Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 57 , Issue 5
Showing 1-50 articles out of 60 articles from the selected issue
  • Masaharu Komiyama, Robert P. Merrill
    1984 Volume 57 Issue 5 Pages 1169-1173
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Two factors which play important roles in determining the concentration profiles in the impregnation of porous catalysts, viz., penetration rate of impregnating solution and the use of acids, were examined. The flow rate of impregnating solution into a spherical dry pellet consisting of polydispersed pores obeyed the equation which assumed constant pressure differential at the liquid front independent of its position in the pellet. The adsorption behavior of nickel ions onto γ-alumina strongly depended on the pH of the solution, and very weakly on the kind of acids used. By controlling the pH of the impregnating solution, it was possible to obtain a surface impregnation, a uniform impregnation and a subsurface impregnation for nickel on γ-alumina.
  • Minoru Sakiyama, Shigeo Murata
    1984 Volume 57 Issue 5 Pages 1174-1178
    Published: 1984
    Released: June 27, 2006
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    The homolytic lattice energy ΔUR of an ionic crystal MxAy was defined as the standard internal energy change at 298.15 K for the following vaporization process to yield neutral species M and A: (l/x)MxAy(c)=M(g)+(y/z)A(g). ΔUR and [ΔUR–(y/xHfo(A,g)] were calculated for formates and acetates and for oxalates and glycolates, respectively, of metals, and were analyzed empirically. ΔUR(formate)\simeqΔUR(acetate) holds for every metal. ΔUR of oxalates and glycolates may be expressed as follows: ΔUR(oxalate or glycolate)=aΔUR(formate or acetate)+b(y/x), where a is the constant close to unity, and b is the constant which is, possibly, close to zero for oxalates and about 40 kJ mol−1 for glycolates. The linear relations in ΔUR were discussed in relation to crystal structure of the salts and carboxyl O–H bond dissociation energy of the corresponding carboxylic acids.
  • Ju-seong Lee, Tamihiko Kato, Akira Fujishima, Kenichi Honda
    1984 Volume 57 Issue 5 Pages 1179-1183
    Published: 1984
    Released: June 27, 2006
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    The current doubling behavior of alcohols was studied on an n-type ZnO polycrystalline electrode. The increase in photocurrent due to alcohols on the ZnO depended on pH of the solution. The photocurrent was almost doubled in alkaline solution. It was found that the ZnO photoanode dissolved in the neutral aqueous solution but the dissolution reaction of ZnO was completely suppressed in alkaline solution at a sufficiently large pH. From the experimental results obtained by the rotating ring disk electrode and gas chromatographic and mass spectrometric analyses, a mechanism of the current-doubling reaction is proposed.
  • Ichiro Okura, Shin Kusunoki, Shigetoshi Aono
    1984 Volume 57 Issue 5 Pages 1184-1188
    Published: 1984
    Released: June 27, 2006
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    The formation of the cation radicals of viologen dyes was established when an aqueous solution containing zinc tetraphenylporphyrintrisulfonate (Zn–TPPS3), viologen dye, and 2-mercaptoethanol was irradiated by visible light. The reduction of viologen has been studied kinetically; its reduction rate may be expressed as follows:
    v=\fracd[V+]dt=\left(\frack3[Zn−TPPS3]01+K1[V2+]+K2[V+]\ ight)\left(\frack4[V2+]k3+k4[V2+]\ ight)\left(\frack6[RSH]k5[V+]+k6[RSH]\ ight),
    where [V2+], [V+], and [RSH] are the concentrations of the oxidized form and the reduced form of viologen, and 2-mercaptoethanol respectively. On the basis of the rate expression, a reaction mechanism containing the complexation of Zn–TPPS3 by viologen was proposed. On the addition of hydrogenase to the above photoirradiation system, hydrogen evolution was observed by the irradiation of visible light.
  • Hiroyuki Kageyama, Kunio Miki, Yasushi Kai, Nobutami Kasai, Yoshio Oka ...
    1984 Volume 57 Issue 5 Pages 1189-1196
    Published: 1984
    Released: June 27, 2006
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    (+)-6-Benzylsparteine (a) crystallizes in orthorhombic systems; P212121, a=10.711(1), b=25.868(4), c=6.804(1) Å, and Z=4;EtMgBr-(+)-6-benzylsparteine (b) also belongs to orthorhombic system; P212121, a=11.020(4), b=23.660(10), c=8.666(6) Å and Z=4; and MgBr2−(+)-6-benzylsparteine toluene solvate (c), orthorhombic system; P212121, a=16.654(3), b=19.723(4), c=8.637(2) Å and Z=4. The structure of a was solved by the direct method and those of b and c by the heavy atom method. Refinements were carried out by the block-diagonal least-squares procedure; R values are: (a) 0.055. (b) 0.169, and (c) 0.118, respectively for 1342, 1445, and 1501 reflections. The a molecule takes a one-boat form, whereas by, coordination to the Mg atom it changes into all-chair form in b and c molecules. The Mg atom has a distorted tetrahedral geometry; b, Mg–N=2.13(4) and 2.19(4), Mg–C 2.34(5) and Mg–Be=2.506(16) Å and N–Ng–N=83.1(14)°; c, Mg–N=2.08(3) and 2.17(3), Mg–Br=2.454(12) and 2.473(12) Å and N–Mg–N=85.8(10)°. The structures of these molecules are compared with those of (−)-sparteine complexes with EtMgBr, t-BuMgCl, and MgCl2. On the basis of the molecular structures determined the activity of these Grignard reagent–(−)-sparteine derivatives for the enantiomer-selective polymerization of MBMA is discussed.
