Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 59 , Issue 2
Showing 1-50 articles out of 70 articles from the selected issue
  • Masahiko Arai, Yutaka Ikushima, Yoshiyuki Nishiyama
    1986 Volume 59 Issue 2 Pages 347-350
    Published: 1986
    Released: June 27, 2006
    JOURNALS FREE ACCESS
    Nickel catalysts supported on porous silicas treated with water, ethanol, and 1-butanol were found to be more active than that supported on untreated silica for ethane hydrogenolysis and furan hydrogenation. To elucidate the reason for the activation, some surface properties of the treated silicas were examined. The treatments decreased the surface area and increased the volume of the macropores, the surface density of hydroxyl groups, and the heat of immersion in water per unit surface area. The state of nickel on the support was examined by temperature programed desorption(TPD) of hydrogen, X-ray diffraction(XRD), and scanning electron microscopy/X-ray microanalysis. The dispersion measured by XRD was not appreciably altered by the treatments, but the TPD snowed more hydrogen desorbed above 150 °C from nickel on the treated supports. The activation of nickel by pretreatment of the support was ascribed to the increase of those nickel atoms which dispersed finely over the support by the increased number of surface hydroxyl groups. This was based on the number of hydroxyl groups per unit surface area. The nickel catalyst supported on the pretreated silicas showed greater thermal stability.
  • Kiyoko Yamamoto, Mikio Hoshino, Masahiro Kohno, Hiroaki Ohya-Nishiguch ...
    1986 Volume 59 Issue 2 Pages 351-354
    Published: 1986
    Released: June 27, 2006
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    Chloro(5,10,15,20-tetraphenylporphyrinato)cobalt(III), CoIII(tpp)Cl, in an aerated dichloromethane(DCM) solution undergoes photooxidation to produce the porphyrin π-cation radicals, CoIII(tpp)Cl2. The formation mechanism of the π-cation radical was investigated by means of optical absorption and ESR spectroscopy: CoIII(tpp)Cl in DCM decomposes photochemically to yield CoII(tpp) and chlorine atoms, which then abstract hydrogen atoms from DCM molecules to yield solvent radicals, ·CHCl2, and HCl. The solvent radicals react with oxygen molecules, resulting in the generation of peroxyl radicals, which then oxidize CoIII(tpp)Cl to produce the π-cation radicals, CoIII(tpp)Cl2.
  • Shin-ichi Nagaoka, Edward T. Harrigan, Masayo Noda, Noboru Hirota, Jir ...
    1986 Volume 59 Issue 2 Pages 355-361
    Published: 1986
    Released: June 27, 2006
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    The zero field splittings of a series of substituted benzenes and related molecules have been examined by means of optical detection of magnetic resonance (ODMR), electron paramagnetic resonance (EPR), and molecular orbital (MO) calculations. It is experimentally shown that D and E values vary remarkably depending on the type of molecule despite the similarlity in the molecular size. In particular, E varies from +0.038 cm−1 for phenylacetylene to −0.0597 cm−1 for aniline reflecting large differences in the spin distributions. The calculation of the zero field splittings of the molecules studied here on the basis of the Pariser-Parr-Pople-type MO’s can give the values reasonably close to those obtained experimentally with a few exceptions. On the basis of the obtained results the natures of the T1 states of substituted benzenes are characterized from the zero field splittings.
  • Kyuya Yakushi, Sukekazu Aratani, Koichi Kikuchi, Hiroyuki Tajima, Haru ...
    1986 Volume 59 Issue 2 Pages 363-366
    Published: 1986
    Released: June 27, 2006
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    The semiconductive (TMTTF)2IO4 salt was prepared by using the electrochemical method. The crystal structure was determined to be isomorphous to the metallic (TMTTF)2X salts. The polarized infrared reflectance spectra of (TMTTF)2IO4 and (TMTTF)2BF4 were measured and were interpreted on the basis of the extended Hubbard model.
  • Hidefumi Hirai, Hidehiko Wakabayashi, Makoto Komiyama
    1986 Volume 59 Issue 2 Pages 367-372
    Published: 1986
    Released: June 27, 2006
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    Colloidal copper dispersions are prepared by reducing copper(II) ions in water with sodium tetrahydroborate or hydrazine in the presence of various protective polymers. The polymers are poly(N-vinyl-2-pyrrolidone), poly(vinyl alcohol), poly(methyl vinyl ether), poly(potassium vinyl sulfate), dextrin, amylopectin, methylamylopectin, methylcellulose, ethylcellulose, and (2-hydroxyethyl)cellulose. The dispersions are black, reddish dark brown, or reddish brown homogeneous solutions, and are stable under nitrogen at room temperature for more than three months. Electron diffraction experiments indicate that copper atoms in the colloidal particles are arranged in an ordered way, which is almost identical with that in a crystal of bulk copper metal. At the charged molar ratio 40 of the monomeric residue of the protective polymer to copper(II) ion, the average diameters of the copper particles, prepared by use of sodium tetrahydroborate, range from 50 to 150 Å, depending on the polymer used. With the use of poly(N-vinyl-2-pyrrolidone) as protective polymer, the size of the copper particles monotonously increases with increase in the degree of polymerization of the polymer and also with decrease in the amount of the polymer.
  • Takao Oi, Takanobu Ishida
    1986 Volume 59 Issue 2 Pages 373-379
    Published: 1986
    Released: June 27, 2006
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    The orthogonal approximation method for the zero-point energy (ZPE) developed previously has been applied to analyze the shifts in the ZPE, δ(ZPE), due to monodeuterium substitutions in methane, ethylene, ethane and benzene in terms of elements of F and G matrices. The δ(ZPE) can be expressed with a reasonable precision as a sum of contributions of individual valence coordinates and correction terms consisting of the first-order interactions between the coordinates. A further refinement in the precision is achieved by a set of small number of second-order terms, which can be estimated by a simple procedure.
