Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 57 , Issue 9
Showing 1-50 articles out of 75 articles from the selected issue
  • Hideki Masuda, Tooru Taga, Kenji Osaki, Hiroshi Sugimoto, Masayasu Mor ...
    1984 Volume 57 Issue 9 Pages 2345-2351
    Published: 1984
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    The crystal structure of the title complex has been determined by the X-ray method. The complex crystallizes in the monoclinic space group P2/c with a=24.171(9), b=14.037(3), c=24.401(9) Å, β=119.68(9)°, and Z=4. The structure was solved by the heavy-atom method and refined to R=0.094 for 3838 reflections. Two independent dimers exist with a crystallographically imposed two-fold axis in the unit cell. The two dimers are in an approximately orthogonal arrangement, and they take very similar conformations. The noticeable structural parameters are the average distances of 2.033(28) Å for OsIV–N, 1.808(3) Å for OsIV–O2−, and 1.997(29) Å for OsIV–OCH3. The two porphinato cores bridged by a μ-oxo oxygen atom rotate around the approximately linear Os–O–Os bond (the average valence angle=178°) by 23(1)° from the eclipsed form. The porphine ring is planar within 0.10 Å, and deviation of the Os atom from the porphinato plane of the four nitrogen atoms is 0.06 Å. These results were compared, in the relation of the specific physicochemical properties in solution, with those of the corresponding RuIV complexes reported previously.
  • Teruyo Yamashita, Minako Sumino, Hiroshige Yano, Shoji Harada, Tatsuya ...
    1984 Volume 57 Issue 9 Pages 2352-2356
    Published: 1984
    Released: June 27, 2006
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    The ultrasonic relaxation absorption has been measured in aqueous solution of dipentylamine, dihexylamine, dioctylamine, N-methylphenethylamine, and N-ethylbenzylamine in the presence of the sodium dodecyl sulfate(SDS) micelle. The relaxation absorption has been ascribed to the base equilibrium of the amines on the surface of the micelle: RR′NH2++OH\oversetkf\undersetkb\ ightleftharpoonsRR′NH+H2O. The rate constants γ±2kf, kb, the apparent base dissociation constant Kb (=kb⁄γ±2kf), and the volume change in the base equilibrium ΔV were obtained, where γ± is the mean activity coefficient for RR′NH2+ and OH. The dependence of the rate constants on Kb revealed that, in the detailed mechanism of the base equilibrium of the amines, RR′\underset(I)NH2++OH\oversetk12\undersetk21\ ightleftharpoons(RR′NH\underset(II)2+···OH)\oversetk23\undersetk32\ ightleftharpoonsRR′N\underset(III)H+H2O, the rate-determining step is the proton-transfer process, (II) \ ightleftharpoons (III). The pKb values of the secondary amines on the surface of the SDS micelle were 0.94–1.26 smaller than the corresponding values in the aqueous solution, and the micellar effect on pKb was smaller than that of the primary amines. From the standpoint of the micellar effect, the structures of the amines solubilized in the micelle were discussed.
  • Sadakatsu Nishikawa, Masayuki Shibata
    1984 Volume 57 Issue 9 Pages 2357-2360
    Published: 1984
    Released: June 27, 2006
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    Ultrasonic absorptions in the frequency range 4.5–220 MHz and sound velocities at 2.5 MHz were measured at 25 °C with aqueous solutions of Butyl Carbitol (diethylene glycol monobutyl ether) over the concentration range 0.497–3.00 mol dm−3. Only a single relaxational process was observed and attributed to a perturbation of the equilibrium AB\oversetk12\undersetk21↔A+B, where A is Butyl Carbitol as the solute and B is water as the solvent participating in the reaction. A data analysis has led to the estimates k12=3.4×107 s−1, k21=2.0×108 dm3 mol−1 s−1, the standard volume change of reaction ΔV°=0.32 cm3 mol−1, and the standard enthalpy change ΔH°=5.4 kJ mol−1. The effect of the hydrophobicity of solute molecules on the water structure is discussed by comparing the present results with previous ones for other aqueous nonelectrolyte solutions.
  • Kumiko Sato, Motomi Katada, Hirotoshi Sano, Michiko Konno
    1984 Volume 57 Issue 9 Pages 2361-2365
    Published: 1984
    Released: June 27, 2006
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    The entitled compound shows an anomalous temperature dependence of the mean-square amplitude of iron atoms derived from the Lamb-Mössbauer factor near the melting point. To clarify the anomaly, the crystal structure of this compound was determined at room temperature by X-ray diffraction. The crystal is monoclinic with space group P21/c, a=20.595(2), b=5.7909(4), c=18.840(2) Å, β=116.870(7)°, U=2004.4(3) Å3, and Z=8. Weissenberg and oscillation photographs taken at a high temperature lead us to propose a model in which the acetylferrocene molecules rotate around the central iron atoms.
  • Mamoru Nango, Shozo Ohta, Masako Maekawa, Akira Katayama, Nobuhiko Kur ...
    1984 Volume 57 Issue 9 Pages 2366-2370
    Published: 1984
    Released: June 27, 2006
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    The transport of chromophore into a membrane in the presence of polyelectrolyte is enhanced much as it is in the presence of simple salt. The presence of polyelectrolyte with different kinds of counterions seem to modify this observed enhancement. The differences in enhanced transport into the cellulose membrane in the presence of polyelectrolyte may suggest a new model for reinterpretation of the transport phenomenon in a biological system.
  • Eiji Chino, Yoshio Matsunaga, Mika Suzuki
    1984 Volume 57 Issue 9 Pages 2371-2375
    Published: 1984
    Released: June 27, 2006
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    Studies on binary systems with nematogenic N-(4-propoxybenzylidene)-4-hexylaniline revealed that 4-nitrophenyl alkanoates, alkyl 4-nitrobenzoates, N-(4-nitrophenyl)alkanamides, and N-alkyl-4-nitrobenzamides are potentially smectogenic. When the Schiff base is mixed separately with a homologous member from 4-nitrophenyl decanoate to tetradecanoate, a stable smectic A phase is induced and its maximum temperature is about 48 °C. The estimated latent transition points to this mesophase of these benzene derivatives are in the range from −25 to 10 °C. On the other hand, only metastable smectic A phases can be produced with hexyl to dodecyl 4-nitrobenzoates, the maximum temperatures being from 15 to 26 °C. While the metastable smectic B phase of the Schiff base is to some extent stabilized by the addition of the alkanoates, it is drastically depressed by the benzoates. The addition of N-(4-nitrophenyl)nonanamide to -dodecanamide produces a stable smectic A phase and also stabilizes the metastable smectic B phase. No smectic A phase is found in mixtures of the Schiff base with N-octyl- to N-dodecyl-4-nitrobenzamides, and the isotropic or nematic-smectic B transition point curves are almost horizontal indicating that these benzene derivatives have transitions to latent smectic B phases between 10 and 20 °C. Results obtained with some related compounds are also presented.