  • Harumichi Kobashi, Reiko Kondo, Hiroki Ikawa, Toshifumi Morita
    1984 Volume 57 Issue 5 Pages 1197-1201
    Published: 1984
    Released: June 27, 2006
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    Effects of solvents and heavy-atom (H–A) containing compounds on the lifetime of the title biradical (1) have been examined to elucidate the decay mechanism of 1 in fluid solutions by means of nanosecond laser spectroscopy. 1 was quenched effectively by H–A compounds such as diethylmercury and iodoethane. The decay rates of 1 showed no explicit correlation with solvent polarities, while a linear correlation was found between the decay rate and the sum of squares of the spin-orbit (S–O) coupling factors of heavy atoms involved in the solvents; chlorobezene, 1,2-dichloroethane, dichloromethane, bromobenzene, and dibromomethane. It has been shown that (i) the biradical lifetime is determined by intersystem crossing (ISC) from the triplet to singlet spin state prior to chemical reactions, (ii) ISC is enhanced by H–A perturbation through the S–O interaction, and (iii) the reactivity of the singlet biradical (11) but not the triplet one (31) sways the product distribution in the triplet-sensitized photodimerization of acenaphthylene.
  • Kunio Esumi, Kimihiko Ogihara, Kenjiro Meguro
    1984 Volume 57 Issue 5 Pages 1202-1204
    Published: 1984
    Released: June 27, 2006
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    The aqueous dispersion of iron oxide by acrylic oligomer surfactants was examined by particle size and zeta potential measurements. Iron oxide particles were suspended in an aqueous iron(III) chloride solution to render the surface positively charged. The iron oxide particles so prepared were then flocculated by the addition of a small amount of acrylic oligomer surfactant. The floes of iron oxide could be redispersed by further addition of acrylic oligomer surfactant. The flocculation and the redispersion processes can be explained in terms of a “two-fold adsorption layer” mechanism of the acrylic oligomer surfactant. The concentrations of acrylic oligomer surfactants needed to achieve flocculation and redispersion decreased with an increase in acrylic content of the oligomer surfactants.
  • Takehiko Ono, Yoshiro Nakagawa, Hisashi Miyata, Yutaka Kubokawa
    1984 Volume 57 Issue 5 Pages 1205-1210
    Published: 1984
    Released: June 27, 2006
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    The structure of Mo–Ti oxide catalysts has been investigated by using IR and XRD techniques. At a low Mo content, MoO3 is highly dispersed on TiO2, an amorphous phase being formed. Simultaneously, a shift of the Mo=O band from 995 cm−1 to 950 and 905 cm−1 takes place. The maximum rate of the oxidation of C2H5OH and C3H6 over Mo–Ti-6(atom% of Mo) is attributable to the weakening of the Mo=O bond. The 18O tracer and kinetic studies of the oxidation of C3H6 over Mo–Ti and V–Ti oxides suggest that a redox mechanism is applicable, the rate constants of reduction and reoxidation step being determined. The promoter action of TiO2 support is attributed mainly to the increase in the rate of reduction step.
  • Yasuo Hara, Ken-ichi Okamoto, Jinsai Hidaka, Hisahiko Einaga
    1984 Volume 57 Issue 5 Pages 1211-1216
    Published: 1984
    Released: June 27, 2006
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    Stopped-flow kinetic and equilibrium studies have been made of the formation of a cobalt(II) complex with N-(8-quinolyl)aminoacetic acid in 0.10 mol dm−3 aqueous sodium chloride containing 12 vol% ethanol at 25 °C. Octahedral mono- and bis-ligand complexes were formed via the two pathways of the reactions of deprotonated and monoprotonated ligand species with the aquacobalt(II) ion. The coordination mechanism is discussed.
  • Seichi Okeya, Shinichi Kawaguchi
    1984 Volume 57 Issue 5 Pages 1217-1221
    Published: 1984
    Released: June 27, 2006
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    When diketene and sodium tetrachloropalladate(II) are mixed in aqueous solution, color of the solution changes promptly from dark red to yellow. During this fast primary reaction about one equivalent of diketene is consumed and acetoacetic acid (H2A) is retained as a trihapto ligand in [PdCl2(HA)] (2). The succeeding steady hydrolysis of diketene (S) proceeds as a pseudo first-order reaction, obeying the rate law: –d[S]/dt=kobsd[S]=(k0+kcat)[S], kcat=kobsdk0=(k1+k2/[H+])[PdII]/[Cl], where k1=2.0×10−5 s−1 and k2=2.96×10−6 mol dm−3 s−1 at 0 °C and μ=1.0 mol dm−3 (HClO4 and NaClO4). A mechanism which postulates complex 2 as the effective catalyst is proposed to explain the observed two-term rate equation.
  • Kenzo Kitayama, Takashi Katsura
    1984 Volume 57 Issue 5 Pages 1222-1226
    Published: 1984
    Released: June 27, 2006
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    Phase equilibria in the systems, Dy2O3–V2O3–V2O5 and Ho2O3–V2O3–V2O5, were established at 1200 °C by changing the oxygen partial pressure from 4.32 to –7.50 Pa in terms of logPo2. In both systems, Ln2O3, LnVO4, LnVO3, VnO2n−1(n=2–7), VO2, and Ln8V2O17(4Ln2O3·V2O5) are stable, and compounds with mole ratio Ln2O3/V2O5=5⁄1 are not stable under the present experimental conditions. On the basis of the established phase diagrams, the standard Gibbs energies of reactions, (1) 3 Dy2O3+2 DyVO3+O2=Dy8V2O17, (2) DyVO3+1/2 O2=DyVO4, (3) 3 Ho2O3+2 HoVO3+O2=Ho8V2O17, and (4) HoVO3+1/2 O2=HoVO4, were determined to be −278, −123.8, −277, and −122.4 kJ, respectively. LnVO4, Ln8V2O17, V2O3, and VO2 have nonstoichiometric compositions. ΔG° values for reactions (2) and (4) fit well on the linear line presented by us.