  • Yukio Sakai, Hiroshi Nakamura, Makoto Takagi, Keihei Ueno
    1986 Volume 59 Issue 2 Pages 381-384
    Published: 1986
    Released: June 27, 2006
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    The extraction of alkaline earth metal ions has been investigated using a mixture of polyethylene glycol mono-p-nonylphenyl ether (PEGP; average number of oxyethylene group, 10) and 4-(1,1-dimethyl-3,3-dimethylbutyl)-2,5-dinitrophenol (2,5-dinitro-4-t-octylphenol, DNP; HL) in 1,2-dichloroethane. The metal extraction takes place with one molecule of deprotonated DNP (L) and an extraneous monoanion (X) for neutralization of the dicationic charge of the metal ion. The ease of extraction generally follows the order, Ba2+>Sr2+>Ca2+>>Mg2+. The nature of the anion present in the aqueous phase strongly affects the extractability. For barium, the extractability decreases in the order ClO4>SCN>I>Cl>NO3. The composition of the extracted complexes for barium and strontium ions proportional to the metal is metal : PEGP : L : X=1 : 1 : 1 : 1. The overall extraction constants were estimated.
  • Tomoji Ohishi, Kazuo Kashiwabara, Junnosuke Fujita, Shigeru Ohba, Tosh ...
    1986 Volume 59 Issue 2 Pages 385-393
    Published: 1986
    Released: June 27, 2006
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    Monomeric (yellow) and dimeric (red) cobalt(III)–dioxygen complexes containing 1,2-bis(dimethylphosphino)ethane (dmpe) have been prepared from [Co(dmpe)2]+ and [Co(dmpe)2]2+, respectively, by air oxidation. The 1,3-bis(dimethylphosphino)propane (dmpp) complex afforded only the monomeric dioxygen complex by either preparative method. The crystal structures of [Co(O2)(dmpe)2]B(C6H5)4 (1) and [Co(O2)(dmpp)2]BF4·H2O (2) have been determined by X-ray analysis. Crystal data for 1; monoclinic, P21a, a=18.011(12), b=18.761(10), c=11.455(6) Å, β=107.78(4)°, V=3686(4) Å3, Z=4, and R=0.064. Crystal data for 2; orthorhombic, Pbcn, a=14.540(5), b=13.123(4), c=13.138(2) Å, V=2507(1) Å3, Z=4, and R=0.076. The complex ions in both 1 and 2 have a trigonal-bipyramidal coordination geometry when the O2 group bonded to the Co atom in the side-on form at a coordination site of the trigonal plane is assumed to be a unidentate ligand. Bond lengths. Co–O (1.858(7)–1.881(4) Å) and O–O (1.414(12) and 1.425(6) Å), and O–O stretching frequencies (877 and 862 cm−1) indicate that both 1 and 2 are the peroxo complexes. The monomeric dioxygen complexes react immediately with SO2 and with concd HCl to afford [Co(SO4)(dmpe or dmpp)2]+ and cis-[CoCl2(dmpe or dmpp)2]+, respectively. The red dimeric trans-[(dmso)(dmpe)2Co(μ-O2)Co(dmpe)2(dmso)](BF4)4 (dmso=dimethyl sulfoxide) complex was isolated and characterized.
  • Ayako Goto, Takeo Higashino
    1986 Volume 59 Issue 2 Pages 395-398
    Published: 1986
    Released: June 27, 2006
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    It was shown that an intermediate, 4,4′(3H,3′H)-biquinazolinylidene (2a) was isolated in the formation process of 4,4′-biquinazolinyl (3a) which was obtained from the reaction of quinazoline (1a) with potassium cyanide, and 2a was readily oxidized to 3a by oxygen in air. The dimerization process was studied kinetically by NMR method. The result showed that the process was essentially similar to that of the benzoin condensation. The introduction of a methyl group into the C2-position of 1a resulted in a lowering of the reaction rate because the activation energy of 2-methylquinazoline (1b) dimerization became higher compared with that of 1a dimerization.
  • Toshio Yoshioka, Masaharu Shimamura
    1986 Volume 59 Issue 2 Pages 399-403
    Published: 1986
    Released: June 27, 2006
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    A new polystyrene-based ion-exchange fiber (IONEX) has a large surface area per unit weight and has been studied for its ability to adsorb and immobilize biologically-active proteins. A strong cation IONEX was found to be able to effectively adsorb hemoglobin and albumin, invertase, and glucose isomerase were readily adsorbed to a strong anion IONEX. The adsorption of these proteins to IONEX was found to take place through an electrostatic force. The adsorption capacity for proteins became exceedingly large (ca. 300 mg g−1) with an increase in the water-holding capacity of the fiber. The activities of the invertase and glucose isomerase immobilized to the fiber exhibited 40–50 and 75–80%, respectively, of those of native enzymes. A continuous inversion of sucrose was also carried out using immobilized invertase. From these results, this fibrous ion exchanger with a high water-holding capacity is considered to be an excellent material for the adsorption and immobilization of proteins.
  • Noboru Ono, Isami Hamamoto, Takashi Kawai, Aritsune Kaji, Rui Tamura, ...
    1986 Volume 59 Issue 2 Pages 405-410
    Published: 1986
    Released: June 27, 2006
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    Treatment of allylic nitro compounds with sodium benzenesulfinate in the presence of 5 mol% of Pd(PPh3)4 in N,N-dimethylformamide (DMF) at 20–70 °C for 1–10 h resulted in the formation of allylic sulfones with predominance of kinetically controlled products. The product distribution is mainly controlled by the electronic nature of substituents of an allyl unit, and the isomerization to the thermodynamically-stable isomers is negligible. On the other hand, the palladium-catalyzed sulfonylation of allylic acetates with sodium benzenesulfinate is accompanied by the isomerization to give the thermodynamically-controlled products selectively. These results can be explained by assuming that allylic nitro compounds are more reactive to the palladium catalyst than allylic acetates and sulfones.
  • Shinkiti Koto, Kazuo Yago, Shonosuke Zen, Fumiya Tomonaga, Shigehiko S ...
