Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 50 , Issue 5
Showing 1-50 articles out of 69 articles from the selected issue
  • Takashi Hayashi, Hajime Saito
    1977 Volume 50 Issue 5 Pages 1023-1027
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Three new poly [bis(amino)phosphazenes] of formulas [NP(NHC6H13)2]n, [NP(NHCH2CHCH2)2]n, and [NP(NHCH2C6H5)2]n have been synthesized by direct aminolysis of (NPCl2)n. The electrical resistivity and thermal stability of a series of poly[bis(amino)phoshazenes], (NPR2) (R: amino group), have been examined. Most polymers showed an increase in resistance with time to an equilibrium value, possibly due to space charge effects, allowance for this conductivity being ohmic up to 500(V/cm). The aliphatic amino derivatives have a lower resistivity and a lower ΔE value than the aromatic amino derivatives. The resistivity of the poly [bis(amino)phosphazenes] was found to decrease in the order, R : NHC2H5>NHC3H7>NHC4H9>NHC6H13>>N(CH3)2. This seems to be predominantly due to the nature of an inductive electron supply of amino side groups. In some polymers the change of energy gap, ΔE, was observed in the range 70–90 °C. The ΔE value was usually lower in the low temperature region than in the high temperature region. All the polymers were found to decompose at about 200 °C, losing the amino side group.
  • Yoshiyuki Hirai, Mitsuyoshi Yukawa, Yoshio Imamura
    1977 Volume 50 Issue 5 Pages 1028-1031
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Polyacrylamides of low molecular weights (average degrees of polymerization(‾DP) : 7.2, 18.3, 21.3, and 45.4) were prepared by radical polymerization, and their PMR spectra were observed over the temperature range of 30–90 °C. From the temperature dependence of the PMR spectra, the values of the energy barrier to the internal rotation about C–N bonds were determined by means of a total line-shape analysis. The energy barriers for the polymers above ‾DP : 18.3 were 10.6 kcal/mol, while those for the polymer of ‾DP : 7.2 were 9.2 kcal/mol. These results were interpreted in terms of the local environment around the amide groups. The intramolecular hydrogen bonding was also investigated.
  • Fumio Hirata
    1977 Volume 50 Issue 5 Pages 1032-1039
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The radial distribution function (RDF) for a water-like system, which has the fundamental characteristics of water, is calculated using the graph-theoretical technique developed by Andersen and Chandler. An interaction potential devised to simulate the hydrogen bond is regarded as a perturbation of the pair interaction between the two molecules of a reference system which consists of hard spheres each having a point dipole at each center. The effect of the hydrogen bond-like potential on the distribution of the molecules is shown explicitly. The results show a tetrahedral coordination similar to that in water. The resulting RDF has qualitatively reproduced the features observed in the experimental RDF curve for water.
  • Yuzo Imizu, Tsutomu Yamaguchi, Hideshi Hattori, Kozo Tanabe
    1977 Volume 50 Issue 5 Pages 1040-1043
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The isomerization of butenes has been studied over four kinds of ThO2 catalysts which differ in starting materials or preparative procedures. The selective ThO2 catalysts for the formation of 1-olefin in the dehydration of 2-alkanol, which were prepared from nitrate and oxalate, were active and gave high cis/trans ratios in the isomerization of 1-butene, whereas the non-selective ThO2 catalyst, which was prepared from chloride, was completely inactive. The isomerization reaction was poisoned by both CO2 and NH3. The activity was enhanced by the treatment with hydrogen, but was reduced by the treatment with oxygen, the selectivity being unchanged with both treatments. The coisomerization of cis-2-butene and cis-2-butene-d8 showed that the isomerization involved an intramolecular hydrogen transfer, and a large isotope effect, 6.0, for the formation of 1-butene and a small isotope effect, 1.5, for the formation of trans-2-butene were observed. With these results, the nature of active sites on thorium oxide, and the reaction mechanism were discussed.
  • Hiroo Ogura
    1977 Volume 50 Issue 5 Pages 1044-1050
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The pyrolysis of acetylene was investigated behind the reflected shock waves in a single-pulse shock tube over the temperature range from 1000 to 1670 K. The major products were 1-buten-3-yne, 1,3-butadiyne, and hydrogen. The main primary C4 product, however, changes from 1-buten-3-yne to 1,3-butadiyne with the increase of temperature. At the lower temperatures the formation of 1-buten-3-yne dominates the pyrolysis of acetylene. The rate of 1-buten-3-yne formation is second order with respect to acetylene concentration, and its second-order rate constant is expressed as follows:
    k(cm^3 mol^-1s^-1)=10^14.39±0.26exp((-46400±1400)/RT)
    The isotopic distribution of 1-buten-3-yne in the pyrolysis of the equimolar C2H2 and C2D2 mixture, proved that the pyrolysis proceeds via a free-radical mechanism. A free-radical chain mechanism initiated by the bimolecular reaction of acetylene, 2C2H2→C4H3+H, was proposed.
  • Kojiro Kan, Yasushi Kai, Noritake Yasuoka, Nobutami Kasai
    1977 Volume 50 Issue 5 Pages 1051-1055
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The molecular structure of [NiCl2{Me2neoMen)P}2], an asymmetric hydrosilylation catalyst of olefin was determined by means of X-ray diffraction. This complex forms dark red monoclinic crystals; a=9.527(1), b=8.048(2), c=19.461(3) Å, β=99.12(1)°, space group P21 with Z=2. The structure, determined by the heavy-atom method, has been refined anisotropically by a least-squares procedure to R=0.099 for 3023 non-zero reflections. The geometry around the nickel atom is trans-square planar [Ni–Cl 2.151(5) and 2.175(6) Å, Ni–P 2.239(5) and 2.230(5) Å], Two neomenthyl groups are located above and below the co-ordination plane.