  • Kazuaki Yamanari, Norimatsu Takeshita, Yoichi Shimura
    1984 Volume 57 Issue 5 Pages 1227-1234
    Published: 1984
    Released: June 27, 2006
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    Several thiolato complexes of [Co(SNNS)(diamine)]+ type were prepared (diamine stands for en=1,2-ethanediamine, R-pn=(R)-1,2-propanediamine, and RR-chxn=(R,R)-1,2-cyclohexanediamine) and characterized from their visible–UV absorption, circular dichroism, and 13C NMR spectra, where SNNS denotes two kinds of open-chain quadridentate ligands, H2endet=3,6-dimethyl-3,6-diazaoctane-1,8-dithiol and R-H2pndet=(R)-3,4,6-trimethyl-3,6-diazaoctane-1,8-dithiol. Both the SNNS ligands gave the two geometrical isomers, cis-α(dark green) and cis-β(dark violet), whereas 3,7-dimethyl-3,7-diazanonane-1,9-dithiolate(2–) ligand gave no stable monomeric complex. Interestingly, stereoselective complex formation was found in Δ-cis-α-[Co(R-pndet)(en or RR-chxn)]+, Δ(SNRN)-cis-β-[Co(endet)(R-pn or RR-chxn)]+, and Δ(SNRN)-cis-β-[Co(R-pndet)(en or RR-chxn)]+, the Δ-cis-α configuration of the former complex being the novel one having the equatorially-oriented terminal chelate rings on the tertiary nitrogen atoms.
  • Masahiko Saburi, Yasuhiko Yokowo, Sadao Yoshikawa
    1984 Volume 57 Issue 5 Pages 1235-1239
    Published: 1984
    Released: June 27, 2006
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    Two possible isomers (trans,cis and trans,trans) of trans-(NO2)-[(Co(NO2)2(ampr)2]ClO4 (ampr=(S)-2-aminomethylpyrrolidine) were isolated separately by fractional recrystallization. The dinitro complexes were converted to the corresponding trans(Cl,NO2)–[CoCl(NO2)(ampr)2]+ complexes. Based on the circular dichroism and 13C-NMR spectral data, it was shown that the less soluble dinitro complex gave the single isomer of the chloronitro complex, while the more soluble one yielded two diastereomeric chloronitro complexes. Thus, the former is assigned to the trans,cis configuration, and the latter to the trans,trans, taking the geometries of the complexes into consideration.
  • Kazuhiko Nakayama, Takashi Komorita, Yoichi Shimura
    1984 Volume 57 Issue 5 Pages 1240-1254
    Published: 1984
    Released: June 27, 2006
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    A large number of mixed-ligand [Pd(N)n(O)4−n]-type complexes (n=1–4) which contain at least one optically active ligand were synthesized and isolated in a systematic manner. (S)-Propylenediamine, (2S)-N1,N1-diethyl-1,2-propanediamine, and (S)-amino carboxylates were employed as one ligand, which is optically active; ammonia, diamines, amino carboxylates, acetates, and dicarboxylates as the other ligand occupying the remaining coordination sites. Isomerism could be detected in the mixed complexes of an unsymmetrical diamine and an amino carboxylate and has been discussed on the basis of 13C NMR and CD spectra. Moreover, the influence of optically inactive ligands on the vicinal CD spectra has been examined, and also the additivity of vicinal CD contributions of two different optically active ligands has been demonstrated.
  • Akiharu Hioki, Shigenobu Funahashi, Motoharu Tanaka
    1984 Volume 57 Issue 5 Pages 1255-1259
    Published: 1984
    Released: June 27, 2006
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    The complex formation reactions of nickel(II) nitrate, nickel(II) acetate, and nickel(II) chloride with 1-(2-pyridylazo)-2-naphthol (PAN) in acetic acid (HOAc) to form the 1:1 nickel(II)–PAN complex have been studied kinetically by using a stopped-flow technique. The second-order rate constants and activation parameters at 25 °C are k=(1.4±0.1)×104 mol−1 kg s−1, ΔH\ eweq=51.2±1 kJ mol−1, ΔS\ eweq=6.4±4 J mol−1 K−1, and ΔV\ eweq=23.4±2.4 cm3 mol−1 for Ni(NO3)2, k=(1.1±0.1)×104 mol−1 kg s,−1, ΔH\ eweq=49.5±1 kJ mol−1, ΔS\ eweq=−1.3±4 J mol−1 K−1, and ΔV\ eweq=15.5±2.6 cm3 mol−1 for Ni(OAc)2, and k=(4.8±0.1)×104 mol−1 kg s−1, ΔH\ eweq=51.4±1 kJ mol−1, ΔS\ eweq=17.0±4 J mol−1 K−1, and ΔV\ eweq=35.4±5.5 cm3 mol−1 for NiCl2. The positive value of ΔV\ eweq strongly suggests a dissociative mode of activation.
  • Yorihiro Yamamoto, Shunichi Haga, Etsuo Niki, Yoshio Kamiya
    1984 Volume 57 Issue 5 Pages 1260-1264
    Published: 1984
    Released: June 27, 2006
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    The rate and products of oxidation of methyl linoleate dispersed in water by Triton X-100 were measured at 50 °C. The oxidation was initiated by water- or oil-soluble azo-initiators. The oxidation proceeded smoothly by both types of initiators without any noticeable induction period and a constant rate of oxygen uptake was observed. Conjugated diene hydroperoxides were formed almost quantitatively. The oxidizability for methyl linoleate in aqueous dispersion was obtained as kp/(2kt)1⁄2=0.032(s·mol/L-oil)−1⁄2 where kp and kt are the rate constants for propagation and termination reactions, respectively. This value was similar to that observed in the homogeneous oxidation in chlorobenzene. L-Ascorbic acid inhibited the oxidation initiated by water-soluble initiator but it could not inhibit the oxidation initiated by oil-soluble initiator. 2,6-Di-t-butyl-4-methylphenol inhibited the oxidation initiated by both initiators. On the other hand, α-tocopherol was effective for the oxidation initiated by oil-soluble initiator and it incompletely inhibited the oxidation initiated by water-soluble initiator.