    1986 Volume 59 Issue 2 Pages 411-414
    Published: 1986
    Released: June 27, 2006
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    The D-glucosylation of methyl 2,3,4-tri-O-benzyl-α-D-glucopyranoside and methyl 2,3,6-tri-O-benzyl-β-D-glucopyranoside by 2,3,4,6-tetra-O-benzyl-α-D-glucopyranose using pyridine and excess trimethylsilyl triflate was carried out in dichloromethane, 1,2-dimethoxyethane, and acetonitrile. In a given solvent, the selectivity of the reaction varied depending on the type of hydroxyl group of the glucosyl acceptors. The D-glucosylation of these acceptors with 6-O-acetyl-2,3,4-tri-O-benzyl-D-glucopyranose employing this reagent system in dichloromethane proceeded with good α-selectivity irrespective of the type of the hydroxyl group. This α-D-glucosylation was applied for the synthesis of O-α-D-glucopyranosyl-(1→4)- and -(1→6)-α-D-glucopyranosyl α-D-glucopyranosides from α,α-trehalose.
  • Yoshikazu Kimura, Michiyo Suzuki, Teruyo Matsumoto, Rumiko Abe, Shiro ...
    1986 Volume 59 Issue 2 Pages 415-421
    Published: 1986
    Released: June 27, 2006
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    Diels-Alder reaction of 2-chloro-1,3-butadiene with anthracene-1,4,9,10-tetrone was found to occur exclusively at the external (C2,3) double bond, giving the adduct in an excellent yield. The adduct was elaborated to 5,12-dihydroxy-1,2,3,4-tetrahydro-2,6,11-naphthacenetrione. The conventional cyanohydrin formation of this sample followed by acid hydrolysis gave (±)-2,5,12-trihydroxy-6,11-dioxo-1,2,3,4-tetrahydro-2-naphthacenecarboxylic acid. The racemic acid was found to be cleanly resolved by forming a salt with (−)-N-methylephedrine, furnishing optically pure (R)-carboxylic acid. Successive treatments of the (R)-carboxylic acid with N,N′-carbonyldiimidazole and methylmagnesium bromide in the presence of trimethylsilyl triflate readily produced optically pure (R)-(−)-7-deoxy-4-demethoxydaunomycinone, the key synthetic intermediate of (+)-4-demethoxydaunomycinone.
  • Yoshikazu Kimura, Michiyo Suzuki, Teruyo Matsumoto, Rumiko Abe, Shiro ...
    1986 Volume 59 Issue 2 Pages 423-431
    Published: 1986
    Released: June 27, 2006
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    Optically pure (+)-4-demethoxydaunorubicin has been prepared by a novel glycosidation reaction of (+)-4-demethoxydaunomycinone with (−)-3-N-trifluoroacetyl-1,4-bis(O-p-nitrobenzoyl)-L-daunosamine in the presence of trimethylsilyl triflate, followed by sequential O- and N-deprotection reactions. Total synthesis of optically pure (+)-4-demethoxyadriamycin has been also accomplished by two different synthetic schemes, starting from (+)-4-demethoxydaunorubicin or by way of (+)-3′-N-trifluoroacetyl-4-demethoxyadriamycin. (+)-4-Demethoxyadriamycin prepared by our hands was fully characterized by its spectral properties.
  • Toshikazu Ibata, Shuji Nakano, Hiroyuki Nakawa, Jiro Toyoda, Yasushi I ...
    1986 Volume 59 Issue 2 Pages 433-437
    Published: 1986
    Released: June 27, 2006
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    The Diels–Alder reactions of 2-methyl- and 2-ethyl-5-methoxy-4-(p-nitrophenyl)oxazoles with N-methyl-, N-ethyl-, and N-phenylmaleimides gave endo- and exo-adducts. When the reactions were carried out in an acetonitrile solution containing a small amount of water as an impurity, N-substituted 3-hydroxy-2-(p-nitrophenyl)-4,5-pyridinecarboximides were obtained via the decomposition of the Diels–Alder adducts, while the methanol was eliminated. The decomposition might be catalyzed by contaminated water at the initial stage of the reaction. The adducts of N-phenylmaleimide and N-ethylmaleimide were shown to undergo the retro-Diels–Alder reaction on heating at 80°C to give the starting maleimides and oxazole. Diethyl azodicarboxylate and 4-phenyl-3H-1,2,4-triazole-3,5(4H)-dione gave the corresponding single adducts. A reaction with dimethyl acetylenedicarboxylate gave p-nitrobenzonitrile (10), dimethyl 2-methyl-5-methoxy-3,4-furandicarboxylate (11), and tetramethyl 3,5-epoxy-3-methoxy-5-methyl-1,4-cyclohexadiene-1,2,4,5-tetracarboxylate (12), although the expected adduct was not isolated. These products were explained on the basis of the Diels–Alder reaction, followed by the retro-Diels–Alder reaction, thus affording 10 and 11, which gave 12 upon cycloaddition with the second molecule of DMAD.
  • Teruo Umemoto, Yoshihiko Gotoh
    1986 Volume 59 Issue 2 Pages 439-445
    Published: 1986
    Released: June 27, 2006
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    FITS reagents reacted with primary alkylmagnesium halides in THF at −78 °C to give the corresponding perfluoroalkyl(Rf)-alkanes in moderate to good yields. But an alkyl-lithium or -copper gave a poor yield of the Rf-product. The reaction of FITS with secondary or tertiary alkylmagnesium halides resulted in low yields of the products. Alkynyl-lithiums or -magnesium halides produced Rf-alkynes in favorable yields. The reaction with aryl or vinylmagnesium halide was complex and the yields of Rf derivatives were low. FITS also reacted smoothly with enolate anions of active methylene compounds such as 2-methyl-1,3-cyclopentanedione, ethyl 2-methylacetoacetate, and ethyl 2-oxocyclopentanecarboxylate in a polar solvent to afford O- and C-perfluoroalkylation products in moderate yields, ratios O-/C-Rf products depending on the reaction temperature. Anions of diethyl 2-methylmalonate and 2-nitropropane afforded C-Rf-compounds only.
  • Teruo Umemoto, Akira Ando
    1986 Volume 59 Issue 2 Pages 447-452
    Published: 1986
    Released: June 27, 2006
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    N-Trifluoromethyl-N-nitrosotrifluoromethanesulfonamide (TNS-Tf) was synthesized in a 58% yield by the reaction of trifluoronitrosomethane with hydroxylamine followed by the treatment with trifluoromethanesulfonyl fluoride in the presence of a base. TNS-Tf was demonstrated to be an effective trifluoromethylating agent photochemically or thermally for aromatics, thiols, disulfides, and uridine derivatives. The insertion reaction by two trifluoromethyl groups of TNS-Tf to the sulfur-sulfur bonds was observed in the reaction with disulfides having electron-withdrawing groups, giving 2 mols of trifluoromethylthio compounds. Furthermore, TNS-Tf served as a good reagent for mild and convenient in situ generation of trifluoromethylcopper complex which converted iodoaromatics to trifluoromethyl-substituted aromatics in good yields. Similarly, N-trifluoromethyl-N-nitrosononafluoro-1-butanesulfonamide (TNS-Nf) was synthesized in a 36% yield. The examination of the reactivity indicated that this type of N-nitroso sulfonamides became to be sources of both perfluoroalkyl radicals contained.