  • Setsuko Tatematsu, Tamotsu Kondow, Toru Nakagawa, Kozo Kuchitsu
    1977 Volume 50 Issue 5 Pages 1056-1059
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The violet emission spectra of CN(B2∑−X2∑), Δv=0, were observed by the photodissociation of BrCN by Lyman-α radiation (121.6 nm). The peak intensities for the vibrational levels v′≥1 relative to v′=0 decreased with the BrCN pressure (up to 2 Torr), whereas at 0.1 Torr or lower the spectrum was essentially independent of the pressure. The relative vibrational populations (v′=0–10) and the effective rotational temperatures were estimated by a band-envelope analysis. The effective rotational temperature, estimated to be 2000±200 K for v′=0–4, was practically independent of the pressure. Within the low-pressure limit the distributions of the excess energy to vibration and rotation were estimated to be 0.50±0.08 and 0.17±0.02 eV, respectively.
  • Kikuo Terada, Akihiko Inoue, Junko Inamura, Toshiyasu Kiba
    1977 Volume 50 Issue 5 Pages 1060-1065
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The preparation and characteristics of 2-mercaptobenzothiazole supported on silica gel (MBT–SG), and its application to the preconcentration and determination of cadmium, copper, lead, and zinc in natural water samples are described. The MBT–SG was prepared by impregnating silica gel with MBT in a dioxane–methyl acetate solvent mixture, drying, washing with deionized water, and finally drying. The chelating capacity of the material was 0.01 meq. Cu/g. Cadmium, copper, lead, and zinc were quantitatively retained on the MBT–SG at pH values of 4.8, 2.5, 4.8, and 6.5 for an aqueous solution, and at pH values of 4.8, 2.8, 4.8, and 6.5 for sea water. A column made of the material provided quantitative recovery of these metals from natural water samples at higher flow rates (2–5 1/h) than other chelating resins, e. g., chelex 100. Cadmium was eluted with hydrochloric acid (1 : 99), copper and lead with acetone–hydrochloric acid mixture (9 : 1), and zinc with an acetate–hydrochloric acid buffer solution (pH 4.0). Then, the quantities of the four metals in their effluents were determined by atomic absorption spectrometry.
  • Kazuo Yamashita, Hideo Imai
    1977 Volume 50 Issue 5 Pages 1066-1069
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The red limit potential of electron photoemission was measured in various polar solvents, and the apparent solvation free energies of the electrons were estimated. The energy state and transformation of photoemitted electrons in solution were discussed as regards the role of dry or damp electrons as an intermediate species. A proportionality between the intermediate solvation free energy and the energy quantum of the optical absorption band maximum of solvated electron in various polar solvents is pointed out.
  • Masaaki Okunaka, Gen-etsu Matsubayashi, Toshio Tanaka
    1977 Volume 50 Issue 5 Pages 1070-1073
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Cationic palladium(II) complexes of the di-t-butylnitroxide radical, [Pd(But2NO)(L-L)]X (L-L=2,2′-bipyridine, 1,10-phenanthroline, N-substituted 2-pyridylmethyleneamine and bis(triphenylphosphine); X=ClO4-and/or BPh4), were prepared. 1H NMR spectra of the complexes indicate that the nitroxide forms a three membered ring with the palladium atom. The N-methyl- and N-ethyl-2-pyridylmethyleneamine complexes exist as two geometrical isomers in solution, whose ratios are 1 : 1 and 1 : 0.2, respectively. In the N-butyl and N-p-tolyl analogs, however, only one of the isomers exists in solution. These results are interpreted in terms of steric repulsion between the t-butyl groups and N-substituents. The bipyridine complex reacts with dialkyl disulfides in the presence of catalytic amounts of bipyridine to give a sulfur-bridged dimeric complex, [Pd(bipyridine)(SR)]2(ClO4)2(R=Me and Pr), and a free nitroxide radical.
  • Misao Umehara, Shinzaburo Hishida, Kunimi Fujieda, Hirooki Sasaki
    1977 Volume 50 Issue 5 Pages 1074-1077
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Bromination and chlorination of 4,4-dimethylbicyclo[6.3.0]undecane-2,6-dione (2) with pyridinium bromide perbromide and sulfuryl chloride gave several α-halo-diones. The substituted positions and the stereochemistry of the halogen atoms have been assigned on the basis of their dehydrohalogenation and spectral data. The chlorination of 2 also gave a tricyclic dione (8) containing a cyclopropane ring. The structure of 8 was determined by means of 13C-NMR, as well as other types of spectroscopy. Dehydrochlorination of 7 gave a 5H-benzocyclo-heptene derivative (18).
  • Sakae Uemura, Akira Onoe, Masaya Okano
    1977 Volume 50 Issue 5 Pages 1078-1081
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The slow addition of SbCl5 to a CCl4 solution of 1,5-cyclooctadiene or cis-cyclooctene gives an isomeric mixture of endo- and exo-2, anti-8-dichlorobicyclo[3.2.1]octanes (1 and 2) or an isomeric mixture of trans- and cis-1,4-dichlorocyclooctanes (12 and 13) respectively in a good yield. The former reaction involves the transannular cyclization, while the latter is accompanied by the transannular hydrogen shift. The addition of 1,5-cyclooctadiene to a CCl4 solution of SbCl5 (reverse addition) affords endo-2,6- and endo, exo-2,6-dichlorobicyclo[3.3.0]octanes (6 and 7) as additional products, besides 1 and 2. In the case of cis-cyclooctene, however, a reverse addition produces only chlorocyclooctane. It has been revealed that a mixture of 6 and 7 is readily isomerized to a mixture of 1 and 2 by the interaction with SbCl5. The 1,4-chlorination of cis-cyclooctene which gives 12 and 13 also occurs with VCl4, SeCl4, PhICl2, and PCl5, although the selectivity and the yield are low compared to the case of SbCl5.