  • Yoshiaki Sato, Chung-gi Shin, Satoshi Sumiya, Yoshiharu Nakajima, Juji ...
    1984 Volume 57 Issue 5 Pages 1265-1270
    Published: 1984
    Released: June 27, 2006
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    This paper describes the synthesis of 3-(3-t-butoxypropyl)-6-hydroxy-2,5-piperazinedione derivatives by the hydroxylation of the corresponding 2,5-piperazinedione with N-bromosuccinimide (NBS) in the presence of water and the subsequent cyclization to 2-oxa-7,9-diazabicyclo[4.2.2]decane-8,10-dione derivatives (11). The reversible interconversion between the spiro[oxolane-2,2′-piperazine]-3′,6′-dione prepared previously and the bicyclo compound 11 was established. The formation mechanisms and the structural confirmation of 11 and the other products are discussed.
  • Yujiro Nomura, Takashi Bando, Yoshito Takeuchi, Shuji Tomoda
    1984 Volume 57 Issue 5 Pages 1271-1275
    Published: 1984
    Released: June 27, 2006
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    The reaction 5-benzylidene-2,3,4,5-tetrahydropyridine (1) with nucleophilic reagents, such as sodium tetrahydroborate, lithium tetrahydridoaluminate, organometallic reagents, pyrrole, or ethyl propiolate, has been studied. The reaction of 1 with sodium tetrahydroborate, lithium tetrahydridoaluminate, phenylmagnesium bromide, butyllithium gave exclusively respective 1,2-adducts. The reaction with pyrrole gave a tricyclic 1:1 adduct while 1 formed a 1:2 adduct with ethyl propiolate.
  • Yujiro Nomura, Takashi Hayama, Yoshito Takeuchi, Shuji Tomoda, Yuko Ka ...
    1984 Volume 57 Issue 5 Pages 1276-1278
    Published: 1984
    Released: June 27, 2006
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    The title reaction performed under typical conditions of the Willgerodt-Kindler reaction afforded “abnormal” product 1,3-thiazines. A mechanism involving the Diels-Alder reaction between N-benzylidenearyl-amine and thiobenzaldehyde has been suggested to explain the formation of 1,3-thiazines.
  • Atsuyoshi Ohno, Hisami Kobayashi, Takehiko Goto, Shinzaburo Oka
    1984 Volume 57 Issue 5 Pages 1279-1282
    Published: 1984
    Released: June 27, 2006
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    1-Propyl-1,4-dihydronicotinamide (PNAH), 1-(3-phenylpropyl)-1,4-dihydronicotinamide (1a), 1-(2-phenylthioethyl)-1,4-dihydronicotinamide (1b), and 1-(4-phenylthiobutyl)-1,4-dihydronicotinamide (1c) and their 4-deuterated analogs are synthesized as NAD(P)H-models and subjected to the reduction of m-nitro-α,α,α-trifluoroacetophenone in the presence or absence of magnesium ion in acetonitrile. Kinetics at 323 K have been studied. Kinetic isotope effect is small (2.33) only when 1a or 1b is employed for the reduction in the presence of magnesium ion, whereas it appears large (≈3.2) under other conditions. The result has been interpreted in terms of steric interference by a proximate phenyl group on the approach of the substrate to form a binary (in the absence of magnesium ion) or ternary (in the presence of magnesium ion) complexes. Thermodynamic parameters for the formation of complexes between the models and magnesium ion have been studied. It has been elucidated that enthalpy of complexation is small for 1a than others. However, the small enthalpy of complexation is compensated by small entropy of complexation affording almost constant free-energy of complexation throughout the models studied.
  • Bu Yong Lee, Yasunobu Inoue, Iwao Yasumori
    1984 Volume 57 Issue 5 Pages 1283-1289
    Published: 1984
    Released: June 27, 2006
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    A combined infrared spectroscopic (IR) and thermal desorption (TD) study of CO adsorption was carried out to reveal the nature of Pd surface which is modified by the addition of ZrO2. The TD spectra of CO from SiO2- or α-Al2O3-supported Pd showed two broad peaks, α at 340 K and β at 530 K. The addition of ZrO2 in a range of atomic ratios of Zr/Pd=0.5–3.0 produced a new broad peak δ at 390–420 K and the β peak shifted toward higher temperature by 16–19 K. The IR spectra of CO on Pd/SiO2 catalysts, consisting of two broad bands: A (2030–2070 cm−1) and B (1880–1920 cm−1), were modified by the addition of ZrO2 to give rise to a new sharp band, Bh (1970–1985 cm−1) and to make the A band narrower. From the correspondence of the variation in intensities and position of the IR bands with those in the fraction of coverage of CO with temperature, the α peak was correlated to the A band, the δ peak to the Bh band, and the β peak to the B band. The changes in the TD peaks and the IR bands caused by added ZrO2 were semiquantitatively compared and are discussed in terms of the electronic and geometric effects; a high electron density state of Pd surface atoms as well as the formation of adsorption sites with specific structure is proposed. A brief study was made for the role of the sites in the catalytic hydrogenation of ethylene and cyclohexene.
  • Tsuyoshi Arakawa, Midori Takakuwa, Gin-ya Adachi, Jiro Shiokawa
    1984 Volume 57 Issue 5 Pages 1290-1294
    Published: 1984
    Released: June 27, 2006
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    The physicochemical properties of an activated Eu(III) ion-exchanged mordenite (Eu–M) have been studied by the measurement of the fluorescence of the europium ion. When Eu–M (the exchanged level; 3.7%) was degassed only above 300 °C, a band emission which peaked at 488 nm appeared. This band emission was associated with the Eu2+ 5d–4f transition. The peak of the band emission shifted linearly to a shorter wavelength with the increase in the exchanged level of the Eu ions. For the Eu–M sample, which was reduced by H2 at 500 °C, the peak position of the band emission was almost 499 nm in all cases, and the quantum yield for a reduced sample was larger than that for a dehydrated sample. The quantum yield for a reduced sample fell off extremely above the exchanged level of 6%. Moreover, the Eu2+–Eu22+ energy transfer in the reduced samples was discussed.