  • Tadashi Okuyama, Wataru Fujiwara, Takayuki Fueno
    1986 Volume 59 Issue 2 Pages 453-456
    Published: 1986
    Released: June 27, 2006
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    Various 2-substituted 1,3-dithiolan-2-ylium perchlorates (1) were prepared by the reaction of 1,2-ethanedithiol with acyl chlorides in the presence of perchloric acid. Treatments of 1 with triethylamine gave 2-alkylidene-1,3-dithiolane (2) when the 2-substituent was a primary or secondary alkyl group. 2-Aryl derivatives of 1 were converted to ortho esters by the reaction with methanol in the presence of silver nitrate. 1,3-Dithian-2-ylium perchlorates and 2-alkylidene-1,3-dithianes were also prepared similarly from 1,3-propanedithiol.
  • Tsuyoshi Satoh, Youhei Kaneko, Kiichi Sakata, Koji Yamakawa
    1986 Volume 59 Issue 2 Pages 457-463
    Published: 1986
    Released: June 27, 2006
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    Aminolysis of α,β-epoxy sulfoxides, easily prepared from 1-chloroalkyl phenyl sulfoxides or chloromethyl phenyl sulfoxide and carbonyl compounds, with alkyl- or arylamines afforded α-amino ketones or α-amino aldehydes in good yields. Treatment of thus obtained α-arylamino ketones with weak Lewis acid led to 2,3-disubstituted indoles.
  • Akihiko Ueno, Fumio Moriwaki, Tetsuo Osa, Fumio Hamada, Koichi Murai
    1986 Volume 59 Issue 2 Pages 465-470
    Published: 1986
    Released: June 27, 2006
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    Host–guest complexation of γ-cyclodextrin bearing two 2-naphthyl moieties (1) has been studied by circular dichroism and fluorescence spectroscopic methods. The exciton coupling band observed in the naphthalene 1La transition region shows that the two naphthyl moieties of 1 take a chiral orientation in the cavity. The guest binding of 1 changes the circular dichroism pattern, finally affording a negative band, but hardly influences the fluorescence pattern in which excimer emission is predominant. These phenomena suggest that a guest molecule is included in the cavity of 1 by extruding two naphthyl moieties from the cavity so as to make the moieties to act as hydrophobic caps. Dimethyl sulfoxide(DMSO) was found to be effective to change both fluorescence and circular dichroism patterns, increasing monomer-like emission and converting the exciton coupling pattern to a simple negative band. These results suggest that the two naphthyl moieties are not in proximal positions in DMSO-rich solutions.
  • Etsuo Niki, Mitsuo Saito, Yasuyuki Yoshikawa, Yorihiro Yamamoto, Yoshi ...
    1986 Volume 59 Issue 2 Pages 471-477
    Published: 1986
    Released: June 27, 2006
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    The activity of uric acid as a chain-breaking antioxidant was studied in the oxidations of methyl linoleate micelles and soybean phosphatidylcholine liposomes in aqueous dispersions at 37°C. Uric acid was found to act as a radical scavenger. Uric acid located in an aqueous phase could trap the radicals in an aqueous phase, but it could not scavenge radicals within the lipid region of micelles and liposomal membranes. The kinetics of the oxidations of lipids in aqueous dispersions inhibited by uric acid was discussed.
  • Kuniaki Itoh, Akira Sera
    1986 Volume 59 Issue 2 Pages 479-482
    Published: 1986
    Released: June 27, 2006
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    Reaction of 1,4-dibromo-2,5-piperazinedione (1) with 3,4-dihydro-2H-pyran (2) under irradiation gave 1 : 1 and 1 : 2-addition products (3,4) and corresponding secondary products (5–7). The adducts were considered to be produced separately by photoinduced free radical addition as well as concomitant ionic addition reactions.
  • Toshio Fuchigami, Ching-Sy Chen, Tsutomu Nonaka, Mou-Yung Yeh, Hsien-J ...
    1986 Volume 59 Issue 2 Pages 483-486
    Published: 1986
    Released: June 27, 2006
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    A general method for the introduction of heteroatoms to the 4-position of a sydnone ring was developed. Various 4-alkylthio- and 4-arylthiosydnones were prepared in excellent yields by the reaction of 3-aryl-4-lithiosydnones (2) with dialkyl and diaryl disulfides. Treatment of 2 with diaryl diselenides, diphenylphosphinous chloride, and arsenic trichloride provided 3-aryl-4-(arylseleno)sydnones, (3-aryl-4-sydnonyl)diphenylphosphine and tris(3-aryl-4-sydnonyl)arsine, respectively, in good yields. It was also found that the reactivity of sydnonyl anions derived from 2 was quite different in some cases from that of the corresponding ordinary aromatic analogues, though the sydnone ring has a somewhat aromatic nature.
  • Toshio Fuchigami, Ching-Sy Chen, Tsutomu Nonaka, Mou-Yung Yen, Hsien-J ...
    1986 Volume 59 Issue 2 Pages 487-491
    Published: 1986
    Released: June 27, 2006
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    The introduction of thio and seleno functional groups to the 4-position of a sydnone ring was successfully attempted using 4-lithiosydnones (2) and 4-bromosydnones (3) as starting compounds. The reaction of 2 with tetraalkylthiuram disulfides, bis[alkoxy(thiocarbonyl)] disulfides, and bis[alkylthio(thiocarbonyl)] disulfides provided 4-sydnonyl dithiocarbamates, O-alkyl S-(4-sydnonyl) dithiocarbonates, and dialkyl 4-sydnonyl trithiocarbonates, respectively in good yields. In addition, treatment of 2 with thiocyanogen and selenocyanogen gave rise to bis(4-sydnonyl) sulfides (11) and bis(4-sydnonyl) selenides (12), respectively. These products, 11 and 12 were also formed by the reaction of 3 with potassium thiocyanate and selenocyanate, respectively. Furthermore, it was found that 3 reacted with selenourea and potassium O-ethyl dithiocarbonate under heating to provide 12 and 11, respectively. It was also found that the reactivity of these sydnone compounds 2 and 3 was quite different in many cases from that of the corresponding ordinary aromatic analogues, though the sydnone ring has a somewhat aromatic nature.