  • Masahiko Kato, Takeji Chikamoto, Toshio Miwa
    1977 Volume 50 Issue 5 Pages 1082-1087
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Studies have been carried out on the photochemical valence bond isomerization of some benzobicyclo-C9H10 hydrocarbons, i. e., benzo[8,9]bicyclo[5.2.0]nona-2,4,8-triene (2), benzo[2,3]bicyclo[6.1.0]nona-2,4,6-triene (3), cis-3a,9b-dihydro-1H-benz[e]indene (6), and benzo[6,7]bicyclo[3.2.2]nona-2,6,8-triene (10), with use of a low pressure mercury lamp. From a comparison of photolysis at low temperatures with that at room temperature, the stereochemical courses are discussed in terms of conformations of these compounds.
  • Takashi Yamada, Kazuko Suegane, Shigeru Kuwata, Hiroshi Watanabe
    1977 Volume 50 Issue 5 Pages 1088-1093
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    As a basic study for synthesis of bottromycin, the syntheses and the reactions of iminodipeptides were investigated. Nine N-benzyloxycarbonyl(Z) iminodipeptides were prepared by the condensation of ethyl Z-amino carboximidates with amino acids according to the method of Ried et al. All the imidates were prepared from the corresponding nitriles, and ethyl N-Z-2-pyrrolidinecarboximidate (IIIf) was also successfully obtained from Z-proline thioamide by the method of Suydam et al. Though Z-(iminoprolyl)glycine was easily deprotected or esterified, its C-terminal could not be elongated because it was likely to cyclize into an imidazolone ring. This side reaction could be avoided by locating a carboxyl group further apart from an imino group in a molecule; i. e., the imidate (IIIf) could be coupled with methyl glycylphenylalaninate, thus affording the desired iminotripeptide, Z–ImPro–Gly–Phe–OMe, in a good yield.
  • Takeshi Yamazaki, Yasuo Wada, Shigeo Tanimoto, Masaya Okano
    1977 Volume 50 Issue 5 Pages 1094-1096
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    In the presence of a Lewis-acid catalyst, such as HgCl2 or ZnCl2, cyclohexyl isocyanide reacted with chlorine and tetrahydrofuran to give, after hydrolysis, 4-chlorobutyl cyclohexylcarbamate in a fair yield. When one of the reactants was replaced by another isocyanide, bromine, or another cyclic ether, the reactions proceeded similarly, but the corresponding carbamate yields were rather poor.
  • Mikio Nakamura, Nobuo Nakamura, Michinori Oki
    1977 Volume 50 Issue 5 Pages 1097-1101
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Studies were carried out on the rates of lithiation of 9-arylfluorenes, in which the aryls are hydrocarbons. The reactivities of these compounds are explained in terms of the effective blocking of the reaction site by the substituent. The steric effect of the substituent which is attached to the aryl group but is over the fluorene ring is found to play a role in the reactivities.
  • Akira Miyashita, Akio Yamamoto
    1977 Volume 50 Issue 5 Pages 1102-1108
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    A variety of stable alkylcopper(I) complexes of composition RCuLn (n=1–3) containing various monodentate tertiary phosphine ligands (L), such as triphenylphosphine, diphenylmethylphosphine, dimethylphenylphosphine, tributylphosphine, triethylphosphine, and tricyclohexylphosphine have been prepared by the reactions of copper-(II) acetylacetonate, dialkylaluminium monoethoxide, and the tertiary phosphines. Similar reactions employing 1,2-bis(diphenylphosphino)ethane(dpe) give (RCu)2(dpe)3. The complexes have been isolated and characterized by elemental analysis, determination of molecular weight, chemical reactions, IR and NMR spectroscopy. All the isolated complexes show considerable thermal stability compared with alkylcopper compounds without phosphine ligand indicating the marked contribution of these phosphine ligands to the stabilization of the copper-carbon bond. The dpe-coordinated alkylcopper complexes are thermally stable in the solid state but readily decompose in solution with hydrogen abstraction accompanied by scission of the C–P bond of dpe to give Ph2PCu-(dpe), Ph2PCH=CH2, and alkane. These alkylcopper complexes initiate the polymerization of vinyl monomers such as acrylonitrile, methacrylonitrile, methyl acrylate, and methyl methacrylate. Alkyl halides and acyl halides react with the alkylcopper complexes to give cross-coupling products of alkyl groups and alkyl-acyl groups.
  • Akira Miyashita, Takakazu Yamamoto, Akio Yamamoto
    1977 Volume 50 Issue 5 Pages 1109-1117
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Thermolysis of isolated alkylcopper(I) complexes having tertiary phosphine ligand(s) RCuLn (R=CH3, C2H5, n-C3H7, i-C4H9) in the solid state and in toluene has been studied in order to clarify the role of the tertiary phosphine ligand in stabilizing the alkylcopper(I) complexes. The distribution of the thermolysis products shows that the thermolysis of the alkylcopper complexes having ethyl or longer alkyl chain proceeds through a β-elimination mechanism. The rate of the thermolysis obeys the first order rate law, −d[RCuLn]/dt=k[RCuLn]. The activation parameters of the thermolysis were obtained from the temperature dependence of k and a compensation effect between ΔH\ eweq and ΔS\ eweq was demonstrated. The activation energy Ea of the thermolysis of RCu(PPh3)2 increases in the order of R=C2H5<n-C3H7<i-C4H9. Coordination of electron-donating tertiary phosphine decreases Ea and a linear relationship between ν(Cu–CH3) frequencies and Ea for thermolysis of the methylcopper complexes was observed. Addition of PPh3 into the toluene solutions of CH3Cu(PPh3)2(diethyl ether)0.5 and C2H5Cu(PPh3)2 causes some retardation of the thermolysis. The major role of the tertiary phosphine ligand in stabilizing the alkylcopper complexes is proposed to strengthen the Cu–C bond by changing the electronic state of copper atom. An energetic consideration based on Chatt and Shaw’s theory is given in order to account for the results concerning the stabilities of the alkylcopper complexes. Photolysis of the alkylcopper complexes takes a quite different decomposition pathway producing mainly RH from RCuLn.