  • Fujiko Iwasaki, Kiyoshi Mutai
    1984 Volume 57 Issue 5 Pages 1295-1298
    Published: 1984
    Released: June 27, 2006
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    The crystal structure of N,N,N′,N′-tetramethylpiperazinediium bis(2,4-dinitrophenolate) dihydrate has been determined by the X-ray method. The crystals are triclinic, space group P\barl, a=11.504(2), b=8.239(2), c=7.119(2) Å, α=106.22(2), β=99.67(2), γ=92.31(2)°, Z=1. The final R is 0.067 for 2743 reflections. Two dinitrophenolate anions are connected by hydrogen bonds, via the water molecules, forming a dimeric unit related by the center of symmetry. N,N,N′,N′-Tetramethylpiperazinediium ion has a chair conformation.
  • Tatsuya Takagi, Hideaki Fujiwara, Yoshio Sasaki
    1984 Volume 57 Issue 5 Pages 1299-1303
    Published: 1984
    Released: June 27, 2006
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    Dipole association between acetonitrile derivatives and polar substances such as tetramethylurea and dibutyl sulfoxide is investigated in nonpolar solvents. Association parameters and thermodynamic parameters are derived and discussed in relation to the substituent constants. 1H and 13C NMR chemical shifts show that the major structures of the associate are antiparallel. Association energies are also determined using semiempirical MNDO MO method, which supports the experimental results for energies as well as structures.
  • Haruhiko Yokoyama
    1984 Volume 57 Issue 5 Pages 1304-1311
    Published: 1984
    Released: June 27, 2006
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    Electric conductivities of the diastereoisomeric salts, Δ(−)589-[Co(NO2)2(en)2]Δ(+)546-[Co(edta)] and Λ-(+)589-[Co(NO2)2(en)2]Δ(+)546-[Co(edta)], were measured in water at 15, 25, and 35 °C. Results were analyzed in terms of the conductivity equations of Fuoss-Hsia and Pitts. The obtained values of the ion-association constant are large and decrease with increasing temperature. The results can not be entirely explained by the electrostatic theories of ion association and suggest the formation of contact ion pairs, attributable to the existence of interactions other than simple electrostatic ones between the complex ions. No appreciable difference is found in the obtained thermodynamic parameters of ion association between the two salts. Ion–solvent interactions and effective sizes of the dissolved complex ions are also discussed in connection with the estimation of the closest distance of approach of the ions.
  • Yukihide Yamashita, Hiroyuki Kobayashi, Akihiro Yoshino, Kensuke Takah ...
    1984 Volume 57 Issue 5 Pages 1312-1316
    Published: 1984
    Released: June 27, 2006
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    The STO-3G method was applied to the protonation of thiophene and chlorothiophenes. The optimized structures and charge densities thus obtained are consistent with the experimental results obtained from the 1H NMR spectral data. In the neutral molecule, the β-chloro substituent lowers the total energy more than the α-one; however, the latter stabilizes the protonated state more than the former.
  • Takashi Ishiwata, Atsuto Tokunaga, Tsutomu Shinzawa, Ikuzo Tanaka
    1984 Volume 57 Issue 5 Pages 1317-1320
    Published: 1984
    Released: June 27, 2006
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    The pulses of the fundamental and its frequency doubled outputs from a tunable dye laser are used to promote a stepwise exciation of the E(0g+)–X1Σg+ transition through the B3Π(0u+) state in molecular bromine. The double resonance is detected by the associated UV emission which originates from the E(0g+) state radiating back to the B3Π(0u+) state. The E(0g+) state is analyzed in detail on the basis of the selection rules of two transition components and the E–B fluorescence spectrum. The molecular parameters are derived as Te=49778.5 cm−1, ωe=150.8 cm−1, ωexe=0.41 cm−1, and re=3.197 Å for the 79Br2 isotope species.
  • Hideshi Okuda, Sumio Ozeki, Shoichi Ikeda
    1984 Volume 57 Issue 5 Pages 1321-1327
    Published: 1984
    Released: June 27, 2006
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    The surface tension of aqueous NaBr solutions of dodecyldimethylammonium bromide has been measured by the drop weight method at different surfactant and NaBr concentrations. By applying the Gibbs adsorption isotherm, surface excess densities of surfactant cation, Na+ and Br are derived as functions of surfactant concentration at different NaBr concentrations. The rational mean activity coefficients of surfactant and NaBr are both approximated by a common expression satisfying the Brφnsted principle for mixed electrolytes and containing the ionic strength as a variable. Surface excess density of surfactant cation increases with increasing surfactant concentration and has a general tendency still increasing even at the critical micelle concentration. Some comparison of the behavior of surface excess densities of ions between the present bromide system and the previous chloride system is made. The Corrin-Harkins plot for the critical micelle concentration consists of two straight lines intersecting at 0.015 mol dm−3 NaBr.
  • Chikara Hongo, Ryuzo Yoshioka, Masanori Tohyama, Shigeki Yamada, Ichir ...
    1984 Volume 57 Issue 5 Pages 1328-1330
    Published: 1984
    Released: June 27, 2006
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    The chemical synthesis of isoleucine leads to a mixture of DL-isoleucine and DL-alloisoleucine. The preparation of DL-isoleucine from the mixture was studied. When the mixture was reacted with 1,5-naphthalenedisulfonic acid in water, DL-isoleucine formed the less soluble 1,5-naphthalenedisulfonate and could be separated in the form of the salt from the mixture. The soluble DL-alloisoleucine salt was easily epimerized by heating in acetic acid in the presence of salicylaldehyde and free isoleucine mixture. Asymmetric transformation between the two diastereoisomeric racemates was carried out by the simultaneous combination of the fractional crystallization of the less soluble DL-isoleucine salt and the epimerization of the soluble DL-alloisoleucine salt. DL-Isoleucine salt was obtained in a yield of up to 95% from a DL-isoleucine–DL-alloisoleucine mixture or even from DL-alloisoleucine.