  • Sannamu Lee, Yasushi Kodera, Kosaku Noda, Haruhiko Aoyagi, Tetsuo Kato ...
    1986 Volume 59 Issue 2 Pages 493-495
    Published: 1986
    Released: June 27, 2006
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    An unusual new amino acid, (2S,3R,4R)-4-chloro-3-hydroxyproline, was stereospecifically synthesized through a four-intermediate from Boc-3,4-dehydro-L-proline. The obtained product was stable in a mild alkaline solution.
  • Etsuo Niki, Jyunichi Tsuchiya, Yasuyuki Yoshikawa, Yorihiro Yamamoto, ...
    1986 Volume 59 Issue 2 Pages 497-501
    Published: 1986
    Released: June 27, 2006
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    The antioxidant activities of α-, β-, γ-, and δ-tocopherols were studied. They were all effective as antioxidant in the oxidations of methyl linoleate in homogeneous solution. When one of the four tocopherols was used alone, they were consumed at the same rate and they suppressed the oxidation for the same period. However, the stabilities of chromanyloxyl radicals derived from the corresponding tocopherols varied considerably and decreased in the order α>β≅γ>δ -chromanyloxyl radicals. α-Tocopherol reacts quite rapidly with β-, γ-, and δ-chromanyloxyl radicals to give α-chromanyloxyl radical and β-, γ-, and δ-tocopherols respectively. Accordingly, when the four tocopherols were used together, α-tocopherol was consumed first, then β- and γ-tocopherols were consumed, and δ-tocopherol began to decrease after most of α-, β-, γ-tocopherols were depleted.
  • Michio Kobayashi, Hiromi Ohkubo, Toshio Shimizu
    1986 Volume 59 Issue 2 Pages 503-506
    Published: 1986
    Released: June 27, 2006
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    An effective synthesis of selenoxides by the oxidation of selenides with t-butyl hypochlorite in the presence of methanol and pyridine followed by hydrolysis is descrived. This oxidation method is particularly effective for the oxidation of selenides which possess electron-withdrawing groups. A synthesis of partially optically active selenoxide with bulky substituents can be achieved using a novel oxidation method.
  • Shinsaku Shiraishi, Makoto Komiyama, Hidefumi Hirai
    1986 Volume 59 Issue 2 Pages 507-510
    Published: 1986
    Released: June 27, 2006
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    β-Cyclodextrin (β-CyD) was covalently immobilized on silica gel by chlorination of silica gel with thionyl chloride or silicon tetrachloride, followed by the reaction of the resulting chlorinated silica gel with β-CyD in pyridine. The amounts of the immobilized β-CyD were 8×10−5 to 1.4×10−4 mol per 1 g of the β-CyD–silica gel composites. On heating, the composites did not exhibit weight decrease up to 250 °C. The β-CyD in the composites formed 1 : 1 complex with phenol in aqueous solutions, and the equilibrium constant for the dissociation of the complex was 6×10−3 mol dm−3 at 25 °C. The immobilized β-CyD exhibited catalytic activity in the cleavage of 4-nitrophenyl acetate at 25 °C, pH 8.7.
  • Akira Mori, Yasutoshi Isayama, Hitoshi Takeshita
    1986 Volume 59 Issue 2 Pages 511-514
    Published: 1986
    Released: June 27, 2006
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    Unlike the benzenoid equivalent, p-methoxyphenol, the cerium(IV) ammonium nitrate (CAN)-oxidation of 5-hydroxy-2-methoxytropone gave C–C coupling products. On the other hand, either by thallium(III) nitrate (TTN) or CAN at 50 °C, 5-hydroxytropolone, a free tropolone, gave 3-methoxy-p-tropoquinone together with p-tropoquinone and 8-oxabicyclo[3.2.1]octenone derivatives, but no dimeric product.
  • Yukito Murakami, Jun-ichi Kikuchi, Toshihiko Takaki, Katsuya Uchimura
    1986 Volume 59 Issue 2 Pages 515-523
    Published: 1986
    Released: June 27, 2006
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    The morphological behavior of various combinations of the following synthetic lipids was investigated in the aqueous dispersion state by means of electron microscopy, differential scanning calorimetry, and fluorescence polarization spectroscopy as well as by turbidity and X-ray diffraction measurements: N+C5Ala2Cn and N+(H)C5Ala2Cn as cationic, (SO3)C5Ala2Cn as anionic, and QC5Ala2Cn as nonionic (n=14, 16). Aqueous dispersions of various combinations of cationic and anionic lipids at the equimolar ratio afforded nonlamellar aggregates, having highly ordered and three-dimensional network structure with repeating distances in the 70–130 Å range, above their phase transition temperatures (Tm). However, any slight loss of the fractional balance retained at the equimolar ratio led to the formation of bilayer aggregates. Under such conditions that allow the formation of nonlamellar aggregates, the high microscopic homogeneity of cationic and anionic lipid molecules was attained, originating from the intramembrane electrostatic interaction between cationic and anionic head moieties to form highly developed ion-pair clusters on the aggregate surface. Meanwhile, the nonlamellar phase appeared above Tm was spontaneously transformed into the normal bilayer phase below Tm as confirmed by electron microscopy and turbidity measurements. The nonlamellar phase was also characterized by the low-angle X-ray diffraction method and was consistent with the highly developed domain with the face-centered cubic lattice.
  • Koichi Narasaka, Yutaka Ukaji, Shigeru Yamazaki
    1986 Volume 59 Issue 2 Pages 525-533
    Published: 1986
    Released: June 27, 2006
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    Reduction of β-hydroxy ketone O-benzyl oximes with lithium aluminum hydride in the presence of sodium or potassium methoxide afforded the corresponding syn-β-amino alcohols in highly stereoselective manner. A lythraceae alkaloid, lasubine II, was synthesized stereoselectively by applying this method.