  • Sei Otsuka, Kikuo Ataka
    1977 Volume 50 Issue 5 Pages 1118-1124
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The oxidative additions of chiral alkyl halides, (S)-(−)-ethyl α-bromopropionate [α]D−18.9° (c 3.3, CHCl3) and (S)-(+)-ethyl α-phenylbromoacetate [α]d+56.4° (c 1.6, C2H5OH) to [RH(R′NC)4]+ (R′=t-Bu, p-CH3C6H4) produced the corresponding adducts, trans-[RhBr(R)(R′NC)4]+ (R=CH3CHCO2Et, PhCHCO2Et), which were well characterized by elemental analysis, IR and 1H NMR spectra. These adducts were found optically inactive, a fact which precludes a concerted mechanism. The reaction of C6H5CHBrCO2C2H5 with [Rh(t-BuNC)4]+ commenced immediately in the absence of light. Taking this system as a typical example, the rate was studied by the stopped-flow method to find a rate equation, R=k[Rh(I)]2[RX]. The relative rate of addition of p-XC6H4CHBrCO2C2H5 to [Rh(t-BuNC)4]+ decreases in an order of Cl>H>CH3 for X. The addition of C6H5CHBrCO2C2H5 to [Rh(p-CH3C6H4NC)4]+ in the dark proceeds only slowly, but rapidly under a low energy photo-irradiation (440 nm) with a large quantum yield (φ 4.8). The addition of CH3CHBrCO2C2H5 requires photo-initiation. The optical activity of (S)-(−)-CH3CHBrCO2C2H5 was completely lost before the oxidative addition commenced. The rate of decrease in optical activity of the system (S)-(−)-C6H5CHBrCO2C2H5/[Rh(t-BuNC)4]+ exhibited approximate second order kinetic behavior, and quantitative racemization took place prior to the completion of the oxidative addition. A chain mechanism appears to be consistent with all these results. Alternate mechanisms are also discussed in the light of the present results.
  • Morio Hirano, Fujio Takahashi
    1977 Volume 50 Issue 5 Pages 1125-1128
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Reduced keratin, which was obtained by reductive cleavage of human hair, was found to form a 1 : 1 complex with nicotinamide adenine dinucleotide (NAD+). The complex exhibited catalytic activity for the oxidation of glyceraldehyde to form glyceric acid. It was found from the results of pH titration, polarograms and NMR measurements that the NAD+-reduced keratin complex binds to glyceraldehyde to form an intermediate, which is susceptible to oxidation by oxygen. It was concluded from kinetic studies that this catalytic reaction showed a homotropic effect.
  • Minoru Hirota, Toshio Suzuki, Kazuhisa Abe
    1977 Volume 50 Issue 5 Pages 1129-1132
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Activation parameters of internal rotation around Car–Ccarbonyl bonds are determined by means of DNMR spectroscopy for 2,6-dihydroxybezaldehyde and some 2,6-dihydroxybenzoates. The ΔG\ eweq and ΔH\ eweq of these compounds are ca. 10 kJ mol−1 higher than those for the reference compounds void of ortho-hydroxyl groups, and the excess stabilization is attributed to the contribution of the intramolecular hydrogen bonding. The intramolecular hydrogen bonding in these compounds were discussed on the basis of their infrared spectra in the νOH region.
  • Akira Takeda, Takashi Sakai, Shohei Shinohara, Sadao Tsuboi
    1977 Volume 50 Issue 5 Pages 1133-1136
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    A new synthesis of pyrocin (1) and related compounds is described. The reaction of 2-benzoyl-4,4-dimethyl-2-buten-4-olide (5b) with 2-methyl-1-propenylmagnesium bromide (6) in the presence of CuCl gave α-benzoylpyrocin (7b) in 90% yield. The product of 7b with a specific rotation of +2.43° was obtained when the reaction was carried out in the presence of (−)-sparteine. α-Acetylpyrocin (7a) was prepared in the similar manner in 63% yield. The treatment of 7a and that of 7b with ethanolic sodium ethoxide gave 1 in 65% and 81% yields, respectively. The reaction of 1 with large excess of SOCl2 in absolute ethanol gave ethyl 3-(1-chloro-1-methylethyl)-5-methyl-4-hexenoate (8) in 82% yield. Similar treatment of 7 with SOCl2 gave ethyl 2-substituted-4-(2-methyl-1-propenyl)-5,5-dimethyl-4,5-dihydrofuran-3-carboxylate (12). Compound 8 was transformed to ethyl trans-(±)-chrysanthemate (2) in 75% yield.
  • Takeo Akiyama, Taro Kitamura, Takao Kato, Haruo Watanabe, Toshio Seriz ...