  • Takayoshi Sasaki, Y\={u} Komatsu, Yoshinori Fujiki
    1984 Volume 57 Issue 5 Pages 1331-1335
    Published: 1984
    Released: June 27, 2006
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    The sorption of ammonia/ammonium ion has been studied on crystalline hydrous titanium dioxide fibers with a layer structure, which are prepared from potassium tetratitanate (K2Ti4O9). From the measurement of the distribution coefficient, it was found that this material strongly preferred ammonium ion to sodium ion. The results of the pH titration curves indicated that this material showed a wide range of acidities toward ammonia/ammonium ion and had 2.63 mequiv/g of an apparent capacity which was about a half of the theoretical ion-exchange capacity. The characterizations of the ammonium adsorbed solid phase at various loading levels were carried out by measuring the X-ray powder diffractograms and the water contents. From these studies, it was concluded that the sorption-desorption reaction of ammonia/ammonium ion on this material took place almost reversibly in three stages.
  • Kazuhiko Nakayama, Takashi Komorita, Yoichi Shimura
    1984 Volume 57 Issue 5 Pages 1336-1347
    Published: 1984
    Released: June 27, 2006
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    The electronic absorption and MCD spectra of [PdCl2L] (L=ethylenediamine(en), 1,3-propanediamine, N,N-dimethylethylenediamine, N,N′-dimethylethylenediamine, N,N-diethylethylenediamine, and N,N-dimethyl-1,3-propanediamine) and trans-[PdCl2(L)2] (L=EtNH2, Me2NH, Me3N, n-BuNH2, i-BuNH2, s-BuNH2, t-BuNH2, and rac-pea (pea=1-phenylethylamine)), and CD spectra of [PdCl2L] (L=(S)-1,2-propanediamine-(S-pn) and (2S)-N1,N1-diethyl-1,2-propanediamine) and trans-[PdCl2(S-pea)2] have been measured over the visible-near UV region, together with the corresponding spectra of [PtCl2L] (L=en and S-pn). The examination of the three kinds of spectra as well as their Gaussian analyses indicates that the splitting pattern of metal d orbitals for the cis type complexes is similar to that for [PdCl4]2−, and that as to the trans complexes the dx2−y2dxz and dyz transitions split largely to give apparent two spin-allowed d-d bands characteristic of the trans complexes. The average energy of the dx2−y2dxz and dyz transitions for the trans complexes is approximately equal to the energy of the dx2−y2dxz,yz (D4h) ones for the cis complexes. The transition energies of dx2−y2dxy and dx2 do not differ largely between both types of complexes. The assignments of high-intensity bands have also been made tentatively.
  • Tetsu Kumagai
    1984 Volume 57 Issue 5 Pages 1348-1351
    Published: 1984
    Released: June 27, 2006
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    The formation constants of zinc chloride and/or perchlorate in ethylene glycol were measured by a cation exchange method using the resin for forced-flow liquid chromatography in three systems: zinc chloride, zinc perchlorate, and zinc chloride and perchlorate together. The values obtained for the formation constants were: logβ1Cl=3.03, logβ2Cl=4.80, logβ1ClO4=2.34, and logβ2ClO4=2.50. The formation constant for the mixed complex of zinc, logkmClO4, was 0.7 at the ionic strength of 0.1. The formation constants of zinc chloride in ethylene glycol containing 5 v/v% of water were 2.73 for logβ1Cl and 4.18 for logβ2Cl, and those containing 10% of water were 2.32 for logβ1Cl and 3.46 for logβ2Cl.
  • Isao Sanemasa, Toyohisa Kobayashi, Cheng Yun Piao, Toshio Deguchi
    1984 Volume 57 Issue 5 Pages 1352-1357
    Published: 1984
    Released: June 27, 2006
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    Equilibrium solubilities of iodine vapor in water were measured by introducing iodine vapor, in equilibrium with solid iodine, into water and by circulating it in a closed system, and Henry’s law constants were determined. Equilibrium distributions of iodine vapor between a gas phase and an aqueous phase were also measured by another method, and partition coefficients were determined. The solubilities of iodine vapor in water estimated from both the Henry’s law constants and the partition coefficients are compared with those of solid iodine reported in the literature. Thermodynamic parameters for the hydration of iodine vapor are evaluated experimentally.
  • Isao Sanemasa, Takemi Mizoguchi, Toshio Deguchi
    1984 Volume 57 Issue 5 Pages 1358-1361
    Published: 1984
    Released: June 27, 2006
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    The gel filtration technique (Hummel and Dreyer method) was applied to determining formation constants of inclusion complexes of α- and β-cyclodextrins. As guest substances, p-nitrophenolate, p-nitrophenol, benzoate, and benzoic acid were used. Formation constants were determined at room temperature (25–30 °C) using Sephadex G-10 gel in aqueous buffered solutions of a constant ionic strength of 0.5 with NaCl or with phosphate buffer, and the results were compared with literature values. The method is applicable to such guest substances as exhibit strong adsorption onto the gel matrix.
  • Toshio Fuchigami, Takushi Goto, Mou-Yung Yeh, Tsutomu Nonaka, Hsien-Ju ...
    1984 Volume 57 Issue 5 Pages 1362-1366
    Published: 1984
    Released: June 27, 2006
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    New sydnone derivatives having heterocyclic substituents such as 4-thiazolyl, 3-thienyl, 2H-1,4-benzothiazin-3-yl, 2H-1,4-benzoxazin-3-yl, and 1,2-dihydro-3-quinoxalinyl groups at the 4-positions were prepared from 4-bromoacetyl-3-arylsydnones (1). Sydnone compounds substituted by a 1,2,3-triazol-4-yl group were prepared via new type phosphonium ylids derived from 1. Electroreduction of 1 was also attempted in order to prepare a syndnone derivatives having a furyl group.
