts with the complex negative ion of antimony pentachloride or tetrachloride. The paramagnetism for these salts is attributed to the aromatic ion radicals, and follows the Curie-Weiss law at higher temperatures, and deviates from it at lower temperatures. This behavior has been interpreted by assuming the linear chain model being applicable, which suggests a remarkable spin exchange interaction in the crystalline salt of phenothiazine·SbCl4, of J/k∼395°K.
  • Hiromasa Kijima, Tomohiro Sato, Masamichi Tsuboi, Akiyoshi Wada
    1967 Volume 40 Issue 11 Pages 2544-2549
    Published: 1967
    Released: March 27, 2006
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    A method is given for calculating cylindrical-polar coordinates of each atom in a helical polymer from a given set of bond lengths, bond angles, and angles of internal rotation. This should be useful for an analysis of an X-ray fiber diagram of the helical polymer.
  • Osamu Kikuchi, Kazuo Someno
    1967 Volume 40 Issue 11 Pages 2549-2553
    Published: 1967
    Released: March 27, 2006
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    ESR spectra were obtained for phenyl nitric oxide radicals derived from phenyl hydroxylamines by oxidation with benzoyl peroxide, and the variation of hyperfine splitting constants with solvent was examined. Hyperfine splitting constants of nitrogen and NH proton varied with the polarity and hydrogen-bonding nature of solvent. This variation was explained by molecular orbital theory where the Coulomb integral of oxygen atom is assumed to vary with solvent. The sigma-pi parameters, QNH (in aH(NH)NQNH), QN and Qo (in aNNQNOQO), were determined from experimental splitting constants of nitrogen and NH proton and the spin density calculated by McLachlan’s method. The values QNH=27.5, QN=30.5 QO=−13.6 were obtained and the latter two values could be used to calculate the nitrogen hyperfine splitting constant for diphenyl nitric oxide radical.
  • Akinori Hasegawa, Masaji Miura
    1967 Volume 40 Issue 11 Pages 2553-2558
    Published: 1967
    Released: March 27, 2006
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    Sodium polyphosphate irradiated with γ-rays was investigated with ESR by varying the degree of polymerization and by replacing sodium ion with other cation. By irradiating at room and liquid nitrogen temperatures and observing ESR at various temperatures, nine kinds of paramagnetic centers were detected. Two of them were attributed to trapped electrons and the others to trapped holes. Four among the latter groups were assigned to radicals on polyphosphate; fragments by bond rupture, –O3PO°· and °·PO3–, radical on end group, –O3PO°·, and radical on chain, –O2P\overset·°OO–.
  • Toshiro Yamashina, Kuniaki Watanabe
    1967 Volume 40 Issue 11 Pages 2558-2563
    Published: 1967
    Released: March 27, 2006
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    The dehydrogenation of ethyl alcohol on LiF single crystal surfaces has been investigated to determine the role of surface dislocations and another defects on the catalysis. The catalytic activity of the single crystal of LiF was greatly influenced by the surface treatments such as the manners of cleaving of the crystal and vacuum heating and so on. After radiation quenching subsequent to vacuum anealing at 350°C for 2 hr, the catalytic activity was greatest in the present work, being over seven times greater than that of nontreated crystal. The catalytic activity after the quenching treatment was found to increase in proportion to logarithm of the dislocation density. In observations with the electron microscope, the small spots concentrated in the center of dislocation was found on the highly activated crystal surface. From the results of kinetic and microscopic observations discussion was made on the catalytic sites of the LiF single crystal.
  • Chikayoshi Nagata, Hiroko Fujita, Akira Imamura
    1967 Volume 40 Issue 11 Pages 2564-2568
    Published: 1967
    Released: March 27, 2006
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    The transition energy and oscillator strength of stacked complexes of pyrene and 3, 4-benzopyrene with DNA bases are calculated using semi-empirical ASMO SGF CI method, and they are compared with those of free pyrene or 3, 4-benzopyrene. Among the assumed stacking models, the intercalation-like one with guanine reproduced well the experimentally observed red shift and decrease of absorption coefficient in DNA aqueous solution, and this result seems to support the intercalation-like stacking of these hydrocarbons with the DNA bases.