  • Kazuki Sato, Rika Kato, Ukon Nagai
    1986 Volume 59 Issue 2 Pages 535-538
    Published: 1986
    Released: June 27, 2006
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    [D-Pro5,5′]-Gramicidin S was synthesized to confirm a prediction that D-D sequence at the corner position had low preference for β-turn. The analog showed much weaker activity than gramicidin S and also showed different CD spectra from those of gramicidin S. The results indicate that the analog can not take stable, gramicidin S-like, β-sheet conformation.
  • Tadao Uyehara, Yasuhiro Kabasawa, Toshiaki Furuta, Tadahiro Kato
    1986 Volume 59 Issue 2 Pages 539-543
    Published: 1986
    Released: June 27, 2006
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    1-Methoxybicyclo[3.2.2]non-6-en-2-ones and the related compounds were derived I) from the Diels-Alder type 1,4-addition products of tropones with ethylene by selective reduction of the α,β-unsaturated carbonyl part (hydrosilylation followed by hydrolysis) and/or II) from bicyclo[2.2.2]oct-5-en-2-ones a) by the ring-enlargement utilizing Tieffeneau-Demjanov type conditions (1, TMS–CN; 2, LiAlH4; 3, NaNO2–AcOH) and/or b) by the related ringexpansion using trimethylsilyldiazomethane and boron trifluoride etherate. These bridged compounds were transformed into the respective [1,3] acyl migration products, cis-bicyclo[4.3.0]non-4-en-7-ones, in practical yields by direct irradiation through a Pyrex filter.
  • Hidefumi Hirai, Hidehiko Wakabayashi, Makoto Komiyama
    1986 Volume 59 Issue 2 Pages 545-550
    Published: 1986
    Released: June 27, 2006
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    Homogeneous hydrations of unsaturated nitriles such as acrylonitrile, methacrylonitrile, and crotononitrile to the corresponding unsaturated amides have been carried out in water at 80°C by use of colloidal copper dispersions as catalysts. The dispersions are prepared by reduction of copper(II) sulfate, copper(II) chloride, and copper(II) acetate with sodium tetrahydroborate in the presence of various polymers. The dispersions with poly(N-vinyl-2-pyrrolidone), poly(vinyl alcohol), methylamylopectin, methylcellulose, ethylcellulose, and (2-hydroxyethyl)cellulose exhibit much larger catalytic activities than the copper precipitates prepared by reduction of the copper salts with sodium tetrahydroborate in the absence of the polymers. For all the catalytic reactions with the colloidal dispersions, selectivity for the unsaturated amides is 100% and formation of any by-products is not detected at all. Electron microscopy shows that no significant structural change occurs in the dispersions during the catalytic hydration. The catalytic activity monotonously increases with increasing amount of poly(N-vinyl-2-pyrrolidone) up to the charged ratio 20 of the monomeric residue to copper(II) ion, showing saturation at the ratio larger than 20. When the degree of the polymerization of poly(N-vinyl-2-pyrrolidone) is varied at a fixed residual molar ratio 40, the activity shows a maximum at the degree of polymerization 1440. The results are interpreted both by the change in the size of the colloidal copper particles and by the difference in the magnitude of the interactions between the polymers and the copper particles.
  • Isao Sekine, Hiroyuki Ishii
    1986 Volume 59 Issue 2 Pages 551-556
    Published: 1986
    Released: June 27, 2006
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    For an effective electrolytic recovery of silver from photographic fixing solutions, polarization measurements and potentiostatic electrolysis were carried out using active carbon as a fluidized bed electrode. The optimum conditions, determined by the electrolytic recovery, required a static bed height was 4 mm, a bed expansion rate 14%, and an initial set potential −0.84 V vs. SCE. The current efficiency in this case was about 75%, and the limiting concentration for recovery of silver was about 5 ppm. The electrolytic duration for recovery of the silver was reduced to about half by enlarging the electrolytic cell. Other products formed during the electrolysis were hydrogen sulfide (H2S) and silver sulfide (Ag2S). When silver deposited under the optimum conditions was dissolved in 5M-HNO3 (1M=1 mol dm−3) of 100 ml, the recovery efficiency of the silver was about 75%.
  • Shigeyoshi Miyagishi, Seiichi Matsumura, Tsuyoshi Asakawa, Morie Nishi ...
    1986 Volume 59 Issue 2 Pages 557-561
    Published: 1986
    Released: June 27, 2006
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    The solid-liquid phase transitions of N-acyl amino acids with different acyl groups were investigated using a differential scanning calorimeter and an infrared spectrophotometer. The enthalpy and entropy changes of the transition increased by 3–5 kJ mol−1 and 8–10 J K−1mol−1, respectively, for an additional methylene group in N-acylglycine, and 7 kJ mol−1 and 18 J K−1mol−1, respectively, in the N-acyl-L,-alanine series. The same thermodynamic quantities of N-acylvalines were only slightly dependend on the acyl chain length, while they varied irregularly for the N-acylleucine series. Both the enthalpy and entropy were smaller for the L-form than for its racemic isomer in the N-acylleucines (C12 and above) and N-acylvalines. The differences of the thermodynamic quantities between the L- and DL-forms seems to result mainly from the difference of the molecular packing in the solid state.
  • Yuri I. Dolzhenko, Tamotsu Inabe, Yusei Maruyama
    1986 Volume 59 Issue 2 Pages 563-567
    Published: 1986
    Released: June 27, 2006
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    The intercalation-deintercalation process of weak interaction organic molecules such as 1-chloronaphthalene and o-dichlorobenzene into highly oriented polycrystalline (C10H21NH3)2CdCl4 films and hexane into (C9H19NH3)2Pbl4 single crystals has been observed in situ by using X-ray technique. The process is highly reversible. Increasing of interlayer spacing is in reasonable agreement with the size of the intercalated molecules and corresponds to the parallel orientation of aromatic ring planes or hexane chains in between two paraffin layers of the host crystals.