  • Kaoru Harada, Shozo Shiono
    1984 Volume 57 Issue 5 Pages 1367-1370
    Published: 1984
    Released: June 27, 2006
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    Catalytic hydrogenation of Schiff bases prepared from α-keto esters with amino acid esters was carried out under various conditions. A significant substituent effect of the alkyl group of the ester moiety of amino acid on the stereoselectivity was observed in the hydrogenation of the Schiff bases prepared from methyl pyruvate with (S)-alanine ester. Higher asymmetric yields were obtained as the ester residue of amino acid ester became bulkier. A clear temperature effect on the asymmetric hydrogenation was also observed. These results could be explained by the chelation mechanism.
  • Yukito Murakami, Jun-ichi Kikuchi, Koji Nishida, Akio Nakano
    1984 Volume 57 Issue 5 Pages 1371-1376
    Published: 1984
    Released: June 27, 2006
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    A peptide lipid bearing the 1,4-dihydronicotinamide moiety, N,N-dihexadecyl-Nα-[1-(6-trimethylammoniohexyl)-1,4-dihydro-3-pyridylcarbonyl]-L-alaninamide bromide [N+C6(NAH)Ala2C16], and its dehydrogenated form, N,N-dihexadecyl-Nα-[1-(6-trimethylammoniohexyl)pyridinium-3-ylcarbonyl]-L-alaninamide chloride bromide [N+C6(NA+)Ala2C16], were prepared. Both lipids formed bilayer membranes when they were dispersed in aqueous media, and the 1,4-dihydronicotinamide and nicotinamide moieties of the respective lipid molecules were placed in the so-called hydrogen-belt domain upon membrane formation. In an aqueous dispersion of the latter dicationic lipid, relatively small multilayered vesicles were predominantly formed while the related monocationic lipids bearing the same double alkyl chain composed much larger vesicles and/or lamellae. Formation of the charge-transfer (CT) complex of the nicotinamide moiety of N+C6(NA+)Ala2C16 with 3-indolylacetic acid was much enhanced in the membrane through tight electrostatic interaction. The bilayer membrane composed of N+C6(NAH)Ala2C16 acted as a potential reductant toward anionic substrates in aqueous media. The high reactivity is gained primarily by the effective incorporation of the substrates into the hydrogen-belt domain through electrostatic, hydrogen bonding, and CT interactions and partly by the proximity effect which becomes valid between the 1,4-dihydronicotinamide moiety and the bound substrate molecule.
  • Koichi Komatsu, Shuzo Shirai, Isao Tomioka, Kunio Okamoto
    1984 Volume 57 Issue 5 Pages 1377-1380
    Published: 1984
    Released: June 27, 2006
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    The title anion (3) having a C3v symmetric structure was generated from newly synthesized tristyrylmethane (4) and was characterized by means of 1H and 13C NMR spectroscopy. The pKa value of 4 was determined as 20.1 in DMSO–EtOH (9:1), indicating considerable conjugative stabilization of the anion 3. The cyclic voltammetry of 3 in acetonitrile exhibited only irreversible one-electron oxidation peak corresponding to the formation of a chemically unstable radical species. Whereas quenching the anion 3 with H2O or Me3SiCl quantitatively afforded the cross-conjugated triene 6 (R=H or Me3Si), the reaction of 3 with the tropylium ion yielded 1,1′-bicycloheptatrienyl (29%), as well as the triene 6 (R=C7H7) (66%), demonstrating that 3 can also acat as a one electron reductant.
  • Shoko Yoshimura, Toshifumi Takao, Haruo Ikemura, Saburo Aimoto, Yasuts ...
    1984 Volume 57 Issue 5 Pages 1381-1387
    Published: 1984
    Released: June 27, 2006
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    Two shorter peptides of a heat-stable enterotoxin (STp), which is produced by enterotoxigenic Escherichia coli strain 18D, were prepared by two different procedures; i) chemical synthesis and ii) Edman-degradation of STp. These peptides (designated as STp(4–18) and STp(5–18)) corresponded to 15 and 14 amino acid residues in the sequence of STp without three and four residues, respectively, of the N-terminus. Peptides STp(4–18) and STp(5–18) prepared by chemical synthesis had the same biological and physicochemical properties as the peptides obtained by the Edman method. Furthermore, they showed almost the same toxicity as native and synthetic STp, and their toxicity was neutralized by anti-native STp antisera. Synthetic STp(4–18) had similar heat-stability to STp, but synthetic STp(5–18) was much more heat-stable. These findings suggest that the sequence from the Cys residue near the N-terminus to the C-terminal residue is extremely important for the unique characters of toxicity and heat-stability of the toxin.
  • Eiichi Narita, Hitoshi Takeuchi, Naoto Horiguchi, Taijiro Okabe
    1984 Volume 57 Issue 5 Pages 1388-1393
    Published: 1984
    Released: June 27, 2006
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    Thermal hydrolysis of titanium(IV) in hydrochloric acid solutions (0.2 mol dm−3 in Ti(IV); 2 mol dm−3 in HCl) was carried out at temperatures up to 110 °C to investigate the effects of heating rate, heating temperature, aging time, and coexisting ions on the particle shape, size, crystal form, crystalline size, and content of water of the hydrous titanium(IV) oxide precipitated. The resulting polycrystalline particles having rutile structure were all distorted ellipsoids at the beginning of the hydrolysis, and gradually changed to spheres with rising temperature or with the duration of time. However, no effects of heating rate on the particle shape and size distribution were observed at the beginning of the hydrolysis. On the other hand, the precipitation rate of titanium(IV) measured at a constant temperature remarkably depended on the temperature; marked changes in the particle size distribution and mean particle size were observed during the reaction. The precipitation rate was well expressed by the rate equation based on the rate-determining step of the surface chemical reaction. The apparent activation energy was 111 kJ mol−1. Although no effects of coexisting cations such as iron(III) and aluminium(III) were recognized, the presence of sulfate and fluoride ions significantly affected the particle shape and size of such precipitates. Anatase-type hydrous titanium(IV) oxide consisting of spherical particles of narrow size distribution was also obtained in the presence of fluoride ion.
