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Articles
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and
Akira Shimoyama*
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Seiichi Miyajima,
and
Yusei Maruyama
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Analitical and Inorganic
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Kazuo Ueno, and
Hiroshi Ishikawa
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Shigenobu Hayashi,
Hideo Hosono,
and
Naoyuki Ueda
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Articles
Orgainc and Biological
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and
Makoto Takagi
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and
Dietrich D
pp
-Tocopherol
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and
Yukio Nishimura
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a Sotler-Pe
an, and
Marko Zupan
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ki*
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Kuniko Shibutani,
and
Katsuyuki Ogura*
Interaction as an Important Driving Force of Host-Guest Complexation.
Further Evidence for the Selective Incorporation of Alkyl Groups in the Polyhydroxy Aromatic Cavity of Calix[4]resorcarene Host
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3
-cephem-4-carboxylate to 3-Formyl-
3
-cephem-4-carboxylate through 3-Hydroperoxymethyl-
3
-cephem-4-carboxylate
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Articles
Applied and Materials
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Copyright (C) 1996 The Chemical Society of Japan
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Accounts
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Copyright (C)
1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 1-16 (1996) [Vol. 69, No. 1, January, 1996]
Organosilicon chemistry has been highlighted by the successful construction and thorough characterization of strain carbocyclic systems: 1) silabenzene, silafulvene, and polycyclic polysilane via silylcarbene rearrangement to silene, 2) a ring-expansion reaction of disilacyclobutene with exo -methylene, and 3) cyclic polysilanes containing unsaturated carbon systems, such as acetylene, allene, and fullerene.
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Headline Articles
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Copyright (C)
1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 17-24 (1996) [Vol. 69, No. 1, January, 1996]
Various derivatives of poly-substituted cobalticinium complexes have been synthesized by using cyclopentadienes having a convertible carboxylic group. By 1 H NMR titration experiments, these complexes were shown to behave as effective anion receptors.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 25-30 (1996) [Vol. 69, No. 1, January, 1996]
Alkyllithium was reacted with a lanthanide salt and 2,6-xylyl (Xy) isocyanide to give (alkaneimidoyl)lanthanide(III). Among a series of LnX3
, CeCl3
furnished (alkaneimidoyl)cerium(III) quantitatively. An analogous reaction of R1
2
Mg also afforded (alkaneimidoyl)cerium(III), which then reacted with a carbonyl compound to produce an
-hydroxy imine.
Copyright (C)
1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 31-39 (1996) [Vol. 69, No. 1, January, 1996]
,
-Dimethyl homoallyl alcohols, upon conversion to the corresponding triflate, undergo smooth cyclization to give cyclopropanes in a selective and stereospecific manner. Various functionalities could be introduced at the
-position of the newly formed cyclopropane ring. Alternatively, a treatment of the reaction mixture with triethylamine effects the clean elimination of a triflic acid to give high yields of 2-propenyl cyclopropanes, which are convertible to cyclopropyl methyl ketones by ozonolysis.
=============================
Articles
General and Physical
=============================
Copyright (C)
1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 41-46 (1996) [Vol. 69, No. 1, January, 1996]
,
MnIII oxidizes glycylglycine to formaldehyde. The reaction has first order kinetics in [MnIII ] and a fractional order each in [peptide] and [H+ ]. The oxidation goes through a free radical intermediate. Evidence for transient existence of the intermediate is given.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 47-52 (1996) [Vol. 69, No. 1, January, 1996]
The rotational dynamics of NO3
-
and SCN-
ions dissolved in liquid ammonia were studied with NMR. Both NO3
-
and SCN-
ions showed an increase in D
as compared with their aqueous solutions. The NO3
-
rotational anisotropy was found enhanced in liquid ammonia. These observations are in line with a weakening of the hydrogen-bond network in liquid ammonia as compared to water.
Copyright (C)
1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 53-58 (1996) [Vol. 69, No. 1, January, 1996]
and
Akira Shimoyama*
Over 130 organic compounds were identified in a heating experiment of insoluble organic matter of the Murchison carbonaceous chondrite from room temperature to 800 °C. The dominant compounds were the aromatic hydrocarbons listed below. They were released over a range of 300-600 °C, and seem to be major constituents of the insoluble organic matter.