  • Kunishige Higashi, Kuniko Hori, Ryokichi Tsuchiya
    1967 Volume 40 Issue 11 Pages 2569-2572
    Published: 1967
    Released: March 27, 2006
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    Applying the continuous variation method to a mixed solution of the hexaaquochromium(III) perchlorate and phthalic acid, the complex formed in the aqueous solution was found to have mole ratios of chromium and ligand material of 1 : 1 and 1 : 3 at pH 1–2 and 3–4 respectively. The formation constants of the chromium(III) complexes with phthalic acid were determined by the pH method. The step-by-step formation constants were found to be log k1=5.52, log k2=4.48, and log k3=2.48 respectively. The solid chromium(III) complex with phthalic acid was also prepared. Though it was found to be an amorphous solid by X-ray diffraction measurement, the composition was close to K3[Cr3(ph)3(OH)6(H2O)6] (ph=C8H4O42−). A curious phenomenon was observed in the moist air; the substance in the dried state jumped, probably due to the absorption of water vapor.
  • Yukio Nakamura, Masaaki Hirata, Shinichi Kawaguchi
    1967 Volume 40 Issue 11 Pages 2572-2574
    Published: 1967
    Released: March 27, 2006
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    The reaction between tris(acetylacetonato)aluminum and bromine in dichloromethane was studied. The main product of this reaction was tris(γ-bromoacetylacetonato) aluminum which was soluble in dichloromethane. A small amount of slightly yellow precipitate was also produced as a minor product. The same compound was obtained in the reaction of tris(γ-bromoacetylacetonato) aluminum with hydrogen bromide in dichloromethane containing water, and identified as bromoaquobis(γ-bromoacetylacetonato) aluminum on the bases of the elemental and water analyses, the ion exchange study, and the infrared spectroscopy.
  • Mutsuo Kodama
    1967 Volume 40 Issue 11 Pages 2575-2579
    Published: 1967
    Released: March 27, 2006
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    The solution equilibria and the kinetics of the substitution reaction between Eriochrom Elack T (BT) and cobalt(II)-EDTA chelate were studied spectrophotometrically. At the pH range from 8.50 to 9.50, BT was found to form only 1 to 1 normal chelate CoD with cobalt(II), the stability constant of which is 1020.0(μ=0.30). Kinetically, the substitution reaction was found to proceed through the following two simultaneous reaction paths,
    i) HD2−+CoY2−\oversetk1+\ ightleftharpoonsCoD+HY3−
    ii) HD2−\oversetrapid\ ightleftharpoonsD3−+H+
    D3−CoY2−−\oversetk2+\ ightleftharpoonsCoD+Y4−
    and k1+ and k2+ were determined to be 0.23 l mol−1 sec−1 and 6.76×102 l mol−1 sec−1, respectively, at 20°C.
  • Yoshihisa Yamamoto, Kazuo Ito, Hayami Yoneda, Masayasu Mori
    1967 Volume 40 Issue 11 Pages 2580-2583
    Published: 1967
    Released: March 27, 2006
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    Co(IV) compounds of the formulae:
    (Remark: Graphics omitted.)
    have been isolated from the reaction product of salicylatotetraamminecobalt(III) chloride and 60% nitric acid. Valency four was ascertained by magnetic measurements (μeff=1.98 B.M. (A), 1.71 B.M. (B)) and iodometry.