    1977 Volume 50 Issue 5 Pages 1137-1141
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The effect of the substituent in the ferrocene nucleus on the photo-ethoxycarbonylation of monosubstituted ferrocene in carbon tetrachloride–ethanol solution is described. The electron withdrawing substituents, such as chloro, bromo, iodo, cyano, and acetyl, retarded the photo-ethyoxycarbonylation, whereas the electron releasing substituents, such as ethyl accelerated the reaction. The electronic effects which affect the formation of the charge transfer complex and those which affect the reactivity of the cyclopentadienyl ring toward the attack of a trichloromethyl radical can be considered for the photo-ethoxycarbonylation.
  • Yozo Miura, Masayoshi Kinoshita
    1977 Volume 50 Issue 5 Pages 1142-1146
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    A variety of substituted N-phenyl-N-phenylthioaminyls (2), Ar–\dotN–S–Ar′, were generated by the photolysis of benzenesulfenanilides (1) in benzene in the presence of di-t-butyl peroxide or by the oxidation of 1 in benzene with lead dioxide. The ESR spectra of the radicals were completely analyzed by labeling some radicals with deuterium and with the aid of a computer simulation technique. The unpaired electron is distributed mainly on the nitrogen atom and the N-phenyl ring. The values of aN were plotted against the σ or σ in the Hammett equation, and it was found that 2, in terms of Walter’s criteria, belong to class S.
  • Hiroshi Hatanaka, Fujio Egami
    1977 Volume 50 Issue 5 Pages 1147-1156
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Amino acids and related oligomers were produced from formaldehyde and hydroxylamine in modified sea mediums at pH 5.5 and 105 °C. The modified sea mediums are characterized by a lower concentration of sodium chloride and a higher concentration of essential transition metal ions (Zn2+, Mo6+ as MoO42−, Fe3+, Cu2+, Co2+, and Mn2+) than in sea water; generally small amounts of clays (kaolin and montmorillonite) were added. About 40 species of amino acids were detected in the automatic amino acid analyzer, and 20 of them were tentatively assigned. Glycine, alanine, and serine among the protein amino acids and β-alanine were further confirmed by thin-layer chromatography. Oligomers with molecular weights of about 200–1000 were produced which gave rise to an amino acid mixture by acid hydrolysis. From the ratio (maximum, about 5) of the content of the amino groups after to before hydrolysis and the molecular size, the oligomers were tentatively regarded as oligopeptides of an unknown nature, resistant to pronase digestion. The large-molecular fraction (M. W. about 700) had a phosphatase-like activity able to hydrolyze p-nitrophenyl phosphate.
  • Mamoru Omori, Kazuo Nagashima, Seishi Yajima
    1977 Volume 50 Issue 5 Pages 1157-1160
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Ferrocene–phenol resin was synthesized from 1-ferrocenylethanol, phenol, and formaldehyde in the presence of an ammonia catalyst. The resin structure was elucidated by chemical and infrared analyses and then confirmed by micro Vickers hardness measurements. To liberate iron atoms from ferrocene skeletons, the resin was pyrolyzed in vacuo at 400 °C. The properties of the iron dispersed in a glasslike carbon matrix were investigated by magnetic susceptibility measurements, ESR, and Mössbauer spectroscopy. The iron atoms coagulated into ferromagnetic iron particles in the glasslike carbon matrix. This coagulation is discussed in connection with the resin structure.
  • Akihiko Ishida, Teruaki Mukaiyama
    1977 Volume 50 Issue 5 Pages 1161-1168
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Dienoxysilanes (2) react with acetals in the presence of TiCl4 and also in the coexistence of TiCl4 and Ti(OiPr)4 to give δ-alkoxy-α,β-unsaturated aldehydes (3–5) in good yields. In the presence of 1,8-diazabicyclo[5.4.0] undec-7-ene or 1,5-diazabicyclo[4.3.0]non-5-ene and molecular sieves 3A or 4A, the elimination reaction of δ-alkoxyl group of α,β-unsaturated aldehydes (3–5) proceeds smoothly to afford the corresponding polyenals in good yields.
  • Morio Suzuki, Jiro Amano, Motonobu Morioka, Hideo Mizuno, Ryoka Matsus ...
    1977 Volume 50 Issue 5 Pages 1169-1172
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Irradiation of an oxygen-free benzene solution of cis-4-flavanol 1a by a mercury lamp in the presence of benzophenone gave 4-flavanone (32%), benzopinacol (85%), cis- and trans-2-(diphenylhydroxymethyl)-4-flavanols (7.6%), and 2-(diphenylhydroxymethyl)-4-flavanone (7.7%), whereas photolysis of cis-4-acetoxyflavane under similar conditions gave cis-2-(diphenylhydroxymethyl)-4-acetoxyflavane(24%), 2,2′-bi-4-acetoxyflavane (6%), and benzopinacol. Photolysis of 1a in acetone gave 4-flavanone (3.6%), trans-4-(1-hydroxy-1-methylethyl)-4-flavanols (9.9%). The cis isomers of the parent and substituted 4-flavanols showed higher reactivities than the corresponding trans isomers.
  • Ryoichi Katakai
    1977 Volume 50 Issue 5 Pages 1173-1178
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Five tripeptide N-hydroxysuccinimide esters with N-terminal L-valine, L-phenylalanine, and L-alanine were polymerized in N,N-dimethylformamide with a variety of concentration of the monomers. The yields and molecular weights of the resulting sequential polypeptides were then compared in order to demonstrate the presence of the steric hindrance of the L-valine residue in polycondensation. The results of the polycondensation and the conformational study of the resulting polypeptides suggest that the side chain of the L-valine residue at the N-terminal position of the monomers hinders the polycondensation of the monomers.