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Copyright (C)
1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 59-66 (1996) [Vol. 69, No. 1, January, 1996]
The photo-thermal phase transition of an aqueous Poly(N -isopropylacrylamide) solution was induced by a focused infrared laser beam, which caused the formation of a single micrometer-sized polymer particle. The radiation force was shown to play an essential role in particle formation.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 67-70 (1996) [Vol. 69, No. 1, January, 1996]
An inversion procedure is used to obtain from the extended principle of corresponding states the interaction potentials over a range of reduced temperature extended from 1 to the onset of ionization. These directly measured potentials agree excellently with the potentials independently known from the crossed molecular-beam technique.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 71-76 (1996) [Vol. 69, No. 1, January, 1996]
The photodissociation dynamics of predissociated C2
H2
(
+
) is internally excited. The average internal excitation of the photofragment is shown to scale linearly with the excess energy of the photodissociation.
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Copyright (C)
1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 77-83 (1996) [Vol. 69, No. 1, January, 1996]
Catalytic properties of lanthanide (Ln) catalysts prepared by impregnation of active carbon (AC) with liq NH3
solutions of Eu or Yb metal were studied for the hydrogenation of ethene. The Ln deposited on AC was changed through varied steps by thermal decomposition and simultaneously the hydrogenation activity varied. Imide or imide-like spices generated during the thermal degradation of Ln amide to nitride showed a high activity even at 203 K.
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Copyright (C)
1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 85-93 (1996) [Vol. 69, No. 1, January, 1996]
Seiichi Miyajima,
and
Yusei Maruyama
A 1 : 1 charge-transfer complex of DAP and CHL shows a drastic conductivity change upon heating or fracture of the crystals. The resultant highly conducting crystal comprises mixed-stackes of neutral donors and acceptors.
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Articles
Analitical and Inorganic
=============================
Copyright (C)
1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 95-100 (1996) [Vol. 69, No. 1, January, 1996]
Adsorption studies of nucleosides nucleotides on nickel(II) hexacyanoferrate(II) have shown typical Langmuir-type adsorption isotherms. The observed adsorption trend is: 5' -ATP<5' -ADP<adenine>5' -AMP<adenosine . Infrared spectral studies of adsorption adducts indicate that adsorption of biomolecules could have taken place via complex formation. We propose that such simple adsorption processes could have prevented the degradation of biomolecules in the chemical evolution on the primitive earth.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 101-105 (1996) [Vol. 69, No. 1, January, 1996]
Kinetics of the title complexes were studied at normal and high pressures up to 1600 bar. For the base hydrolyses of the chloro and bromo complex the pseudo-first-order rate constants depart slightly positively from the proportionality to the [OH- ]. The magnitudes (19.1 and 19.7 cm3 mol-1 ) of the activation volume are in line with the SN 1 CB mechanism.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 107-110 (1996) [Vol. 69, No. 1, January, 1996]
Kazuo Ueno, and
Hiroshi Ishikawa
Cuprate whiskers having different crystal phases, Bi2 Sr2 CaCu2 Ox (Bi-2212), Bi2 Sr2 CuOx (Bi-2201), and Bi4 Sr8 Cu5 Ox (Bi-485), in the Bi-Sr-Ca-Cu-O system have been obtained by heating melt-quenched glass precursors. The crystal phase and composition of the whiskers are able to be controlled by changing the precursor composition and heating conditions.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 111-115 (1996) [Vol. 69, No. 1, January, 1996]
Shigenobu Hayashi,
Hideo Hosono,
and
Naoyuki Ueda
New thallium mixed valence compound Tl2 Nb2 O6+x (0.1<x<1.1 ) with a defect pyrochlore structure was synthesized by introducing excess oxygens under oxygen pressure up to 2 MPa. 205 Tl NMR spectra showed abnormal behavior that the absorption due to Tl+ decreased drastically to ca. 1/60 as x increased. Optical and electrical properties demonstrated the presence of the mixed valence states of Tl in these oxides.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 117-123 (1996) [Vol. 69, No. 1, January, 1996]
A novel nitridomolybdenum(VI) complex (NEt4
)2
[MoVI
N(bdt)2
Cl] (bdt2-=1,2
-benzenedithiolate) was synthesized by the reaction of (NEt4
)[MoVI
NCl4
] with Li2
bdt. The physical properties and reactivity with O2
and H2
O were studied. The activation effect of the bdt ligand on the nitrido ligand by the competitive donation of S(p) to Mo(d) is described.