  • Masayo Noda, Shin-ichi Nagaoka, Noboru Hirota
    1984 Volume 57 Issue 9 Pages 2376-2382
    Published: 1984
    Released: June 27, 2006
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    The triplet states (3ππ*) of purine, benzimidazole, and indazole are investigated in benzoic acid crystals by electron paramagnetic resonance (EPR) and optical detection of magnetic resonance (ODMR) techniques. Well resolved phosphorescence spectra were obtained at 4.2 K. The T1 states of purine and benzimidazole are located at 26409 and 26536 cm−1, respectively. The zero field splittings (ZFS) are D=0.1042 cm−1, |E|=0.0608 cm−1 for purine, and D=0.1123 cm−1, |E|=0.0270 cm−1 for benzimidazole. The decay rate constants of the triplet sublevels are determined at 1.5 K and are compared with those of indole. From the angular dependence of the EPR signals, the probable orientations of purine and benzimidazole in benzoic acid hosts are determined. From the observed hyperfine splittings (hfs) spin distribution of the T1 state of purine is estimated. (ρ6=0.20, ρ8=0.27, and ρ2=0.12). The effects of the nitrogen substitution in the pyrole ring of indole on the ZFS and spin distribution are discussed.
  • Kenji Kano, Tomonori Konse, Naomi Nishimura, Tanekazu Kubota
    1984 Volume 57 Issue 9 Pages 2383-2390
    Published: 1984
    Released: June 27, 2006
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    The electrochemical behavior of adriamycin has been studied by means of cyclic d.c. and a.c. voltammetry with a hanging mercury drop electrode, quinizarin being used as a model compound. Both adriamycin and quinizarin are strongly adsorbed on the mercury electrode with their aromatic ring planes oriented parallel to the electrode surface, and give two sets of reduction waves. The first wave, due to the quinone moieties of the adsorbed adriamycin and quinizarin, has been explained on terms of a two-step one-electron surface redox reaction. The formal standard redox potentials, semiquinone formation constants, and charge transfer rate constants of the surface redox reaction of the quinone moieties have been determined. Although the reduced form of adriamycin is not very stable chemically, it is converted to a stable and electrochemically active form for a few minutes at pH 4.54. The second wave appearing at more negative potential would be due to a kinetic or catalytic process.
  • Kenzabu Tasaki, Yuji Sasanuma, Isao Ando, Akihiro Abe
    1984 Volume 57 Issue 9 Pages 2391-2395
    Published: 1984
    Released: June 27, 2006
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    The energy difference between the two rotational isomers, i.e., Cs and C1, of isopropyl methyl ether has been elucidated from the observed vicinal 13C-1H coupling constant. The conventional Gutowsky method based on the simple rotational isomeric state model tends to give an underestimate, especially when the energy difference is large. A more elaborate treatment, which takes account of the overall profile of the torsional potential energy curve, has been attempted. Adoption of JT=11.0–12.0 Hz for the trans coupling gave a value of 2.2±0.2 kcal mol−1 for the energy difference EcsEc1. This result is consistent with the range (2.4±0.6 kcal mol−1) estimated by the matrix-isolation method as reported by Nakata et al.
  • Tamaki Maeda, Iwao Satake
    1984 Volume 57 Issue 9 Pages 2396-2399
    Published: 1984
    Released: June 27, 2006
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    The surfactant ion and counterion activities of aqueous 1-dodecylpyridinium chloride with and without KCl were determined by using ion-selective electrodes. In the concentration range above the critical micelle concentration (cmc), the surfactant ion activity (a+) was found to decrease gradually with increasing surfactant concentrations, while the reverse change was found for the counterion activity (a). As a result, the mean activity increased slightly but regularly with increasing concentrations. The concentration dependences of a+ and a became progressively smaller as the salt concentration increased. An application of the charged phase separation model led to an apparent degree of counterion association to the micelle (β) of 0.70 regardless of the salt concentration. On the basis of these observations, the estimations were made for the concentration of monomeric surfactant ion (C+) and the activity coefficients of counterion (γ) and surfactant ion (γ+) above the cmc. The values of C+ and γ+ decreased appreciably, while that of γ increased with increasing concentrations. The value of β was also estimated from the concentration dependence of a and the validity of this method was discussed.
  • Yoshinori Koga, Harutoshi Takeo, Shigeo Kondo, Chi Matsumura, Shinnosu ...
    1984 Volume 57 Issue 9 Pages 2400-2403
    Published: 1984
    Released: June 27, 2006
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    The rotation-vibration bands of a transient molecule, sulfine, (methanethial S-oxide), have been observed by FT-IR and analyzed with the aid of microwave data, a part of which has been newly obtained in this study. The band center frequencies for ν5 and ν9 are determined to be 1175.75 cm−1 and 762.07 cm−1, respectively. The good agreement between the observed and simulated band contours clarifies that the origin of these bands is sulfine.
  • Shiro Miyake, Shigekazu Kusabayashi, Shunsuke Takenaka
    1984 Volume 57 Issue 9 Pages 2404-2407
    Published: 1984
    Released: June 27, 2006
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    Some homologous series of cyanothiophene and cyanofuran compounds have been prepared. 4-Alkoxyphenyl 3-(5-bromo-2-thienyl)acrylate (1) and 4-alkoxyphenyl 3-(5-cyano-2-thienyl)acrylate (2), and 4-alkoxy-phenyl 4-(5-bromo-2-furylcarbonyloxy)benzoate (3) and 4-alkoxyphenyl 4-(5-cyano-2-furylcarbonyloxy)benzoate (4) give rise to a nematic phase. For compound 4, a smectic A phase which commences from the hexyloxy homolog has a bilayer (SA2) arrangement of the molecules. The thermal stabilities of the mesophases are lower than those of the corresponding benzonitrile compounds. This arises from an increased molecular breadth around the terminal portion and the change of the dipole moment arising from the terminal cyano group bending with respect to the long molecular axis.