  • Haruko Ito, Junnosuke Fujita, Kazuo Saito
    1967 Volume 40 Issue 11 Pages 2584-2591
    Published: 1967
    Released: March 27, 2006
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    In order to study the nature of absorption bands in square-planar metal complexes of d8 type, a number of platinum (II), palladium (II) and gold(III) complexes containing l-propylenediamine and l-cyclohexanediamine were prepared and their circular dichroism (CD) and rotatory dispersion (RD) as well as absorption spectra (AB) were measured. Three or four absorption bands corresponding to dd transitions were observed for each platinum(II) and palladium(II) complex. All the complexes, except for [Au(l-pn)2]Cl3, [Au(l-chxn)2]Cl3 and [PdCl2(l-pn)], give two possitive CD bands in the wavelength region from visible to 210 mμ, which are assigned to the spin-forbidden and spin-allowed A1→E transition. Both [Au(l-pn)2]Cl3and [Au(l-chxn)2]Cl3 exhibit only one strong positive CD band corresponding to the ligand field transition probably mixed with charge transfer transition. [PdCl2(l-pn)] gives a weak negative and a strong positive band corresponding to the transitions, A1→A2 and A1→E, respectively. The CD strength of the bis-l-diamine complexes is almost twice those of the mono-l-diamine complexes. The vicinal effect of l-cyclohexanediamine was about twice as strong as that of l-propylenediamine. Absorption spectra of the [MX4]n (M=Pt2+, Pd2+ and Au3+, X=Cl and Br) show a shoulder and two bands in the ultraviolet region adjacent to the ligand field bands. The shoulder band was assigned to the symmetry forbidden, and the two strong bands to the symmetry allowed pπdx2y2 and pσdx2y2 charge transfer transitions. In the [MBr4]n, the pπdx2y2 band splits into two components, corresponding to A1g→A1u and the other A1g→Eu transition.
  • Noboru Sugiyama, Choji Kashima, Makoto Yamamoto, Ryotaro Mohri
    1967 Volume 40 Issue 11 Pages 2591-2593
    Published: 1967
    Released: March 27, 2006
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    Three compounds, ethyl 5-hydroxy-4, 6-dioxoheptanoate, ethyl 2-methyl-5-hydroxy-5-(1-hydroxyethyl)-4-oxotetrahydrofuroate and 5-phenyl-2-ethoxy-2-(1-hydroxyethyl)-3-oxotetrahy-drofuran, which have structures closely related to altenin, were synthesized from 3-acetoxy-2, 4-dioxopentane. These compounds produced the black spot disease in pears. As these compounds all possess the reductone grouping, it appears that this grouping is responsible for the phytopa-thogenic activity.
  • Noboru Sugiyama, Choji Kashima, Makoto Yamamoto, Tadao Takano, Ryotaro ...
    1967 Volume 40 Issue 11 Pages 2594-2596
    Published: 1967
    Released: March 27, 2006
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    The three reductones, 3-hydroxy-2, 4-dioxopentane, ethyl 2-hydroxy-1, 3-dioxovalerate and ethyl 2-hydroxy-3-oxobutyrate, were synthesized. These compounds were examined for the pathogenic activities to the pear. The pathogenic activities of reductones have some relations with the endiol contents. The center of pathogenic activity in altenin is shown to be the endiol carbonyl grouping.
  • Nobuyuki Ashikari, Izumi Kawashima, Takehisa Kawashima
    1967 Volume 40 Issue 11 Pages 2597-2603
    Published: 1967
    Released: March 27, 2006
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    The crosslinking reactions of several unsaturated polyolefins with organic peroxides were carried out in an attempt to establish the dependence of the crosslinking efficiency on the reaction conditions, especially the reaction temperature and the peroxide concentration. Usually, the efficiency gradually increased up to a certain temperature and then decreased abruptly. This efficiency decrease can be considered to be due to (1) a decrease in the hydrogen abstraction, which is one reaction producing crosslinks, and (2) an increase in the termination rate in a chain reaction arising from opening up the double bond, which is another reaction producing crosslinks. Except for cases in which an extremely high temperature was employed or when a very high concentration of peroxide was used, the efficiency decrease by scission reaction upon an elevation of the temperature seems to be comparatively small.