  • Toyoshige Tanabe, Toshikazu Nagai
    1977 Volume 50 Issue 5 Pages 1179-1183
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The reactions of several arydiazomethanes with sulfur dioxide in the presence of 2-methyl-1-morpholinopropene gave cyclic sulfones, thietane 1,1-dioxides, indicating the existence of sulfene as a reaction intermediate. The stereoselectivity of the sulfene-enamine cycloaddition showed that the less thermodynamically stable cis orientation was generally preferred. On the other hand, the reactions in the presence of 1-morpholinocyclohexene, which has a labile proton β to the morpholino moiety, afforded acyclic or cyclic sulfones, depending on the substituents of diazomethanes. The mechanism of these reactions is discussed.
  • Kameji Yamane, Kunihide Fujimori, Je-Kyun Sin, Tetsuo Nozoe
    1977 Volume 50 Issue 5 Pages 1184-1190
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The reaction of 3-phenylpyrrolo[2,3-b]tropone (7) with phosphoryl chloride gave 8-chloro-3-phenyl-1-azaazulene (5). When 5 and 7 were treated with N-chlorosuccinimide, 2,8-dichloro-3-phenyl-1-azaazulene (6) and 2-chloro-3-phenylpyrrolo[2,3-b]tropone (8) were obtained respectively. 6 was also obtained from 8 by treatment with phosphoryl chloride. The reactions of 5 and 6 with nucleophilic reagents gave the corresponding substituted products (14am and 15am). 8-Hydrazino-3-phenyl-1-azaazulene (14m) and 2-chloro-8-hydrazino-3-phenyl-1-azaazulene (10), which had been obtained by the reaction of 5 and 6 with hydrazine hydrate, were decomposed by treatment with copper(II) sulfate in acetic acid to give 3-phenyl-1 -azaazulene (2) and 2-chloro-3-phenyl-1-azaazulene (11) respectively.
  • Ken-ichi Sato, Juji Yoshimura, Chung-gi Shin
    1977 Volume 50 Issue 5 Pages 1191-1194
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    3,6-Anhydro-1,2-O-isopropylidene-α-D-ribo-hexofuranos-3-ulose (2) was converted into 5,6-di-O-acetyl-1, 2-O-isopropylidene-α-D-ribo-hexofuranos-3-ulose (5) by the protection of the carbonyl function with hydroxylamine, followed by acetylation and removal of the protecting group with chromium(II) acetate. Nitromethane condensation of 2 and 5 at room temperature gave the corresponding 3-nitromethyl derivatives having D-gluco- and D-allo-configuration, respectively. The difference in the stereoselectivity was explained by the easiness of isomerization of the initial product to thermodynamically stable epimer, because the reaction temperature was essential to control the selectivity in the same reaction of 1,2 : 5,6-di-O-isopropylidene-α-D-ribo-hexofuranos-3-ulose. Reaction of 2 with hydrogen cyanide in dry pyridine followed by acetylation gave the corresponding 3,5,6-tri-O-acetyl-3-cyano derivative of D-allo-type, whereas, the reaction in water gave instantly 3-(hydroxycarbonimidoyl)-1,2-O-isopropylidene-α-D-allofuranose 3′,5-lactone, by the participation of the C5-hydroxyl group.
  • Mariko Kamimori, Hirochika Sakuragi, Tadashi Suehiro, Katsumi Tokumaru ...
    1977 Volume 50 Issue 5 Pages 1195-1200
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Monosubstituted phenyl radicals produce only aryl spin adducts in the reaction with nitrones described in the title, while polyhalo-substituted phenyl radicals add to solvent benzene, in competition with the formation of aryl spin adducts, to give arylcyclohexadienyl radicals, which in turn are trapped by the nitrones giving nitroxides incorporating the solvent benzene (Scheme 3).
  • Tadashi Masamune, Akio Murai, Mitsuo Takasugi, Akira Matsunaga, Nobuka ...
    1977 Volume 50 Issue 5 Pages 1201-1205
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    A modification of the isolation procedure and the details of the structure elucidation of rishitin (1) are described.
  • Akio Murai, Kouichi Nishizakura, Nobukatsu Katsui, Tadashi Masamune
    1977 Volume 50 Issue 5 Pages 1206-1216
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The regio- and stereo-selective synthesis of rishitin (1) from (−)-α-santonin (2) is described. The transformation involves twelve steps including two known processes, the overall yield amounting to 2.9% from the santonin (2).
  • Nobukatsu Katsui, Akira Matsunaga, Haruo Kitahara, Fujio Yagihashi, Ak ...
    1977 Volume 50 Issue 5 Pages 1217-1225
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The isolation and structure elucidation of lubimin (3) and oxylubimin (4), stress metabolites from diseased white potato tubers, are described.
  • Akio Murai, Mitsunori Ono, Tadashi Masamune
    1977 Volume 50 Issue 5 Pages 1226-1231
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    1-(2,3-Epoxypropyl)-1-cyclohexanol (1) and its methyl analogues (2 and 3), when treated with base in 75% aqueous dimethyl sulfoxide, gave the corresponding oxetanes (9–11) as the main products, while treatment of compound 1 under anhydrous conditions afforded the oxolane dimer (17) as the sole identified product.
  • Mutsuji Sakai
    1977 Volume 50 Issue 5 Pages 1232-1234
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Dimethyl methylenesuccinate (1) was found to equilibrate with dimethyl mesaconate (3) at elevated temperatures. Thermal rearrangements of 1 and 3 were studied kinetically and a plausible mechanism is proposed.