  • Manabu Niwase, Kyoko Kubota, Kazuhiko Yoshida, Takeshi Sakaizumi, Masa ...
    1984 Volume 57 Issue 9 Pages 2408-2410
    Published: 1984
    Released: June 27, 2006
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    The microwave spectra of acrylaldehyde oxime and its deuterated derivative (CH2=CH–CH=NOD) were observed in the frequency region from 8.5 to 35 GHz. The several a-type R-branch transitions in the ground vibradonal state were identified and the following rotational constants in MHz were determined to be: A=34117±96, B=2363.007±0.011, and C=2210.616±0.011 for normal species and A=33950±103, B=2274.301±0.010, and C=2131.981±0.011 for deuterated species. The most plausible molecular structure to which the spectrum assigned is attributed has been deduced to be a s-trans syn geometrical conformer from the rotational constants experimentally determined. The dipole moment component μa in the ground vibrational state was determined to be 0.59 D from the Stark effects of J=2←1 transitions. The rs coordinates of the OH hydrogen atom have been determined and the orientation of the OH bond in the molecule has been discussed.
  • Yutaka Tamaura, Takashi Yoshida, Takashi Katsura
    1984 Volume 57 Issue 9 Pages 2411-2416
    Published: 1984
    Released: June 27, 2006
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    Conditions for the synthesis of a pure green rust II with a definite chemical composition and its transformation reaction to Fe3O4 under a nitrogen atmosphere were studied. A pure green rust II with the composition of (Fe3+)1(Fe2+)2(SO42−)(OH)5−2n(O2−)n was obtained by the air oxidation of an aqueous solution containing (0.05 mol dm−3) FeII and (0.3 mol dm−3) SO42− ions at pH 6.8 and 25 °C. This iron composition differs from those estimated previously; therefore, the green rust II synthesized here is designated as green rust II(FeIII1–FeII2). This green rust II is spontaneously transformed into Fe3O4 under a nitrogen atmosphere at 50–75 °C. It has been accepted that green rust II is transformed to Fe3O4 by oxidation. The above evidence suggests that the green rust II can be transformed into Fe3O4 not only by oxidation but also spontaneously without oxidants.
  • Yutaka Tamaura, Mervelina Saturno, Kaoru Yamada, Takashi Katsura
    1984 Volume 57 Issue 9 Pages 2417-2421
    Published: 1984
    Released: June 27, 2006
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    A mechanism of the transformation of γ-FeO(OH) to Fe3O4 and/or green rust II in an aqueous solution containing FeII ion in the presence or absence of the SO42− ion at 298 K is described. γ-FeO(OH) is dissolved by two mols of FeII ions adsorbed on the surface of γ-FeO(OH), and a dissolved species (DS) is formed, which is then transformed to Fe3O4 or green rust II. The equilibrium of the formation of green rust II from γ-FeO(OH) is represented by:
    K=[H+]2⁄(Kh2[Fe2+]2[SO42−]) K=2.14×108,
    where Kh is the hydrolysis constant of Fe2+. This equation shows that, for a given proton concentration(pH), higher concentrations of Fe2+ and SO42− ions facilitate the formation of green rust II from γ-FeO(OH). When little green rust II is formed, the DS is transformed to Fe3O4.
  • Hiroshi Kawaguchi, Tomoharu Ama, Takaji Yasui
    1984 Volume 57 Issue 9 Pages 2422-2427
    Published: 1984
    Released: June 27, 2006
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    The isomerization reaction among three geometrical isomers of [Co(ida)(mida)] was studied in a basic aqueous solution. It has been found that the reaction scheme is u-fac\ ightleftharpoonsmer\ ightleftharpoonss-fac. The rates of these isomerization paths have been determined as the functions of pH and temperature. The rate of the u-fac\ ightleftharpoonsmer change is considerably faster than that of the mer\ ightleftharpoonss-fac change. The CD loss of the optically active u-fac isomer is caused by the isomerization process of u-fac\ ightleftharpoonsmer. The isomerization of the [Co(ida)2] system has also been measured, and the rate data analysed according to the same scheme as that used for the [Co(ida)(mida)] system. It is suggested that the isomerizations of the [Co(ida)(mida)] and [Co(ida)2] systems proceed through a conjugatebase intermediate.
  • Hideaki Monjushiro, Katsuo Murata, Shigero Ikeda
    1984 Volume 57 Issue 9 Pages 2428-2434
    Published: 1984
    Released: June 27, 2006
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    Inelastic electron tunneling (IET) spectra were obtained for o-hydroxybenzoic acid(OHBA), o-aminobenzoic acid (OABA) and o-mercaptobenzoic acid (OMBA) adsorbed on aluminium oxide (AlOx) grown on aluminium film and were analyzed by referring IR results. OHBA is adsorbed on AlOx with both two functional groups, carboxyl and hydroxyl radicals. In the case of OABA, the adsorption occurs mainly with carboxyl group and the interaction between amino group and AlOx is rather weak. Mercapto group of OMBA forms two kinds of hydrogen bonding, and a dissociated species on AlOx. These results indicate that the surface of AlOx used in this study is highly hydrated and hydroxyl groups on the oxide are reactive with the proton donating sites of the chemical species. IET spectra of o-fluoro- and o-chlorobenzoic acid were also observed for comparison.
  • Taeko Izumi, Takeshi Tezuka, Sachiko Yusa, Akira Kasahara
    1984 Volume 57 Issue 9 Pages 2435-2439
    Published: 1984
    Released: June 27, 2006
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    Fifteen new oxo crown ethers having a ferrocene unit as an integral part of the ring member are reported. These oxo crown ethers were synthesized by the reaction of 1,1′-bis(chloroformyl)ferrocene with oligoethylene glycols or heterocyclic dialcohol compounds such as 2,6-bis(hydroxymethyl)pyridine by the high dilution method. Complexing ability of these compounds with alkali, alkaline earth, and transition metal cations was measured by the solvent extraction method.