  • Syed Ahamed Mohamed Farook, Seshaiyer Viswanathan, Ramachandran Ganesa ...
    1984 Volume 57 Issue 5 Pages 1394-1400
    Published: 1984
    Released: June 27, 2006
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    This paper deals with the kinetics of bromine addition to unsaturated compounds in presence of added bromide ions at 22, 30, 38, 46, and 54 °C. The substrates used were acrylamide (AAm), methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), t-butyl acrylate (tBA), methacrylamide (MAAm), methyl methacrylate (MMA), ethyl methacrylate (EMA), methyl crotonate (MC), and ethyl crotonate (EC). The kinetics was followed potentiometrically. The activation parameters (ΔH\ eweq, ΔS\ eweq, and ΔG\ eweq) were calculated and compared. Estimation of product ratio of bromohydrin to dibromide showed the absence of any correlation of the product formation with reactivity of the substrates. The observed parameters are discussed in relation to the proposed reaction mechanisms.
  • Vindhya Prasad Tewari, Krishna Behari Lal, Arun Kumar Srivastava
    1984 Volume 57 Issue 5 Pages 1401-1404
    Published: 1984
    Released: June 27, 2006
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    With systematic approximations to Roothaan equation it has been possible to deduce the IOC-ω-technique (inclusion of overlap charges in ω-technique) which apparently approximates the SCF-equations by bringing in an approximate correction for the two center-two electron repulsion integrals and represents a better version of PPP (Pariser-Parr-Pople) method by involving the hybrid integrals which have been completely neglected in PPP-approximations. In the present communication a new version of IOC-ω-Technique has been used for evaluating the π-bond energies, heats of formation and resonance energies of some conjugated hydrocarbons. The calculated values are found to be in excellent agreement with the experimental data and with some previously calculated values.
  • J. R. Merchant, Gail Martyres, N. M. Shinde
    1984 Volume 57 Issue 5 Pages 1405-1406
    Published: 1984
    Released: June 27, 2006
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    Aarylamines react with polyhaloalkanes in the presence of copper bronze to yield azophenines.
  • Tomoo Miyazaki, Azuma Matsuura, Hisao Takeuchi
    1984 Volume 57 Issue 5 Pages 1407-1408
    Published: 1984
    Released: June 27, 2006
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    The vibrational energy levels and infrared absorption intensities of carbon monoxide have been calculated with due consideration for the mechanical and electrical anharmonicities of vibration by the use of ab initio molecular orbital calculation in which the C-I treatment and polarization functions were introduced.
  • Nobuya Nagashima, Ei-ichiro Suzuki, Masamichi Tsuboi
    1984 Volume 57 Issue 5 Pages 1409-1410
    Published: 1984
    Released: June 27, 2006
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    On cooling an aqueous solution of zinc pig-insulin to −40 °C, 108 water molecules per insulin molecule have been found (by NMR) unfrozen. This number is nearly equal to what was found crystallographically of the water molecules located within 4.7 Å of the protein molecule.
  • Yoshio Matsunaga, Izumi Suzuki
    1984 Volume 57 Issue 5 Pages 1411-1412
    Published: 1984
    Released: June 27, 2006
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    Smectic A liquid crystals are formed not only in systems with normal alkyl esters but also with esters of branched alkyl groups such as t-butyl, 1,2-dimethylpropyl, and 1-ethylpropyl.
  • Yoshio Matsunaga, Nobuhiko Miyajima
    1984 Volume 57 Issue 5 Pages 1413-1414
    Published: 1984
    Released: June 27, 2006
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    2-Methylation of the ester butyl and pentyl groups in the phenyl-substituted compounds and also of the ester propyl, butyl, and pentyl groups in a number of the alkoxy-substituted compounds resulted in the production of nematic liquid crystals.
  • Hiroyuki Kawano, Tsutomu Kenp\={o}
    1984 Volume 57 Issue 5 Pages 1415-1416
    Published: 1984
    Released: June 27, 2006
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    By means of molecular effusion from a Knudsen cell and of thermal positive ionization on a glowing polycrystalline rhenium filament, the vapor pressure P (in atm) of LiCl or NaBr was measured as a function of cell temperature T (in K). The following equations were established empirically.
    log10P(LiCl)=(7.948±0.102)−(10954±76)⁄T for 662–848 K,
    log10P(NaBr)=(7.716±0.072)−(11138±55)⁄T for 669–882 K.
  • Yukiyoshi Sasaki, Hideo Imoto, Osamu Nagano
    1984 Volume 57 Issue 5 Pages 1417-1418
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Single-crystal X-ray analysis has shown that the title compound is tetragonal, P42/mbc, with a=13.705(2), c=7.271(1) Å. The structure is made of octahedra of trans-Sn(CH3)2O4 and tetrahedra of MoO4. These polyhedra share apices to form a three-dimensional structure.
  • Akira Tatehata, Shigeru Natsume
    1984 Volume 57 Issue 5 Pages 1419-1420
    Published: 1984
    Released: June 27, 2006
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    Four diastereoisomers of the type [Co(S- or (R-pn)(phen)2]3+ (pn=1,2-propanediamine; phen=1,10-phenanthroline) were prepared and characterized by absorption, circular dichroism (CD), and 1H NMR spectra. High stereoselectivity in the formation of the diastereoisomers was observed and the Λ-isomer of [Co(S-pn)(phen)2]3+ was formed in preference to the Δ-isomer.
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