  • Naoki Toshima, Kyoji Aoki, Hidefumi Hirai
    1977 Volume 50 Issue 5 Pages 1235-1238
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Photoreduction of N-Acetyldiphenylmethyleneamine (1) in 2-propanol was studied both by the ESR spectroscopy of irradiated imine 1 in a matrix solvent at −196 °C and by the deuteration analysis of acetone formed from 2-propanol-d in the photoreduction process. The ESR spectrum consists of a broad singlet and a quartet. The latter is assigned to the CH3CH(OH)\dotCH2 radical, which can be produced by β-hydrogen abstraction by the excited imine 1 from 2-propanol, but not by the excited benzophenone. Formation of acetone-d on irradiation of 1 in 2-propanol-d suggests that the imine 1 in the excited state has a hydrogen abstracting character.
  • Kazuo Mukai, Toshiko Tamaki
    1977 Volume 50 Issue 5 Pages 1239-1244
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The g- and D-tensor values of p- and m-phenylenebis(galvinoxyl) biradicals in several solvents have been determined from their asymmetric frozen ESR spectra. The spectra suggested that only one conformer out of two possible ones, “propeller” and “anti-propeller” structures, exists in each biradical. The D-tensor values were calculated for the two possible conformers, based on assumed molecular structures and spin distribution. The results indicate that the “propeller” structure with a 30° twist angle is preferable for the m-phenylenebis(galvinoxyl). In the case of the p-phenylenebis(galvinoxyl), a considerable accordance between the measured and calculated values for the two conformers with a 30° twist angle was obtained. Notable solvent effects in the g- and D-tensor values were observed for the m-phenylenebis(galvinoxyl), but not for the p-phenylenebis(galvinoxyl).
  • Isao Taniguchi, Koji Machida, Norio Sato, Taro Sekine
    1977 Volume 50 Issue 5 Pages 1245-1250
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The differential capacity and the surface tension at the electrode-electrolyte interface of a dropping-mercury electrode were measured in 0.5 M H2SO4 and 0.5 M Na2SO4 solutions for various concentrations of benzoic acid. On the basis of the Frumkin-Damaskin theory, the adsorption of benzoic acid on mercury was studied in the acid solution, and the parameters involved in the F-D theory were determined: A=1.6 μJ cm−2 (Γm=6.5×10−10 mol cm−2), B0=597 l mol−1, a=−0.35–2.5 E/V, and C′=5.95 μF cm−2. The experimental values of the capacity and the surface tension are in good agreement with the theoretical values calculated by using the parameters obtained. The absence of an anodic maximum in the capacity-potential curve in the presence of benzoic acid was determined to be associated with a strong repulsive force between the adsorbed molecules. The value obtained for the maximum surface excess of benzoic acid is explained in terms of adsorption of the acid molecules for a vertical orientation on the electrode surface. This conclusion was supported by comparing the B0 value for benzoic acid with those for phenol and aniline. The adsorption of benzoic acid in neutral solutions is also discussed.
  • Yoshio Homma, Yukio Murakami
    1977 Volume 50 Issue 5 Pages 1251-1255
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    In order to determine the optimum irradiation conditions to produce the 61Cu for nuclear medical use, excitation curves and thick-target yield curves were determined for the α reactions producing 61Cu, 57Co, and 58Co, and 3He reactions producing 61Cu, 56Co, 57Co, and 58Co, both from natural cobalt. The 59Co(α, 2n) 61Cu and the 59Co(3He, n) 61Cu reactions give cross section peaks of 340 mb and 6 mb at 25 MeV and 35 MeV, respectively. The 61Cu thick-target yields for these reactions at 40 MeV were 6 mCi/μAh and 110 μCi/μAh, respectively. A simple and reliable anion-exchange method was developed to provide carrier-free 61Cu. The purity of 61Cu was determined with a Ce(Li) spectrometer. Photopeak efficiencies have been calculated at principal γ-ray energies of 61Cu, 64Cu, and 67Cu, for a 1/2 in. NaI scintillation camera. Alternative nuclear reactions and the methods for producing 61Cu are compared.
  • Mikio Morita, Kunio Hirosawa, Toshio Sato
    1977 Volume 50 Issue 5 Pages 1256-1258
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The electronic absorption spectra of naphthalene, anthracene, and naphthacene in dried, molten zinc chloride were measured and found to be almost the same as those of aromatics–aluminum chloride complexes in the solid state. ESR measurements were also made; they confirmed the presence of radicals. From these results, it was concluded that the aromatics reacted with molten zinc chloride to form EDA-complexes, i. e., σ-complexes and cation radicals.
  • Kazuaki Harata
    1977 Volume 50 Issue 5 Pages 1259-1266
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    α-Cyclodextrin, which is a cyclic oligosaccharide consisting of six D-glucose residues, forms a 1 : 1 complex with sodium 1-propanesulfonate. The crystal structure was determined by the X-ray method. The crystal is orthorhombic, and the space group is P21212 with cell dimensions of a=21.608(2), b=16.700(2), and c=8.302(1) Å, and Z=2. The structure was solved on the basis of 2219 diffractometer data and refined by the block-diagonal leastsquares method to the final R-value of 0.077. The α-cyclodextrin molecule is nearly hexagonal with diagonal distances of 8.40–8.59 Å between the glycosidic oxygen atoms. The framework of the crystal is built up of a stack of α-cyclodextrin rings along the c axis in head-to-tail arrangement, with channel-type structure. The adjacent α-cyclodextrin molecules along the channel are linked by six O(3)···O(6) hydrogen bonds. The guest 1-propanesulfonate anions are located in channels, having statistical disorder. The primary hydroxyl groups of α-cyclodextrin exhibit gauche-trans conformation, and they form hydrogen bonds with the sulfonato group resulting in oxygen-oxygen distances of 2.72–2.80 Å. The propyl group is in contact with the O(2), O(3) side of the α-cyclodextrin ring. The sodium ion is located outside the channel, and is surrounded by five oxygen atoms which form a distorted trigonal bipyramid.