  • Yoshihisa Watanabe, Tetsuo Ohta, Yasushi Tsuji, Takao Hiyoshi, Yasuo T ...
    1984 Volume 57 Issue 9 Pages 2440-2444
    Published: 1984
    Released: June 27, 2006
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    Various nitroarenes having chloro, methyl, or methoxy substituents were reduced to the corresponding aminoarenes in high yields using formic acid in the presence of a catalytic amount of RuCl2(PPh3)3. For example, 4-chloronitrobenzene was converted in 99% conversion with 98% selectivity at 125 °C for 5 h. 4-Nitroacetophenone was reduced chemoselectively to 1-(4-nitrophenyl)ethanol in 74% isolated yield under the same reaction conditions. Formic acid could also be employed as reductant for hydrogenation of heterocyclic compounds such as quinoline, indole, and quinoxaline in the presence of the ruthenium catalyst. 2-Methylquinoline was hydrogenated to 1,2,3,4-tetrahydro-2-methylquinoline in 93% conversion with 100% selectivity.
  • Minoru Hirota, Kazuhisa Abe, Masamichi Shibata, Hiroko Suezawa, Kaoru ...
    1984 Volume 57 Issue 9 Pages 2445-2449
    Published: 1984
    Released: June 27, 2006
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    In contrast to cis-4-hydroxy-2-tetralincarboxylates, cis-4-hydroxy-2-chromancarboxylates take diaxial conformation having 4-pseudoaxial-OH and 2-axial-COOR groups preferably. The preferred conformations of these compounds were rationalized by molecular force field (MM 1/MMP 1) calculations on the corresponding 2-tetralin- and 2-chromancarbaldehydes as model compounds.
  • Toshikazu Ibata, Tsuyoshi Yamashita, Makoto Kashiuchi, Shyuji Nakano, ...
    1984 Volume 57 Issue 9 Pages 2450-2455
    Published: 1984
    Released: June 27, 2006
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    The BF3-catalyzed decomposition of m- and p-substituted α-diazoacetophenones in excess of methyl thiocyanate and ethyl thiocyanate gave the corresponding 2-methylthio-, and 2-ethylthio-5-aryloxazoles, respectively in good yields along with s-alkyl-n-aroylmethylthiocarbamates and α-ethoxyacetophenones. However, yields of 2-dimethylamino-5-aryloxazoles by the reaction of dimethylcyanamide with α-diazoacetophenones were poor. 5-Dimethylamino- or 5-alkoxy-4-aryl-2-methyloxazoles were prepared by the reaction of N,N-dimethyl-α-(p-nitrophenyl)diazoacetamide or alkyl aryldiazoacetates with nitriles. When ethyl phenyldiazoacetate or methyl p-chlorophenyldiazoacetate were used, ketazines of alkyl arylglyoxylates were obtained together with oxazoles.
  • Kazuyuki Shimizu, Kazuyuki Nakayama, Masayasu Akiyama
    1984 Volume 57 Issue 9 Pages 2456-2462
    Published: 1984
    Released: June 27, 2006
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    Acylation of a series of N-benzyloxy α-amino acid derivatives with N,N-phthaloyloglycine shows that the yield decreases with increasing bulkiness of the substituent even by the acyl chloride or mixed anhydride procedure, and that the use of an excess reagent or a double acylation technique is needed to attain a good yield. The low reactivity of the benzyloxyamino group enables us to utilize N-benzyloxy α-amino acid N-hydroxysuccinimide esters without N-protection in the acylation of the usual amino group. In an attempt to lengthen the chain of an N-hydroxy peptide, a hexapeptide anilide having an N-hydroxy-DL-alanylglycyl sequence was synthesized via N-benzyloxy peptides. The complex forming tendency of the hexapeptide with iron(III) is examined.
  • Makoto Nitta, Shuji Okada, Masami Kato
    1984 Volume 57 Issue 9 Pages 2463-2467
    Published: 1984
    Released: June 27, 2006
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    The reaction of dichlorocarbene with 1,5-dimethyl-6-methylenetricyclo[3.2.1.02,7]oct-3-en-8-one, its corresponding alcohol derivative, and 1,5,8-trimethyl-6-methylenetricyclo[3.2.1.02,7]oct-3-en-8-endo-ol occurs on the exocyclic double bond to give exo and endo adducts with preferential formation of the exo adduct. Dichlorocarbene addition to 1,3,5-trimethyl-6-methylenetricyclo[3.2.1.02,7]oct-3-en-8-one (1d) occurs on the endocyclic double bond from the exo side, while the reaction occurs on the exocyclic double bond from both the exo and endo sides in the case of the corresponding alcohol derivative. The stereoselectivity or site selectivity was discussed on the basis of the stereoelectronic and homoconjugative effects as well as the steric effect of the reaction. Several chemical transformations, along with the derivation of bis adducts of dichlorocarbene, were also studied for confirmation of the structure of mono adducts. 1,3-Dipolar cycloaddition of 1d and its dichlorocarbene adduct with mesitonitrile oxide, giving the adducts on the exocyclic double bond, was also studied to suggest a possible causative factor to control the electrophilic addition in the indicated direction.
  • Yoshiharu Inoue, Fumio Tanimoto, Hisao Kitano
    1984 Volume 57 Issue 9 Pages 2468-2473
    Published: 1984
    Released: June 27, 2006
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    Addition of formic acid to 5-vinyl-2-norbornene(1) and subsequent hydrolysis afford 6-vinyl-exo-2-norbornanol(5) and 5-vinyl-exo-2-norbornanol(6). Similarly, from 5-ethylidene-2-norbornene(2) are formed 6-ethylidene-exo-2-norbornanol(14), 5-ethylidene-exo-2-norbornanol(15), and 6-ethyltricyclo[2.2.1.02,6]heptan-3-ol(16). The hydroboration of 2 also leads to the formation of 14 and 15. Thus, the vinyl- and ethylidene-exo-norbornanols, 5, 6, 14, and 15, and the corresponding endo-norbornanols, 9, 10, 21, and 22, have been synthesized. A structural analysis of these products by 13C NMR revealed that under certain conditions, the ethylidene group of 2 exerts a great influence upon the reactivity of the norbornenyl ring double bond. Moreover, the fact that 16 derived from the addition of formic acid to 2 consists of both exo- and endo-hydroxy epimers is inconsistent with the previous observations that the exo-isomer is generally the sole product in related systems.