  • Tadashi Sasaki, Toshiyuki Yoshioka
    1967 Volume 40 Issue 11 Pages 2604-2607
    Published: 1967
    Released: March 27, 2006
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    The corresponding isoxazolines and isoxazoles were prepared by 1, 3-dipolar cycloaddition with olefinic and acetylenic dipolarophiles by two methods, a) and b). Here, method a) means the routine method via nitrile oxide formation, while method b) means the new type of reaction named in the title. Method b) is concluded to be superior to method a) for the purpose of preparing isoxazoles and isoxazolines. The mechanism of the thermal 1, 3-dipolar cycloaddition is discussed.
  • Tadashi Sasaki, Toshiyuki Yoshioka
    1967 Volume 40 Issue 11 Pages 2608-2613
    Published: 1967
    Released: March 27, 2006
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    Phenyl-, furyl-, and 5-nitro-2-furylacrylonitrile oxides were prepared in situ from the corresponding hydroxamoyl chlorides and a base. They reacted with styrene or aery 1 amide as a dipolarophile to give the corresponding 3, 5-disubstituted isoxazolines in very low yields. These results show that the reactivity of such nitrile oxides was reduced by the presence of a conjugated double bond. Phenyl- and 5-nitro-2-furylacrylonitrile oxides were treated with α-morpholinostyrene to afford 3-styryl-5-morpholino-5-phenyl- and 3-(5-nitro-2-furylvinyl)-5-morpholino-5-phenylisoxazole respectively. The former product was further treated with hydrochloric acid to give 3-styryl-5-phenylisoxazole in a good yield. Phenylacrylonitrile oxide was heated in ethanol with cyanoguanidine, leading to 3-styryl-5-guanidino-1, 2, 4-oxadiazole. 5-Nitro-2-furylacrylhydroxamoyl chloride was treated with sodium azide to give the azido-aldoxime.
  • Yasuhide Yukawa, Yuho Tsuno, Toshikazu Ibata
    1967 Volume 40 Issue 11 Pages 2613-2617
    Published: 1967
    Released: March 27, 2006
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    Kinetic studies of the Wolff rearrangement of α-diazoacetophenone were performed in t-butyl alcohol, by the volumetric measurement of the evolved nitrogen, using a solution of silver benzoate in triethylamine as a catalyst. A pseudo-first-order rate constant was obtained accompanying the induction period. The effects of the concentrations of silver benzoate and triethylamine on the reaction rate were studied. The concentration of silver ions was determined by the gravimetric measurement of silver chloride in the course of the reaction. The silver ions were found to be consumed only in the initial stage of the reaction. On the basis of these results, a novel reaction mechanism, in which the active entity of the catalyst was thought to be a silver ion-triethylamine complex, was proposed.
  • Yasuhide Yukawa, Yuho Tsuno, Toshikazu Ibata
    1967 Volume 40 Issue 11 Pages 2618-2623
    Published: 1967
    Released: March 27, 2006
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    The substituent effect on the reaction rates of the Wolff rearrangement of meta- and parasubstituted α-diazoacetophenones was studied in t-butyl alcohol, isopropyl alcohol, and t-butyl alcohol-toluene mixed solvents, and also on the decomposition rates in toluene, using a solution of silver benzoate in triethylamine as a catalyst. Similar substituent effects were observed regardless of the solvents used. Strong electron-releasing conjugative substituents at the para position, such as methoxy and ethoxy groups, retard the reaction rate greatly. The other substituents accord roughly with the Hammett relationship, having small negative ρ-values. The decomposition rate constants in toluene were apllicable to the Yukawa-Tsuno equation, which has a negative γ-value:
    logkk0=−0.45(σ−2.7ΔσR+)−0.05
    proving that the resonance stabilization on the reaction origin are caused by the electron-releasing substituent at the para position. The results of the kinetic isotope effects (no apparent kinetic isotope effect was observed within the range of experimental error) of the Wolff rearrangement of carbonyl-14C, and phenyl-1-14C labeled α-diazoacetophenone under the same reaction conditions favor the two-step mechanism to the concerted one for the elimination of nitrogen and the migration of the alkyl group.