  • Nobuaki Kanamaru, Jiro Tanaka
    1986 Volume 59 Issue 2 Pages 569-573
    Published: 1986
    Released: June 27, 2006
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    Nanosecond laser photolysis (nslp) of N-methylindole (NMI) was investigated using XeCl laser (308 nm) so that excitation is performed at the red edge of the first absorption band. At least three transient absorptions were observed i.e. those to be ascribed to Sn←S1, Tn←T1 transitions and ion-pair like species with peaks at ≈700 nm, ≈460 nm, and ≈380 nm, respectively. The transient absorptions were found to be produced by monophotonic processes. The lifetimes of the triplet state and the ion pair were determined to be ≈3.1 μs and ≈29 μs, respectively, in degassed solutions. Transient photoconductivity (tpc) measured on the same system indicated that there are both rise and decay components. Its fastest decay component of ≈26 μs, is close to that of the transient absorption ascribed to the ion pair. This result provides another example of monophotonic electron ejection through fluorescent states of aromatic amines in polar solvents, such as, acetonitrile.
  • Hideo Sekiyama, Nobuhiro Kosugi, Haruo Kuroda, Toshiaki Ohta
    1986 Volume 59 Issue 2 Pages 575-579
    Published: 1986
    Released: June 27, 2006
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    X-Ray absorption spectra of the sulfur K-edges of SO42−, SO32−, S2O32−, and S2Ox2− (x=5–8) were measured with synchrotron radiation. The spectra show similarly strong absorption bands which originate in bound-state transitions to antibonding 3p-type orbitals and in shape resonances related to 3d-type orbitals. The K-edge spectrum for the terminal sulfur atom in S2O32−, however, shows only a bound-state transition. Differences in chemical environments and bonding around the X-ray absorbing atoms are discussed to interpret the spectra.
  • Hideko Kiriyama, Yukiko Mizuhashi, Junji Ootani
    1986 Volume 59 Issue 2 Pages 581-585
    Published: 1986
    Released: June 27, 2006
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    Crystal structures of the title compounds were determined by X-ray diffraction method. The crystal data and the final R values are: [(CH3)3NH]2TeI6, cubic, Pa3, a=13.210(2) Å, V=2305.2(9) Å3, Z=4, R=0.057 for 263 observed unique reflections and [(CH3)3NH]2TeI7, tetragonal, P4⁄nmm, a=13.921(3), c=6.224(2) Å, V=1206.4(8) Å3, Z=2, R=0.051 for 553 reflections. The structure of hexaiodo complex is a modified K2PtCl6 type. The discrete[TeI6]2− octahedra are practically regular with a Te–I distance of 2.952(2) Å. The trimethylammonium cations lie on the unit cell triad axes and form trifurcated, weak hydrogen bonds of NH···3I. In contrast, the TeIV coordination in the heptaiodo complex is an elongated octahedron with Te–I(1)=2.934(1) and Te–I(2)=3.124(4), 3.100(4) Å. These TeI6 octahedra form linear trans TeI5 chains running along c by sharing each pair of opposite vertices. Extra iodine atoms also stack along c with nearly equidistant I–I separations of 3.091(6) and 3.133(6) Å. The trimethylammonium cation is distributed randomly over four configurations in a cavity formed by two [TeI5]nn and two [I]2nn columns. Thus, the chemical constitution of the heptaiodo complex can be expressed as di-trimethylammonium catena-μ-iodo-tetraiodo tellurate(1-) catena-diiodide(1-), [(CH3)3NH]2n2n+[TeI5]nn[I]2nn.
  • Hiroshi Maeda, Tsuyoshi Hiramatsu, Shoichi Ikeda
    1986 Volume 59 Issue 2 Pages 587-591
    Published: 1986
    Released: June 27, 2006
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    In the solution of fully neutralized poly(L-glutamic acid) in the absence of supporting electrolytes, the α-helix was induced by the addition of five transition metal chlorides in the following order: CuCl2\gtrsimCdCl2>ZnCl2>NiCl2>CoCl2. The induction did not occur by the addition of BaCl2, CaCl2, or MgCl2. The induction by transition metal cations was inhibited in the presence of a supporting electrolyte (NaCl). Distortion of circular dichroism (CD) spectra occurred as the induction of the α-helix proceeded, which was shown to be recognizable when apparent aggregation number m exceeded about 100. Conformation of the polypeptide in these aggregates was expected to be the α-helix based on the conformation in the precipitates obtained at these mixing ratios which gave distorted CD spectra, which was determined by infrared absorption spectra.
  • Akira Kira, Masashi Imamura, Seiichi Tagawa, Yoneho Tabata
    1986 Volume 59 Issue 2 Pages 593-597
    Published: 1986
    Released: June 27, 2006
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    The pulse radiolysis of a Freon mixture (FM), an equivolume mixture of CFCl3 and CF2BrCF2Br, at 77 K gave transient absorption bands with peaks at 360, 490, and 530 nm, whose decay was enhanced by cation scavengers: propylamine, triethylamine, N,N′-diethylaniline, and biphenyl. The degree of the enhancement was independent of the difference in the ionization potential between the matrix and the solute molecules. In the FM matrix, positive-charge transfer from biphenyl cations to some other solute molecules showed energy dependence similar to that observed in the s-butyl chloride matrix. The rate of inter-solute positive-charge transfer was faster in the FM matrix than in the s-butyl chloride matrix. These results were discussed in relation to current electron transfer theories.
  • Kohei Uosaki, Susumu Kaneko, Hideaki Kita, A. Chevy
    1986 Volume 59 Issue 2 Pages 599-605
    Published: 1986
    Released: June 27, 2006
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    The electrochemical behaviors of van der Waals face of p-InSe single crystal electrodes in 0.5M H2SO4 and 1M NaOH (1M=1 mol dm−3) with and without illumination have been thoroughly investigated. In 0.5M H2SO4, relatively large cathodic dark current was observed and the onset potentials for the current in dark and under illumination were ca. −0.8 V (vs. Ag/AgCl) and ca. −0.5 V, respectively, at as-prepared electrode. The current seemed to be mainly due to hydrogen evolution reaction. The dark current decreased significantly and the photo-current increased by removing surface steps. These results and impedance analyses show that the surface steps create surface states which act as recombination centers and mediators for charge transfer. Both the dark- and photocurrent onset potentials in 1M NaOH were more negative than those in 0.5M H2SO4 by ca. 0.5 V. The dark current was quite large and the photocurrent was small in 1M NaOH even after removing surface steps. By depositing Pt on p-InSe, the photocurrent onset potential shifted towards positive by several hundred mV. The reaction mechanism of photoelectrochemical hydrogen evolution was discussed by considering the above results.