  • Hideyuki Ikehira, Shigeo Tanimoto
    1984 Volume 57 Issue 9 Pages 2474-2478
    Published: 1984
    Released: June 27, 2006
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    Carbanions produced by deprotonation at the ring C-4 of 2,2-disubstituted 1,3-dithianes undergo a Wittig type rearrangement to give the anions of 2,2-disubstituted tetrahydrothiophene-3-thiols. After being trapped with several alkyl halides, these afford the corresponding 2,2-disubstituted 3-(alkylthio)tetrahydrothiophenes, which are difficult to prepare by other synthetic routes.
  • Teiji Chihara, Erika Waniguchi, Tamie Wakabayashi, Kazuo Taya
    1984 Volume 57 Issue 9 Pages 2479-2483
    Published: 1984
    Released: June 27, 2006
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    Some Girard’s derivatives of 4-phenylbenzophenone were prepared in ethanol solution, in the presence of Amberlite IRC-50 as a catalyst. Supported samples of the derivatives were then prepared by addition of silica gel to the solution, followed by evaporation of the ethanol. The supported samples were reduced with lithium tri-t-butoxyhydroaluminate by being suspended in THF solution. Hydrolysis, followed by extraction of the product, yielded 4-acetyl-α-phenylbenzyl alcohol in an 80% selectivity. In the same way, 4-acetylbenzaldehyde yielded 1-(4-formylphenyl)ethanol in an 81% selectivity. Relatively unhindered carbonyl groups were preferentially protected. Utilization of Girard’s reagents was successfully made as a protecting reagent and also as an extracting reagent of carbonyl compounds.
  • Tetsuo Furuno, Masami Ishibashi, Hirokazu Naora, Tatsushi Murae, Hiros ...
    1984 Volume 57 Issue 9 Pages 2484-2489
    Published: 1984
    Released: June 27, 2006
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    Bitter quassinoids, shinjulactones B, D, and E were isolated from Ailanthus altissima SWINGLE. Shinjulactone B is the first example of natural bitter principles with a 1,2-seco-1-nor-6(5→10)abeo-picrasane skeleton and shinjulactones D and E are a hexahydro derivative and a 6α-hydroxy derivative of ailanthone, respectively.
  • Motoo Tori, Masaki Takai, Yuzo Matsumoto, Yoshihiko Moriyama, Takahiko ...
    1984 Volume 57 Issue 9 Pages 2490-2495
    Published: 1984
    Released: June 27, 2006
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    Epoxidation of alnus-5-en-3β-yl acetate with m-chloroperbenzoic acid gave a 5β,6β-epoxide as a main product together with a 5α,6α-epoxide as a minor product. Treatment of the α-epoxide with BF3·OEt2 afforded a 1(10),5-diene and a mixture of 6α-hydroxy-12- and -18-ene derivatives. The 12-ene was converted into daturadiol (=olean-12-ene-3β,6β-diol).
  • Shin Yoshimura, Masami Ishibashi, Takahiko Tsuyuki, Takeyoshi Takahash ...
    1984 Volume 57 Issue 9 Pages 2496-2501
    Published: 1984
    Released: June 27, 2006
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    Four bitter quassinoid glycosides, shinjuglycosides A, B, C, and D were isolated from seeds of Ailanthus altissima SWINGLE and their structures were established to be 2-β-D-glucopyranosides of chaparrin, shinjulactone A, amarolide 11-acetate, and amarolide, respectively, from spectral data and enzymatic or acid-catalyzed hydrolysis.
  • Hiroaki Nagamatsu, Tadashi Okuyama, Takayuki Fueno
    1984 Volume 57 Issue 9 Pages 2502-2507
    Published: 1984
    Released: June 27, 2006
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    Hydrolysis of N-salicylidene-2-methoxyethylamine is kinetically investigated at 30 °C. Intramolecular general base catalysis by the o-O substituent takes place in the neutral pH region. Nucleophilic catalysis by morpholine was also found to be operative. Added boric acid accelerates the hydrolysis above pH 5.5 while it decelerates the hydrolysis below pH 5.5. The hydrolysis rate as the function of the boric acid concentration follows a saturation curve in harmony with a reaction sequence involving a rapid equilibrium formation of a borate-substrate complex followed by its breakdown. The morpholine catalysis is inhibited by boric acid in accord with the slow reaction of morpholine with the complex. The water reaction of the complex is considered to involve a rearrangement of the complex and an intramolecular transfer of the boron-coordinated hydroxide ion to the iminium carbon.
  • Hiroaki Nagamatsu, Tadashi Okuyama, Takayuki Fueno
    1984 Volume 57 Issue 9 Pages 2508-2514
    Published: 1984
    Released: June 27, 2006
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    Effects of boric acid on the formation of the Schiff base from salicylaldehyde and 2-methoxyethylamine (or glycinate) were examined in aqueous solution. From the formation constants in the absence and presence of boric acid, the equilibrium constants for the borate-Schiff base complexation were determined. The structure of the complex was deduced from the UV spectral analysis. Formation of the Schiff base was found to be accelerated by boric acid (pH 7–10). A mechanism for the reaction involving the complex is presented.