=============================
Articles
Orgainc and Biological
=============================
Copyright (C)
1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 125-130 (1996) [Vol. 69, No. 1, January, 1996]
and
Makoto Takagi
A monomer-type surfactant, 10-(p -vinylphenyl)decanoic acid, has been prepared and used as an emulsifier for the preparation of surface-template resins. The adsorption on the metal-imprinted resins was far more than that on the unimprinted resins. The selectivity (Cu2+ /Zn2+ ) of metal ions was 3.7 for the Cu2+ -imprinted resins and 1.6 for the unimprinted resins.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 131-135 (1996) [Vol. 69, No. 1, January, 1996]
and
Dietrich Dpp
Irradiation of triazene 1-oxides in benzene, ethanol, and cyclohexane, using a 125-W high-pressure mercury lamp, and chromatographic separation gave hydroxyazobenzene (in ethanol), p ,p' -disubstituted biaryl derivatives (in cyclohexane) and p -substituted biaryl derivatives (in benzene).
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 137-139 (1996) [Vol. 69, No. 1, January, 1996]
-Tocopherol
Metal ion-exchanged montmorillonites were found to be efficient catalysts for the condensation reaction of trimethylhydroquinone with isophytol to afford
-tocopherol in high yield. The condensation reaction proceeded smoothly in various solvents. The catalyst was easily recovered by filtration of the reaction mixture after the reaction was completed, and could be reused.
Copyright (C)
1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 141-145 (1996) [Vol. 69, No. 1, January, 1996]
Reaction of (diphenylmethylene)(2,4,6-tri-t -butylphenyl)phosphine with elemental sulfur afforded the corresponding methylenephosphine P -sulfide, which was isomerized by photo-irradiation to 1,2-thiaphosphirane derivative. The structure of the methylenephosphine P -sulfide was analyzed by X-ray crystallography and compared with that of the thiaphosphirane.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 147-156 (1996) [Vol. 69, No. 1, January, 1996]
and
Yukio Nishimura
The ion-molecule reactions of CF3 + with monosubstituted benzenes [PhX: X=OH , CH2 OH, CH2 CH2 OH, CH(OH)CH3 , OCH3 , OC2 H5 ] have been studied at near-thermal energies using an ion-beam apparatus. The reaction mechanisms are discussed based on product ion distributions and semiempirical calculations of reaction pathways.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 157-161 (1996) [Vol. 69, No. 1, January, 1996]
Mn2
(CO)10
is utilized for the one-pot preparation of unsymmetrical ketones and
-diketones. By successive treatments of Mn2
(CO)10
with two kinds of alkyllithiums, unsymmetrical ketones are obtained in high selectivity. Unsymmetrical
-diketones are generated when the above reaction is carried out in the presence of P(OMe)3
and is quenched with NBS.
Copyright (C)
1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 163-168 (1996) [Vol. 69, No. 1, January, 1996]
All glycine residues are involved in intermolecular hydrogen bonding in LB films of oligoglycine amphiphile monolayers. The strength of the hydrogen bonds is increased with increasing numbers of the glycine residues in a molecule. The oligoglycine units in the monolayer have a conformation similar to that of (Gly)n II according to FTIR spectra.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 169-175 (1996) [Vol. 69, No. 1, January, 1996]
a Sotler-Pean, and
Marko Zupan
Stereochemistry of the fluoro-alkoxylation of phenyl-substituted alkenes with F-TEDA depends on the structure of alkene. Relative rates of reactions correlate with ionization potentials of alkenes. Hammett correlation analysis gave the reaction constant 
+=-1.42
.