  • Minoru Igarashi, Hiroshi Midorikawa
    1967 Volume 40 Issue 11 Pages 2624-2627
    Published: 1967
    Released: March 27, 2006
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    l-Menthyl alkylidenecyanoacetates have been prepared. The reaction of the esters with hydrogen peroxide in the presence of a base is accompanied by a partial asymmetric synthesis, as is shown by the hydrolysis of the resulting epoxy esters to epoxy acids.
  • Susumu Hirase, Choji Araki
    1967 Volume 40 Issue 11 Pages 2627-2629
    Published: 1967
    Released: March 27, 2006
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    Carrabiose (3, 6-anhydro-4-O-β-D-galactopyranosyl-D-galactose) was synthesized by a series of reactions involving the condensation of methyl 2-O-p-tosyl-3, 6-anhydro-α-D-galactopyranoside with tetra-O-acetyl-α-D-galactopyranosyl bromide, followed by deacetylation, detosylation, and removal of the glycosidic methoxyl group. From the resulting disaccharide, several crystalline derivatives were prepared. All of these derivatives were identical in every respect with the corresponding compounds, which had been obtained from natural sources.
  • Shigeru Matsutani, Ichiro Kawasaki, Takeo Kaneko
    1967 Volume 40 Issue 11 Pages 2629-2635
    Published: 1967
    Released: March 27, 2006
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    Studying the synthesis of nupharamine, a minor alkaloid isolated from Nuphar japonicum DC, N-methylnupharamine was synthesized and its stereoisomers were characterized.
  • Takao Takaya, Hataaki Yoshimoto, Eiji Imoto
    1967 Volume 40 Issue 11 Pages 2636-2640
    Published: 1967
    Released: March 27, 2006
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    The preparation of cis-3,4-ureylenethiophane (23) was attempted through three different routes. cis-3-Carbomethoxyamino-4-carbomethoxythiophane (20A), which had been obtained by the Lossen rearrangement of N-phenylsulfonyloxythiophane-cis-3, 4-dicarboximide (19), was selectively hydrolyzed to cis-3-carbomethoxyamino-4-carboxythiophane (21A), the modified Curtius rearrangement of which gave N-carbomethoxy-cis-3, 4-ureylenethiophane (22A). The alkaline hydrolysis of 22A afforded 23. However, an attempt to prepare 23 through two sulfone derivatives, (6) and (14), was unsuccessful.
  • Teruaki Mukaiyama, Shin-ichi Aizawa, Tatsuaki Yamaguchi
    1967 Volume 40 Issue 11 Pages 2641-2644
    Published: 1967
    Released: March 27, 2006
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    The preparation of 1-dimethylamino-1-ethylthioethylene (ketene-N, S-acetal) from N, N-dimethylamino-S-ethylthioacetamidium iodide and the reactions of the ketene-N, S-acetal with some electrophilic reagents were investigated. One equivalent of phenyl isocyanate and two equivalents of diphenylketene reacted with the ketene-N, S-acetal to produce substituted acrylanilide and 2, 3-dihydro-α-pyrone derivative, respectively. On the other hand, the reactions of the ketene-N, S-acetal with carbon disulfide in the presence of elemental sulfur and with electrophilic oleflns, such as acrylonitrile and methyl acrylate, gave 5-dimethylaminotrithione and substituted cyclobutenes, respectively, by eliminating ethyl mercaptan. Further, it was found that α, β-unsaturated carbonyl compounds, such as acrolein and methyl vinyl ketone, afforded bicyclic compounds, 2, 10-dioxabicyclo[4. 4. 0]decadiene-3, 8 derivatives.