  • Tsuneo Sato, Yoshihiro Hayakawa, Ryoji Noyori
    1984 Volume 57 Issue 9 Pages 2515-2525
    Published: 1984
    Released: June 27, 2006
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    A stereocontrolled, general synthesis of chiral C-nucleosides has been achieved through a common lactonic C-β-glycoside intermediate which is readily obtainable from non-carbohydrate materials. Osmium tetraoxide-catalyzed vic-dihydroxylation of 8-oxabicyclo[3.2.1]oct-6-en-3-one gives, after acetonidation, (1R*,5S*,6S*,7R*)-6,7-isopropylidenedioxy-8-oxabicyclo[3.2.1]octan-3-one as a single stereoisomer. Baeyer-Villiger oxidation of the ketone affords the key intermediate, 2-(2,3-O-isopropylidene-β-ribofuranosyl)acetic acid lactone. The optically pure lactone having the natural D configuration is obtained through optical resolution of the seco acid by the Pirkle’s method followed by relactonization. α-Aminomethylenation of the lactone with t-C4H9OCH[N(CH3)2]2 yields 2-(2,3-O-isopropylidene-β-D-ribofuranosyl)-2-(dimethylaminomethylene)acetic acid lactone, which undergoes base-assisted condensation with urea followed by deprotection to furnish naturally occurring pseudouridine. Analogously, construction of heterocycles using thiourea and guanidine converts the aminomethylene lactone to unnatural pyrimidine C-nucleosides, 2-thiopseudouridine and pseudoisocytidine, respectively. Showdomycin in natural form can be prepared by two schemes. One approach consists of ozonolysis of the α-dimethylaminomethylene lactone, Wittig reaction using (C6H5)3PCHCONH2, and acid hydrolysis. The second entry makes use of 2-(2,3-O-isopropylidene-)3-D-ribofuranosyl)acetic acid lactone as the intermediate, which is converted to 2-(2,3-O-isopropylidene-)8-D-ribofuranosyl)-2-furfurylideneaceticacid lactone by the aldol reaction with furfural and dehydration. Methanolysis of the furfurylidene lactone and t-butyldimethylsilylation are followed by ozonolysis, Wittig condensation with (C6H5)3PCHCON2, and hydrolysis to give the maleimide C-nucleoside. In addition, 6-azapseudouridine and 6-aza-2-thiopseudouridine are obtainable via intramolecular ring closures of the semicarbazone and thiosemicarbazone of methyl 2-(2,3-O-isopropylidene-β-D-ribofuranosyl)glyoxylate followed by deprotections, respectively. These overall transformations are accomplishable under complete stereochemical control.
  • Masaki Matsui, Yoshihiko Miyamoto, Katsuyoshi Shibata, Yoshimi Takase
    1984 Volume 57 Issue 9 Pages 2526-2530
    Published: 1984
    Released: June 27, 2006
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    When phenothiazine and phenoxazine were ozonized in dichloromethane, the cation radicals and the ozonate anion radical were detected, whereas, in the ozonization of phenoxathiin and thianthrene, these radicals were not observed. Formation of these radicals was more favorable as greater was the polarity of the solvent and lower was the oxidation potential of the substrate. Ozonization of phenothiazine and phenoxazine in polar solvents was explained by the electron-transfer mechanism accompanied by the electrophilic ozone attack, and that of phenoxathiin and thianthrene by the electrophilic ozone attack alone.
  • Tomio Shimizu, Yoshiyuki Hayashi, Kazuhiro Teramura
    1984 Volume 57 Issue 9 Pages 2531-2534
    Published: 1984
    Released: June 27, 2006
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    3-Substituted 2-isoxazolines or isoxazoles were obtained from the reaction of primary nitro compounds [methyl nitroacetate, 2-nitro-1-phenylethanone, (nitromethyl)benzene, 1-nitropropane, and (phenylsulfonyl)nitromethane] with dipolarophiles in refluxing mesitylene in the presence of a small amount of p-toluenesulfonic acid. The formation of these products can be explained in terms of 1,3-dipolar cycloaddition of nitrile oxide generated by a dehydration of the primary nitro compounds. On the other hand, 4,5-decamethylene-3-phenylsulfonyl-2-isoxazoline N-oxide was obtained from a similar reaction of (phenylsulfonyl)nitromethane with cyclododecene. The formation of the isoxazoline N-oxide can be explained on the basis of the intermediacy of 3,4-bis(phenylsulfonyl)furazan 2-oxide.
  • Juji Yoshimura, Toshio Yasumori, Tatsuya Kondo, Ken-ichi Sato
    1984 Volume 57 Issue 9 Pages 2535-2537
    Published: 1984
    Released: June 27, 2006
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    The title compound was stereoselectively synthesized from methyl 2,6-dideoxy-4-O-methyl-β-L-thero-hexopyranosid-3-ulose (11) through the successive conversions; cyanomesylation, reductive spiro aziridine formation, reductive ring-opening to the methyl-branched amino sugar, oxidation to the corresponding nitro sugar.
  • Toshio Yasumori, Ken-ichi Sato, Hironobu Hashimoto, Juji Yoshimura
    1984 Volume 57 Issue 9 Pages 2538-2542
    Published: 1984
    Released: June 27, 2006
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    The title compound was synthesized from methyl 4-O-benzyl-2,6-dideoxy-β-L-threo-hexopyranosid-3-ulose (19) through cyanomesylation, reductive spiro aziridine formation, and reductive ring-opening. When (2-methoxyethoxymethyl) group was used as the protecting group at O-4 of the above intermediate, it could not be removed at the final stage.
  • Haruo Ikemura, Shoko Yoshimura, Saburo Aimoto, Yasutsugu Shimonishi, S ...
    1984 Volume 57 Issue 9 Pages 2543-2549
    Published: 1984
    Released: June 27, 2006
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    A peptide with the amino acid sequence proposed for a heat-stable enterotoxin (STh) produced by a human strain SK-1 of enterotoxigenic Escherichia coli was synthesized by a conventional method. Synthetic STh evoked fluid secretion in suckling mice at a dose of 0.8 ng, which is similar to the effective dose of native STh. The fluid secretion was completely inhibited by antisera raised against the native toxin. Furthermore, synthetic STh showed the same 1H-NMR spectrum and heat-stability as native STh.
  • Haruo Ikemura, Hiroyuki Watanabe, Saburo Aimoto, Yasutsugu Shimonishi, ...
    1984 Volume 57 Issue 9 Pages 2550-2556
    Published: 1984
    Released: June 27, 2006
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    For examination of the structure-activity relationship of STh, five shorter analogs of STh lacking one to five N-terminal amino acid residues of STh were synthesized. The synthetic peptides were confirmed to have the same intramolecular disulfide linkages as those in native STh. These peptides caused fluid accumulation in the intestine of suckling mice at almost the same molar levels as that of native STh. The toxicities of these peptides were also neutralized by antisera raised against native STh. These results indicated that the toxic and antigenic sites of STh are both located in the amino acid sequence between the Cys residue at the 5th position from the N-terminus and the C-terminal Tyr residue.