  • Tohru Kishi, Masashi Tanaka, Jiro Tanaka
    1977 Volume 50 Issue 5 Pages 1267-1271
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The fluorescence spectra of 5-hydroxytryptamine (serotonin) in acidic media have been studied by means of fluorescence polarization, temperature dependence of fluorescence, and kinetics of the protonation in H2O and D2O. The red-shifted emission appearing by protonation in the excited state is ascribed to the protonated form of serotonin at C4. In order to confirm the assignment of electronic spectra, the absorption spectra of the single crystal of 5-methoxyindole-3-acetic acid have been measured by means of reflection technique, the directions of transition moments being determined by polarization analysis. Calculation was carried out on the energy levels of the excited state for serotonin and its protonated forms, and the directions of transition moments were compared with the experimental results.
  • Takayuki Yano
    1977 Volume 50 Issue 5 Pages 1272-1277
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Chloroform was pyrolyzed in the absence and in the presence of one of three additives—D2, CH4, and CD4, over the temperature range of 1000–1200 K in a single-pulse shock tube. The main products of the decomposition of chloroform by itself were tetrachloroethylene and hydrogen chloride. On the other hand, tetrachloroethylene, trichloroethylene, dichloromethane, and hydrogen chloride were the major products in the presence of D2, while in the chloroform–methane systems they were tetrachloroethylene, trichloroethylene, 1,1-dichloroethylene, vinyl chloride, ethane, and hydrogen chloride. From the deuterium distribution of the products, as determined by mass spectrometry, it is found that the hydrogen atoms of trichloroethylene and 1,1-dichloroethylene mainly came from chloroform and methane respectively, while the hydrogen atoms of vinyl chloride came from both chloroform and methane. The change in the product distribution resulting from the addition of deuterium or methane and the hydrogen isotopic distribution suggest that the mechanism is composed of Cl atom elimination in the initiation step and successive reactions involving “hot” molecule reactions. The hydrogen isotopic distribution of vinyl chloride may indicate that the three-centered hydrogen elimination (αα) process competes with the four-centered (αβ) process in the decomposition of “hot” 1,1-dichloroethane.
  • Haruo Iwahashi, Yo-ichi Ishikawa, Shin Sato, Kinko Koyano
    1977 Volume 50 Issue 5 Pages 1278-1281
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    It was shown that cyclohexyl radicals formed by the γ-radiolysis of cyclohexane were trapped by phenyl t-butyl nitrone (PBN) to give a nitroxide with a well defined ESR spectrum. We measured the yield of this nitroxide. In order to establish the radical and electron scavenging properties of PBN, we measured the effect of this compound on the yields of hydrogen and nitrogen by adding dinitrogen oxide in cyclohexane together with PBN. The results suggested that PBN is able to scavenge not only free radicals but also electrons. The following relative rates were obtained: k(e+PBN→PBN)/k(e+N2O→N2O)=0.7 and k(H+PBN→HPBN)/k(H+C6H12→H2+C6H11)≈200 at room temperature. The G-value of the scavengeable hydrogen atoms from cyclohexane was estimated to be 3.4±0.4.
  • Hiroshi Hiratsuka, Yoshie Tanizaki, Toshihiko Hoshi
    1977 Volume 50 Issue 5 Pages 1282-1286
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Electronic absorption spectrum of 2-ethylthio-1,3-diazaazulene (ESDA) is investigated by means of dichroism analysis using the stretched PVA film. Seven π-π* bands and an allowed n-π* band are assigned. The experimental assignment of π-π* bands is in good agreement with the theoretical result using the PPP calculation. The effect of substituent groups on 1,3-diazaazulene (DA) is discussed by making use of a correlation diagram of SCF MO’s of ESDA, 2-ethoxy-1,3-diazaazulene (EODA), DA, and the substituent groups. Configuration analysis of wave functions for ESDA and EODA is carried out, and the substituent effects of the ethylthio and ethoxyl groups are compared. The result shows that the ethylthio group perturbs the electronic structure of DA more strongly than the ethoxyl group.
  • Fumio Watari
    1977 Volume 50 Issue 5 Pages 1287-1294
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    Studies were carried out on the infrared spectra (33–4000 cm−1) of eight isotopic trimethylarsine–boranes, (CH3)3AsBH3, (CH3)3As10BH3, (CH3)3AsBD3, (CH3)3As10BD3, (CD3)3AsBH3, (CD3)3As10BH3, (CD3)3AsBD3, and (CD3)3As10BD3, in the solid state at low temperature, and on the Raman spectra (0–4000 cm−1) in the solid state and in solution of dichloromethane at room temperature. The spectra were interpreted on the basis of C3V molecular symmetry, complete assignments for all fundamentals except the internal torsion being made. Normal coordinate calculations were carried out utilizing a symmetry force field in order to confirm the assignments. One of the methyl rocks was found to be mixed with the borane rock, making the assignments of these frequencies complicated. The As–B and As–C force constants were found to have the values 1.849 and 3.087 mdyn/Å, respectively.
  • Kikuko Hayamizu, Osamu Yamamoto
    1977 Volume 50 Issue 5 Pages 1295-1297
    Published: 1977
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The 13C spin-lattice relaxation time T1 in the liquid crystalline compound p,p′-azoxyanisole; (PAA; 4,4′-dimethoxyazoxybenzene) was observed in the nematic and isotropic liquid phases. From the obtained T1’s of the ring and the methyl carbons, the anisotropic rotational diffusion constants were determined. It is concluded that the rotational reorientation around the molecular axis is faster by an order of 103 than the rotational motion around the axis perpendicular to the molecular axis in the nematic and isotropic liquid states.
feedback
Top