Copyright (C)
1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 177-187 (1996) [Vol. 69, No. 1, January, 1996]
ki*
Reactivities of carbon radicals generated at the rotameric positions (ap and sc ) by the title method were investigated by the product analysis. The fate of the radicals was significantly influenced not only by the rotational isomerism but by various conditions such as solvent, phase, and method of radical generation.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 189-193 (1996) [Vol. 69, No. 1, January, 1996]
Peroxidase-catalyzed oxidative polymerization of phenol has been carried out in an aqueous organic solution to give a new class of polyphenol. Polymerization conditions have been investigated with respect to the polymer yield, solubility, and molecular weight. TG analysis showed that the resulting polymer had high thermal stability.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 195-205 (1996) [Vol. 69, No. 1, January, 1996]
Tetracyanoethylene and dicyanoketene acetals were found to catalyze alcoholysis of epoxides in good yields. The favorable chemoselectivity without cleavage of tetrahydropyranyl ether and ethylene acetal groups were demonstrated. A novel regioselectivity associated with anchimeric assistance of the ethereal group in the side chain was observed in the ring opening reaction of terminal and 1,2-disubstituted epoxides.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 207-215 (1996) [Vol. 69, No. 1, January, 1996]
Kuniko Shibutani,
and
Katsuyuki Ogura*
A practical synthesis of (R )-1-benzyl-3-hydroxy-2,5-pyrrolidinedione was developed by lipase PS-catalyzed hydrolysis of its acetate. This reaction proceeds smoothly in an aqueous dioxane with a high enantioselectivity (E>3000 ). This methodology is applicable to the kinetic resolution of 3-hydroxypyrrolidines and 3-hydroxypiperidines.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 217-220 (1996) [Vol. 69, No. 1, January, 1996]
Interaction as an Important Driving Force of Host-Guest Complexation.
Further Evidence for the Selective Incorporation of Alkyl Groups in the Polyhydroxy Aromatic Cavity of Calix[4]resorcarene Host
Circular dichroism spectroscopy with inhibition techniques indicates that the alkyl groups in alkylbenzenes as solvents and those in alkyl benzoates as guests are incorporated in the aromatic cavity of calix[4]resorcarene in a highly selective manner.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 221-228 (1996) [Vol. 69, No. 1, January, 1996]
Directed toward the synthesis of verticillols, 10-cyanoverticillene was settled as a key intermediate. Bond formation of cyano chloride to the key compound with lithium bis(trimethylsilyl)amide at 60 °C proceeded smoothly with moderate yield. The NOE experiment indicates that it possesses the same stereostructure as in the case of verticillol, in which C1-C2 bond takes an axial orientation.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 229-233 (1996) [Vol. 69, No. 1, January, 1996]
3
-cephem-4-carboxylate to 3-Formyl-
3
-cephem-4-carboxylate through 3-Hydroperoxymethyl-
3
-cephem-4-carboxylate
Aerobic oxidation of 3-iodomethyl-3
-cephem-4-carboxylate in N
-methyl-2-pyrrolidone gave 3-hydroperoxymethyl-3
-cephem-4-carboxylate as a primary product which was subsequently converted mainly to either 3-formyl-3
-cephem-4-carboxylate or 3-hydroxymethyl-3
-cephem-4-carboxylate depending on the additives.
=============================
Articles
Applied and Materials
=============================
Copyright (C)
1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 235-240 (1996) [Vol. 69, No. 1, January, 1996]
The oxidative coupling of methane on MgO-MgSO4 was improved by a small addition of CCl4 , which promoted the transformation of MgSO4 to MgO and deposited chlorine species on the surface of the catalyst.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 241-244 (1996) [Vol. 69, No. 1, January, 1996]
A mixture of CO2 and H2 O was introduced to a low-temperature microwave plasma. From the results of steam chromatography and mass spectrometry, it was found that the products contained methanol. The most adequate plasma energy density for the formation of methanol was found to be 0.26 GJ kg-1 of W /FM .
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 245-253 (1996) [Vol. 69, No. 1, January, 1996]
Reversible and irreversible electrochromism of copper phthalocyanine thin films is analyzed in detail from the viewpoints of control of the scan range to admit the first oxidation peak and size of the anions used as an electrolyte.
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1996 The Chemical Society of Japan
Bull. Chem. Soc. Jpn.,
69, 255-259 (1996) [Vol. 69, No. 1, January, 1996]
Oxygen permeation through a liquid membrane containing bovine hemoglobin (Hb) was measured by the electrochemical reduction of the permeated oxygen. The oxygen permeation was facilitated (facilitation factor ca. 10). It was analyzed by a dual-mode model to give the diffusion coefficient of the mobile oxygen-carrier Hb and the solution-diffusion coefficient of oxygen.
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