  • Shigeo Nishimura, Shin-ichi Ohbuchi, Kiyoshi Ikeno, Yasuhiro Okada
    1984 Volume 57 Issue 9 Pages 2557-2564
    Published: 1984
    Released: June 27, 2006
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    Catalytic hydrogenation of 2-naphthol (NL) with the six platinum metals has been studied in t-BuOH at 80 °C and 4–5 MPa H2 pressure. Selectivities for formation of 1,2,3,- and 5,6,7,8-tetrahydro-2-naphthols (ac- and ar-TLs) have been determined by application of a kinetic equation. ar-TL was formed more predominantly than ac-TL over all the metals. The hydrogenation of ac- and ar-TLs has also been studied under the same conditions for comparison. The hydrogenation of NL and ar-TL was accompanied by extensive hydrogenolysis to give decalins over Os, Ir, and Pt, whereas the hydrogenolysis occurred only slightly over Ru, Rh, and Pd. In general the hydrogenolysis occurred to much lesser extents with ac-TL. The amounts of 2-decalone formed in hydrogenation of ar-TL have been determined by application of the kinetic equation. The 2-decalone was the cis isomer only except with Pd. For formation of the cis products at the ring juncture, hydrogenation of ar-TL was highly stereoselective with Ru, Rh, Os, and Ir, while hydrogenation of ac-TL was the most stereoselective with Os and Ir. The course of hydrogenolysis and the stereochemistry of hydrogenation are discussed from the comparative results on NL, ar-TL, and ac-TL.
  • Fumio Kawaizumi, Isao Yajima, Hiroyasu Nomura, Yutaka Miyahara
    1984 Volume 57 Issue 9 Pages 2565-2568
    Published: 1984
    Released: June 27, 2006
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    The viscosities of LiCl, KCl, and CsCl have been measured in water and aqueous solutions containing 0.398 mol/dm3 of 18-crown-6 (CR) at 25 °C. The B-coefficients of the alkali metal chlorides in water have been obtained using the theoretical values of the A-coefficients. The viscosity coefficients of 18-crown-6 itself have been determined in water and methanol. In systems containing crown ether, the viscosity increment due to the complex formed in solutions, Δη[CR–M+]Cl, has been evaluated by subtracting from the observed viscosity the increment attributed to non-coordinated crown ether and alkali metal chlorides in solutions. The two complex ions, [CR-K+] and [CR-Cs+], have nearly the same values of the B-coefficients, and these values are, in turn, approximately equal to that of 18-crown-6 in water. Measurements done on KCl in methanol containing 18-crown-6 have led to the finding that in methanol, 18-cown-6 and the [CR-K+] ion take effectively the same B-value.
  • Yukio Tanaka, Norio Ohtomo, Kiyoshi Arakawa
    1984 Volume 57 Issue 9 Pages 2569-2573
    Published: 1984
    Released: June 27, 2006
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    The structure factor Sm(Q) for liquid ethyl alcohol (C2D5OD) at room temperature was obtained by means of the time-of-flight (TOF) neutron diffraction method using electron LINAC. An analysis of the diffraction data was carried out and the molecular structure in liquid phase was determined as follows: the O–D,C–O, and C–C bond lengths are 0.960±0.010 Å, 1.410±0.010 Å and 1.510±0.010 Å, respectively.
  • Byong-Tae Chang, Guy Campet, Jean Claverie, Paul Hagenmuller
    1984 Volume 57 Issue 9 Pages 2574-2577
    Published: 1984
    Released: June 27, 2006
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    The behaviors of polycrystalline LaxSr1−xTiO3(x≤0.05) electrodes in a photoelectrochemical cell for water decomposition have been investigated in aqueous NaOH electrolyte. The lanthanum substitution for strontium resulted in impressive visible photosensitization of the corresponding electrodes under anodic polarization. This visible photoresponse is based on the relatively deep subband gap states introduced into the forbidden band by lanthanum doping, in analogy with the polished undoped SrTiO3 electrodes reported previously.
  • Hironobu Umemoto, Shigeru Tsunashima, Shin Sato, Nobuaki Washida, Shir ...
    1984 Volume 57 Issue 9 Pages 2578-2580
    Published: 1984
    Released: June 27, 2006
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    The rate constants of the reactions of hydrogen and deuterium atoms with four ketenes have been measured using a pulse radiolysis-resonance absorption technique. For hydrogen atoms, the temperature dependence was also examined in the range of 240–440 K. The rate constants were well expressed by these Arrhenius equations: k(H+ketene)=3.9×106exp(−975⁄T); k(H+methylketene)=74×106exp(−881⁄T); k(H+ethylketene)=4.4×106exp(−728⁄T); k(H+dimethylketene)=6.0×106exp(−773⁄T), in units of m3 mol−1 s−1. No isotope effect between H and D atoms could be observed except for the gas-kinetic-collision frequency.
  • Fujiko Iwasaki, Kin-ya Akiba
    1984 Volume 57 Issue 9 Pages 2581-2583
    Published: 1984
    Released: June 27, 2006
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    The crystal structure of 3,4-dimethyl-2,5-diphenyl-3,4-dihydro-3a-thia-1,3,4,6-tetraazapentalene has been determined by the X-ray method. The crystals are orthorhombic, space group Pbcn, a=14.533(4), b=9.285(3), c=11.305(2) Å, V=1525.4(6) Å3, Z=4, Dx=1.343 Mg m−3. The final R value is 0.060 for 1107 reflections. The molecule has an exact C2 symmetry, with the central S–C bond coincident with the 2-fold axis of the crystal symmetry. The length of 1.904 Å of the two equivalent S–N bonds indicates that the molecule is a tetraaza analogue of the thiathiophthenes. The length of this S–N bond is 9% longer than the N–S single bond and significantly less than the sum of the van der Waals radii.
  • Sekiichiro Nakama, Hiroko Shimada, Ryoichi Shimada
    1984 Volume 57 Issue 9 Pages 2584-2590
    Published: 1984
    Released: June 27, 2006
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    The polarized Raman and infrared spectra of 2-chloro- and 2-bromopyrimidines were studied. Assignments of the normal vibrations for these molecules were made on the basis of polarization behaviors of the Raman and infrared bands and also through the normal coordinate calculation.
  • Tsunetoshi Kobayashi, Zen-ichi Yoshida, Hiroshi Awaji, Tokuzo Kawase, ...