  • Ken Murayama, Yasuo Kato, Saichi Morimoto
    1967 Volume 40 Issue 11 Pages 2645-2647
    Published: 1967
    Released: March 27, 2006
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    Highly crystalline polymers were synthesized by the polymerization of p-benzene-bis(ω-S-alkylthiosulfate) (Remark: Graphics omitted.). Sodium sulfide was effective as a catalyst, but polymers obtained showed much more sulfur content than the theoretical value. The polymers (n≥2) possessed rubber-like characteristics.
  • Yasuo Ariyoshi, Tetsuo Shiba, Takeo Kaneko
    1967 Volume 40 Issue 11 Pages 2648-2654
    Published: 1967
    Released: March 27, 2006
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    For the purpose of making a total synthesis of bacitracin A, a protected heptapeptide with a ring structure, Nα- (formyl-L-isoleucyl)-cyclo-(L-lysyl-δ-tosyl-D-ornithyl-L-isoleucyl-D-phenyl-alanyl-im-benzyl-L-histidyl-α-methyl-β-L-aspartyl) was first prepared by a high dilution method. After deformylation, it was coupled with a tetrapeptide corresponding to the N-terminal part of bacitracin A, the benzyloxycarbonyl-L-isoleucyl-S-benzyl-L-cysteinyl-L-leucyl-D-glutamic acid (α-azide)-γ-t-butyl ester, to afford an undecapeptide derivative. This was converted to a hydrazide, which was then coupled with β-benzyl-D-isoasparaginate to give the Nα-(benzyloxycarbonyl-L-isoleucyl-S-benzyl-L-cysteinyl-L-leucyl-γ-t-butyl-D-glutamyl-D-isoleucyl)-cyclo-(L-lysyl-δ-tosyl-D-ornithyl-L-isoleucyl-D-phenylalanyl-im-benzyl-L-histidyl-β-L-aspartyl)-D-isoasparagine β-benzyl ester. The removal of all protecting groups from it gave a free dodecapeptide, which has the same amino acid sequence, including optical properties, as that of the structure of bacitracin A proposed by Stoffel and Craig; it is different from the latter only in having the thiazoline ring replaced with the cysteine residue. The synthetic dodecapeptide was tested for biological activity and for the formation reaction of the thiazoline ring.
  • Yasuo Ariyoshi, Tetsuo Shiba, Takeo Kaneko
    1967 Volume 40 Issue 11 Pages 2654-2658
    Published: 1967
    Released: March 27, 2006
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    An optical active 2-(2-methylbutyryl)thiazole-4-carboxylic acid obtained from bacitracin F by an acid hydrolysis was synthesized starting from L-isoleucine. Applying the usual methods for the peptide synthesis, 2-(2-methylbutyryl)thiazole-4-carbonyl-L-leucyl-D-glutamic acid α-methyl-γ-t-butyl ester corresponding to the N-terminal tetrapeptide of bacitracin F, was then synthesized from the thiazole carboxylic acid. UV spectrum of the synthetic tetrapeptide was very similar to that of bacitracin F.
  • Heimei Yuki, Junichi Hotta, Yoshio Okamoto, Shunsuke Murahashi
    1967 Volume 40 Issue 11 Pages 2659-2663
    Published: 1967
    Released: March 27, 2006
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    The anionic copolymerization of styrene (M1) and 1, 1-diphenylethylene (M2) was investigated. 1, 1-Diphenylethylene, which can not homopolymerize by itself, was copolymerized with styrene by means of an anionic initiator. The copolymerization reaction seemed to proceed without termination or chain transfer, and gave a high molecular alternating copolymer under appropriate reaction conditions. The monomer reactivity ratio, r1, was obtained from the copolymer composition at the complete consumption of M1, assuming the rate constant k22=0. The monomer reactivity ratio was affected by the solvent (n-hexane, benzene, toluene, or THF), but not by the catalyst (n-BuLi, Na-dispersion, Na-naphthalene, or K-dispersion) or the reaction temperature. It was 0.4 in toluene at 30°C.