  • Yoshichika Bando, Takahito Terashima
    1986 Volume 59 Issue 2 Pages 607-612
    Published: 1986
    Released: June 27, 2006
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    Films containing Co ultrafine particles were prepared by hydrogen reduction of periodically multilayered CoO–SiO films which were formed by alternating deposition of CoO and SiO. The films containing Co particles maintained the periodicity similar to the original films. Using samples of CoO single layer sandwiched between SiO layers, highly dispersed Co particles in the reduced sample were observed by transmission electron microscopy. The average size of the Co particles was almost as large as the thickness of CoO layer. The coercivities of the multilayered films containing Co particles were measured at room temperature and 77 K; they decreased with decreasing particle size from 20 nm to 3nm. Superparamagnetism was observed for the Co particles with average sizes below 4nm at room temperature. The formation and the magnetic property of the Co ultrafine particles in the Co–SiO system is dicussed.
  • Jung-Sung Kim, Woo-Sik Jung, Hiroshi Tomiyasu, Hiroshi Fukutomi
    1986 Volume 59 Issue 2 Pages 613-616
    Published: 1986
    Released: June 27, 2006
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    The kinetics of formation of bis(oxalato)oxovanadate(IV) [VO(ox)2(H2O)]2− (hereafter water molecule will be omitted) from the reaction of bis(glycinato)oxovanadium(IV) [VO(gly)2] with oxalate has been studied by the stopped-flow method. The reaction was found to consist of two consecutive steps, a relatively slow step (k1) and a fast one (k2). The values of rate constants k1 and k2 were independent of the concentration of free oxalate and of the pH of solution ranging from 4.2 to 6.5. Similar behavior was also observed in the acid decomposition of [VO(gly)2]. A mechanism passing through an intermediate, [VO(ox)(gly)], was proposed.
  • Yoshihisa Yamamoto, Eiko Toyota
    1986 Volume 59 Issue 2 Pages 617-620
    Published: 1986
    Released: June 27, 2006
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    The title paramagnetic cobalt(III) complexes, (Remark: Graphics omitted.),(X3: Cl2·NO3, (NO3)3), both green color, have been isolated and characterized by analytical, spectroscopic and magnetic methods. The effective magnetic moments are 1.7 BM, suggesting an unpaired spin. The 1H NMR spectra indicate that the unpaired spin on the complexes is localized over the π-orbitals of the chelated ligand. In the XPS, the high binding energy area at 286–289 eV of the C ls peak of both the complexe is larger than that for the corresponding diamagnetic cobalt(III) complex. The cobalt 2p peaks do not have satellites in the same manner as the usual diamagnetic cobalt(III) complexes. It can be concluded that an unpaired spin on complexes is not located on the cobalt atom, but is located over the π-orbitals of the chelated ligand of complexes.
  • Hisanori Imura, Satoru Matsumora, Nobuo Suzuki
    1986 Volume 59 Issue 2 Pages 621-626
    Published: 1986
    Released: June 27, 2006
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    Partition coefficients of dimethyldithiocarbamic acid and its copper(II) chelate have been determined in various organic solvents −0.10 mol dm−3 aqueous perchlorate solution systems at 25 °C. The effects of inert organic solvents are explained with the aid of the regular solution theory. Also, a linear free-energy relationship between the partition coefficient of the copper(II) chelate and that of the reagent is demonstrated. The partition coefficient of the copper(II) chelate is compared with that of bis(2,4-pentanedionato)copper(II) and various factors governing the partition coefficients of these chelates are discussed with the aid of the scaled particle theory.
  • Reizo Kato, Hayao Kobayashi, Akiko Kobayashi, Yukiyoshi Sasaki
    1986 Volume 59 Issue 2 Pages 627-630
    Published: 1986
    Released: June 27, 2006
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    New multi-sulfur 1,2-dithiolene complexes in which the 1,2-dithiolene moiety is extended by incorporating heterorings have been prepared and characterized by IR spectroscopy, X-ray diffraction method, and cyclic voltammetry. Partial oxidation of these complexes are expected to provide the multi-dimensional molecular conductors. Electrochemical properties of these complexes are compared with those of the dmit-complexes (dmit=2-thioxo-1,3-dithiole-4,5-dithiolate).
  • Takayuki Kobayashi, Jean M. Friedt
    1986 Volume 59 Issue 2 Pages 631-634
    Published: 1986
    Released: June 27, 2006
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    The anomalous states produced by electron capture decay of 57Co in CoCl2·2H2O and CoCl2·6H2O are investigated using conventional Mössbauer emission spectroscopy and a γ-X ray coincidence method which allows to isolate events with a reduced influence of the Auger electron self-irradiation. The formation of the anomalous electronic and structural configuration is assigned to the self-radiolysis of the water ligands. The mechanism involves both the nearest and the next nearest H2O coordination shell according to the densities of these ligand molecules in the respective shells.
  • Ushio Sakaguchi, Tasuku Ito
    1986 Volume 59 Issue 2 Pages 635-638
    Published: 1986
    Released: June 27, 2006
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    The structure of Δ-(8-methyl-1,3,6,10,13,16,19-heptaazabicyclo[6.6.6]icosane)cobalt(III) perchlorate monohydrate, Δ-[Co(C14H33N7)](ClO4)3·H2O, has been determined by single crystal X-ray diffraction techniques. Crystal data are the following: space group P212121, a=16.379(2) Å, b=16.388(2) Å, c=9.753(1) Å, V=2617.9(5) Å3, Z=4, 3983 nonzero structure factors (|Fo|>3σ(|Fo|)), R=0.0447, and Rw=0.0491. The geometry of the cation can be approximated very closely by a composite of [Co(sen)]3+ and [Co(sep)]3+, where sen=1,1,1-tris(4-amino-2-azabutyl)ethane and sep=1,3,6,8,10,13,16,19-octaazabicyclo[6.6.6]icosane.
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