    1984 Volume 57 Issue 9 Pages 2591-2595
    Published: 1984
    Released: June 27, 2006
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    Photoelectron spectra of tetrathiafulvalene (TTF) and 6,6′-bi(1,4-dithiafulvenyl) (BDTF) were measured and compared with each other. The first photoelectron spectral band of BDTF is only slightly shifted relative to that of TTF, though the BDTF molecule is lengthened compared with the TTF molecule by two sp2 carbon atoms. From the LCGO model orbital interaction analysis, this apparent anomaly is ascribed to the near cancellation of the effects of two main factors, the energy and the terminal atomic orbital coefficient differences between the central olefinic group π orbitals. Orbital interaction analysis as demonstrated in this work may be useful for molecular design, especially for orbital energy control.
  • Kazuaki Harata
    1984 Volume 57 Issue 9 Pages 2596-2599
    Published: 1984
    Released: June 27, 2006
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    The crystal structure of β-cyclodextrin–hexamethylenetetramine (1:1) complex hexahydrate was determined by the X-ray diffraction method. The crystal ismonoclinic with the space group P21, Z=2, a=15.285(3), b=10.345(2), c=20.118(2) Å, and β=102.14(1)°. The structure was solved by inspection of a Patterson map and the trial-and-error method combined with the rigid-body least-squares technique and refined by the block-diagonal least-squares method to the R-value of 0.056 for 4369 reflections (sinθ⁄λ<0.55). The β-cyclodextrin molecule is slightly distorted from the regular heptagonal structure. The orientation of two primary hydroxyl groups is statistically disordered. The secondary hydroxyl groups form intramolecular hydrogen bonds between adjacent glucose residues. The guest hexamethylenetetramine molecule, being located roughly at the center of the β-cyclodextrin ring, is in van der Waals contact with the interior surface of the host molecule. Two out of four nitrogen atoms of hexamethylenetetramine form N···H–O hydrogen bonds with water and adjacent β-cyclodextrin molecules. β-Cyclodextrin molecules are stacked along the crystallographic b axis, with which the plane through seven glycosidic oxygen atoms makes an angle of 46.7°, forming a “cage-type” packing. Water molecules occupy the intermolecular spaces between β-cyclodextrin molecules.
  • Hiroshi Nishida, Naoko Takada, Masaji Yoshimura, Takaaki Sonoda, Hiros ...
    1984 Volume 57 Issue 9 Pages 2600-2604
    Published: 1984
    Released: June 27, 2006
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    Tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (TFPB) anion was highly lipophilic, practically insoluble in water, and durable against acid and oxidants. Partition equilibria of alkali TFPB between water and organic solvents and the stability in acid media are described and compared with the properties of the parent tetraphenylborate and of some fluorine-containing homologues.
  • Kazuhiko Ozutsumi, Hitoshi Ohtaki
    1984 Volume 57 Issue 9 Pages 2605-2611
    Published: 1984
    Released: June 27, 2006
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    The structures of mono(glycinato)copper(II) and tris(glycinato)cuprate(II) complexes in solution were determined by means of X-ray diffraction at 20 °C. The radial distribution curve obtained for solution A, in which comparable amounts of hexaaqua- and mono(glycinato)copper(II) complexes coexisted (the mole ratio CglyCCu=0.700, where Ci represents the total concentration of species i), showed that the mono(glycinato)copper(II) complex combined with four water molecules, two of which were at the distance of (1.98±0.01) Å at the equatorial position and the other two were of (2.27±0.01) Å at the axial one. The equatorial Cu–OH2 bond length within the mono(glycinato)copper(II) was longer than that within the hexaaquacopper(II) ion (1.94 Å), whereas the axial Cu–OH2 bond distance within the former complex was shorter than that within the latter (2.43 Å). Both lengths of the Cu–O and Cu–N bonds within the mono(glycinato)copper(II) ion were (1.99±0.02) Å. Thus the [Cu(gly)(OH2)4]+ complex has an axially elongated octahedral structure. The X-ray scattering data of solution B with the CglyCCu mole ratio of 13.7, in which almost all Cu(II) ions formed the tris(glycinato)cuprate(II) complex were well explained in terms of a regular octahedral structure of the complex having the same Cu–O and Cu–N bond distances of (2.02±0.01) Å. The structure of the bis(glycinato)copper(II) complex was not determinable owing to its low solubility.
  • Kazuhiko Ozutsumi, Hitoshi Ohtaki, Asao Kusumegi
    1984 Volume 57 Issue 9 Pages 2612-2617
    Published: 1984
    Released: June 27, 2006
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    The structure of thallium(I) formate aggregates in concentrated aqueous thallium(I) formate solutions was investigated by the X-ray diffraction method at 25 °C for solutions A (10.77 mol dm−3) and B (3.493 mol dm−3). The former solution had the density of 3.189 g cm−3 and the CH2OCTl mole ratio of 2.59, where Ci represents the total concentration of species i, and was an almost saturated solution at room temperature. From the analysis of the X-ray diffraction data of solution A, thallium(I) formate was found to be present as a tetramer Tl4(O2CH)4. The nearest interatomic distances between thallium(I) and atoms within the formate ions in the tetramer were determined as Tl–O: 2.79(1) Å and Tl···C: 3.33(2) Å. The nonbonding Tl···Tl distances within the aggregate were estimated to be 3.92(1) Å, 4.34(1) Å, and 4.79(1) Å. The Tl–OH2 bond length was also determined to be 3.22(3) Å, which was much larger than the distance expected from the sum of the ionic radius of thallium(I) ion (≈1.4 Å) and size of a water molecule (≈1.4 Å). A comparison of the radial distribution function of solution A with that of solution B, which had the CH2OCTl mole ratio of 13.5, indicated that the aggregate decomposed by dilution. Raman spectra of four different thallium(I) formate aqueous solutions of 3.493 to 10.77 mol dm−3 were measured and the frequencies of the C–O and C=O stretchings of formate ions in the solutions were compared with those of free formate ion. Band shifts of the two frequencies observed for concentrated thallium(I) formate solutions indicated the existence of bridge-type formate ions coordinated to thallium(I) ions, and the result agreed with that observed by the X-ray diffraction analysis. Densities, refractive indices, viscosities and conductivities were measured for thallium(I) formate aqueous solutions with varying concentrations.
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