  • Teruzo Asahara, Hideo Kise
    1967 Volume 40 Issue 11 Pages 2664-2667
    Published: 1967
    Released: March 27, 2006
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    The effects of the addition of several oxygen- and nitrogen-containing compounds on the cationic telomerizations of butadiene with its hydrochloride were investigated. The addition of both acetonitrile and ethyl ether to an ethyl bromide solution of ferric chloride or a methylene chloride solution of titanium tetrachloride resulted in large decreases in the catalytic activities of the solutions at low temperatures. On the other hand, the addition of nitroethane to an ethyl bromide solution of aluminum chloride increased the activity of the catalyst, although the addition of nitrobenzene decreased it. The addition of ethyl ether to ferric chloride or titanium tetrachloride led to the formation of telomers with lower molecular weights and larger degrees of unsaturation, whereas a nitroethane - aluminum chloride catalyst gave telomers with higher molecular weights. The monomolecular addition complexes of several Lewis acids and Lewis bases were isolated, and the catalytic abilities of the complexes in halogenated hydrocarbons were investigated. The structures of the higher telomers were analyzed and will be discussed.
  • Waichiro Kawakami, Miyuki Hagiwara, Yoshihiko Hosaki, Sueo Machi, Tsut ...
    1967 Volume 40 Issue 11 Pages 2668-2675
    Published: 1967
    Released: March 27, 2006
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    The effect of agitation on the γ-ray induced polymerization of ethylene was studied in a gaseous system at a pressure of 400 kg/cm2 and at a temperature of 30°C, with dose rates ranging from 9.0×102 to 3.8×105 rad/hr. Both the rate and the degree of polymerization decreased upon agitation to I. 50% of those in the polymerization without agitation. The kinetical analysis of the experimental results has shown that this decrease in the rate and in the degree of polymerization is mainly due to a decrease in the absolute propagation rate. Further, it was found that agitation has no effect on initiation and transfer reactions. The termination was not effected by agitation under a high dose rate, but it was slightly promoted at lower dose rates.
  • Kenjiro Meguro, Miyoko Ochi, Noritaka Matsushita
    1967 Volume 40 Issue 11 Pages 2675-2681
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    Surface-active polyethenoxy silicic esters were prepared by the reaction of tetraethyl silicate with various polyethenoxy higher alkyl ethers by the use of tetrabutyl titanate as a catalyst. Their properties as surfactant were compared with those of conventional nonionic surfactants. These compounds are soluble in many kinds of organic solvents, and have good dispersing power on such inorganic pigments as titanium oxide in organic media. The dispersing characteristics of these compounds in the inorganic pigments were tested in benzene, carbon tetrachloride, and monochlorobenzene by measuring the sedimentation volume. It was found that the compounds containing a chain of more than six ethenoxy groups were soluble in water. The surface tension of these water-soluble polyethenoxy silicic esters were determined in various concentration regions. In this paper, the preparation and properties of these compounds will be described.
  • Tatsuo Yonekubo
    1967 Volume 40 Issue 11 Pages 2682-2683
    Published: 1967
    Released: March 27, 2006
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  • Kenichiro Nakamura, Shinichi Kikuchi
    1967 Volume 40 Issue 11 Pages 2684-2685
    Published: 1967
    Released: March 27, 2006
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  • Toshitsugu Ozeki, Masakatsu Kusaka
    1967 Volume 40 Issue 11 Pages 2686-2688
    Published: 1967
    Released: March 27, 2006
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  • Ginzaburo Suzue, Katsuo Tsukada, Shozo Tanaka
    1967 Volume 40 Issue 11 Pages 2688-2689
    Published: 1967
    Released: March 27, 2006
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  • Mitsuru Hiroi
    1967 Volume 40 Issue 11 Pages 2689-2690
    Published: 1967
    Released: March 27, 2006
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  • Kuniyoshi Masuzawa, Hiroaki Uchida
    1967 Volume 40 Issue 11 Pages 2691-2693
    Published: 1967
    Released: March 27, 2006
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